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By K. H. Kilgren

At high formation pressures the distillate produced from a gas-condensate reservoir may be black in color. In this event the dense gas phase existing above the dew point is correspondingly dark. Volumetric phase data and an analysis of a reservoir fluid exhibiting these characteristics, together with a description of the visual equilibrium cell in which these observations were made, are presented in this paper. INTRODUCTION Previously the author, like many others in the oil and gas industry perhaps, tacitly assumed that the expressions black or dark oil system, crude oil system and bubble-point system were synonymous. Crude oil reservoir fluids are bubble-point systems and yield a black or dark stock-tank oil of relatively low API gravity. Conversely, a clear or amber colored trap distillate of high API gravity is assumed indicative of a dew point system or a gas-condensate reservoir fluid. This broad classification appears satisfactory for shallow reservoirs, but as the following study demonstrates, may be misleading when applied to deep reservoirs. Theoretically, there is no reason to exclude the possibility of producing a dark, low-gravity distillate from a gas-condensate reservoir. At sufficiently high values of pressure and temperature, heavy, dark-colored hydrocarbons may exist in the vapor state of a multi-component system. If enough dark-colored components are present in the reservoir vapor phase, the resulting condensate will be dark. The reservoir fluid investigated in the present study supports this contention. Stock-tank production was black in color and measured 29" APT gravity. From outward appearances, the liquid closely resembled a medium gravity crude oil. Experimental measurements proved the reservoir fluid was in reality a gas-condensate system. Volumetric phase data for this high-pressure system and a description of the visual cell in which the study was conducted successfully are presented in this paper. THEORY Phase behavior of a reservoir fluid can be predicted accurately with reference to a pressure-temperature phase diagram. If the reservoir temperature is lower than the critical temperature of the hydrocarbon fluid in place, bubble-point behavior will be observed. If the reservoir temperature lies between the critical and cricondentherm temperature, dew point behavior and retrograde condensation will occur. For reservoir temperatures above the cri- condentherm, only a single gas phase can exist in the reservoir regardless of pressure. Providing the composition of the reservoir fluid were known, it would be possible to predict the critical temperature and estimate the phase behavior from equilibrium relationships. However, the usual practice is to obtain a sample of reservoir fluid, subject it to varying pressures at the reservoir temperature and observe the phase behavior experimentally. The latter method was used to obtain the data reported here. WELL AND TRAPPING INFORMATION A summary of pertinent data for the well from which the reservoir fluid was sampled is presented in Table 1. This well is located offshore Louisiana. Except for the pressure which substantially exceeds hydrostatic pressure, the information does not appear unusual. Prior to the sampling program, the well was produced for 22 hours at a stock tank oil rate of 139 B/D. Average trapping conditions and gauging data for the six-hour test period that followed are summarized in Table 2. Samples of the first-stage trap gas and liquid were obtained during the latter portion of the test period. Ambient temperature remained 5 to 10F below trap temperature and presented no problem for sampling. Surface wind and moderate foaming of stock-tank oil presented some difficulty in obtaining accurate stock-tank gauges. SAMPLE ANALYSIS Compositions of the gas and liquid samples are shown in Table 3. The trap gas was analyzed by isothermal chromatography which revealed only a trace of heptane in the stream. The trap liquid was initially analyzed by low-temperature fractional distillation, yielding a bottom product of heptane and heavier components. Specific gravity of this fraction was measured and the mol weight was determined by freezing point depression. The hexane and lighter overhead gas collected during distillation was

Jan 1, 1967

By L. E. Murr, P. J. Smith

A study has been made by transmission electron microscopy of thin foils of 304 stainless steel fatigued external to the electron microscope in reversed bending, and of thin foils fatigued directly within the microscope in alternating tension. The build-up of stacking faults in the thin foils during fatigue zoas correlated with the dislocatirm structures found in thin films prepared fror fatigued bulk specimens. The performance of the special devices designed for fatigue of thin foils so outlined and the importance of alternative methods of preparation of more uniform fatigue specimens bY vapor deposition are emphasized. INVESTIGATIONS on fatigued bulk aluminum1,' and stainless stee13j4 have revealed the existence of dislocation substructure on examination by transmission electron microscopy of electrolytically thinned foils representative of these bulk specimens. While this technique has proved extremely valuable, it has several shortcomings. First, the method of fatiguing bulk specimens and then thinning to foil for electron-transmission observation allows only one observation of internal structure at any one portion of the fatigue life. Second, thinning the bulk fatigued specimens to foil results in the loss of at least one original surface. Thus, what one sees in the remaining electron-transparent sections is an internal dislocation or fault structure which in many cases cannot be correlated with the original surface markings. This is an undesirable feature, since it is well-known that metal surfaces play an important part in the fatigue process.5 An obvious third undesirable feature of the thinning-from-bulk technique is the fact that static observations have difficulty (in the case of fatigue) explaining the mechanism of a dynamic process. What is required then is a method whereby a selected thin area can be continuously observed either while undergoing cyclic deformation or at various fixed stages of fatigue deformation. While Murr and wilkov6 have reported some success with an apparatus designed to fatigue thin metal foils directly within the electron microscope, the nature of the specimen-mounting procedure and the mechanical features involved in the adaptation of the fatigue device to the electron microscope make this method difficult to operate. It was not possible, for example, to make frequent observations of a selected area because of difficulty in maintaining a chosen area in a stable viewing position inside the electron microscope. Except for the build-up of a dislocation substructure and what are commonly referred to as "slip striations", little else has been reported from observations on thin-foil sections prepared from bulk fatigue specimens. segal17 has found "slip striations" in stainless-steel fatigued specimens which were electropolished from both sides, but gave no explanation as to their origin or identity in terms of lattice imperfections. The research to be reported in this paper was undertaken with the following objectives in mind. First, an attempt was made to devise a technique or techniques whereby thin metal foils could be fatigued and repeatedly observed by transmission electron microscopy. Second, it was hoped that some correlation could be made between deformation striations found in fatigued thin transmission specimens and thin foils prepared from bulk fatigued specimens. These investigations illustrate quite convincingly that a feasible method is available for the direct study of the fatigue mechanism and similar dynamic phenomena in thin transmission specimens inside the electron microscope. I) EXPERIMENTAL METHODS Three modes of specimen fatigue and observation of fatigue damage were used. These involved fatigue of thin-foil specimens in a special arrangement external to the electron microscope and observation of a selected area at various stages in the fatigue life, the fatigue of thin-foil transmission specimens inside the electron microscope, and the fatigue of bulk specimens external to the electron microscope followed by thin-foil preparation for direct observation at predetermined stages. Design of the External Fatigue Clip and Specimen Holder for the Hitachi H.U.11 Electron Micro-scope. The purpose of the fatigue clip was to provide a reversed bending fatigue stress to a thin-foil transmission specimen outside the electron microscope. In order to accomplish this, a flat-bottomed, U-shaped brass clip was made as shown

Jan 1, 1965

By W. F. Hosford, E. W. Kelley

Deformation studies have been conducted at room temperature on single crystals of magnesium and magnesium alloys with thorium and with lithium. Single crystals oriented to suppress shear on the easily activated basal slip systems were deformed by plane-strain compression. Compression along the C axis was accommodated by {1011} banding. Compression perpendicular to the unconstrained c axis activated {1012} twinning, and, after virtually complete twinning, deformation continued by {1011) banding in the twinned material. Compression perpendicular to the constrained c axis was accommodated by the simultaneous operation of (1012) twinning against the constraint and (1011 ) banding. Although this orientation was favorable for {1010)(1210) prism and {1011}(1~10) pyramidal slip, these modes were not observed in pure magnesium or in Mg-0.5 pct Th. However, {10i0)(1~10) prism slip was observed in crystals of Mg-4 pct Li during compression perpendicular to the constrained c axis. Fracture in all materials occurred parallel to (1124) or {l~il) depending on the orientation and composition of the specimen. THE mechanical behavior of the hcp metals is strongly anisotropic. Although several slip systems have been reported the slip is cpmmonly in the directions of closest packing, the (1210),' and this does not produce strains parallel to the c axis. Hence the inherent anisotropy. The deformation mode most easily activated in magnesium at room temperature is (0001)(1210)- basal slip. Also {1010}(1~10) prism slip and {1011)(1210) pyramidal slip have been reported, primarily at elevated temperatures.2"4 However, at room temperature the shear stresses to activate the prism and pyramidal modes are roughly a hundredfold greater than that required for basal slip.'j4 Thus prism and pyramidal slip may be expected only under special conditions of loading. Strains normal to the basal plane can be produced by twinning, however. Many twinning modes have been reported for magnesium,' with (1012) twinning the most common and relatively easy to activate. Magnesium can deform by (1012) twinning when stressed along the c axis jn tension, but not in compression. In contrast, (1011) twinning is activated by compression along the c axis and not by tension. In addition to primary twinning, secondary twinning or slip can occur within the reoriented material of primary twins.' In general at least five independent shear systems must be active to bring about an arbitrary shape change such as that in the individual grains of a deforming polycrystalline material.' Because basal slip can_ provide only two independent shear systems and (1012) twinning can only accommodate an extension of the c axis, other deformation modes must be active in magnesium for an arbitrary shape change to occur. The purpose of this investigation has therefore been to study the various deformation modes in magnesium at room temperature, with special emphasis on those modes that are less easily activated. The effect of the alloying elements, thorium and lithium, has also been investigated. In polycrystalline aggregates, unambiguous identification of deformation modes is extremely difficult and the direct evaluation of the resolved shear stresses to activate them is not feasible. On the other hand, uni-axial tension and compression experiments on single crystals may not activate some of the- deformation modes because basal slip and/or {1012) twinning cannot be suppressed in most orientations. However, it should be possible to activate all possible deformation modes using oriented single crystals and plane-strain compression. Identification of active deformation systems and evaluation of the resolved shear stresses required to activate them should be facilitated. Wonsiewicz and Backofen have recently completed an investigation of the plasticity of pure magnesium crystals at various temperatures utilizing plane-strain compression and selected crystal orientations. This technique has also been used in the present work. The seven orientations selected for study are indicated in Table I. Plane-strain compression along the c axis (orientations A and B) should activate some deformation mode _other than basal, prism, or pyramidal slip, or (1012) twinning. In orientations C and D, prism or pyramidal slip would be expected to take place. When the compressive load is applied perpendicular to an unconstrained c axis (orientations E and F) the three slip modes should be suppressed but not (10i2) twinning. In orientation G, basal slip should occur.

Jan 1, 1969

By D. B. Hunter, H. W. Rosenberg

The titanium-rich portion of the Ti-Pd system was investigated from 0 to 75 wt pct Pd by metallo-graphic and X-ray techniques. A 0 eutectoid occurs at 24 wt pct Pd and 1190°F. Two compoutzds are indicated in the region below 75 wt pct Pd, Ti,Pd and Ti2Pd3. The solubility of palladium its a titanium is low, probably less than 1 pct. In 1960 Rudnitskii and Birunl published a complete version of the Ti-Pd phase diagram. However, their work was in disagreement with the earlier literature in that they reported only one inter metallic compound, whereas three had been reported earlier. In view of these discrepancies, it was therefore necessary to redetermine those portions of the diagram of immediate interest. The following account describes our work on the system over the range of 0 to 75 wt pct Pd. MATERIALS AND METHODS Distilled titanium sponge and elemental palladium were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 10 to 50 g blended compacts that were melted into buttons by arc melting under gettered argon on a water-cooled copper hearth. Weighing of the ingredients before and after melting showed that negligible weight changes occurred. Therefore, no analyses were undertaken and the compositions of all alloys are nominal. All alloys were fabricated by hot rolling at 1700°F to 0.070-in.-thick sheet. Scale was removed by sandblasting and pickling in a 5 pct HF-35 pct HNO,, balance H20 solution. For metallographic examination, specimens were mounted after heat treatment transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and then electro-polished using a solution containing 600 ml me-thanol, 60 ml perchloric acid, 360 ml butyl cello-solve, and 2 ml "Solvent X". Unless otherwise specified, etching of alloys containing up to 42 pct Pd was carried out by swabbing with a 12 pct HN03-1 pct HF aqueous etch where a bright etch was required, or by a 1 pct hydrofluoric in saturated oxalic acid solution where contrast between phases was required. The Ti-52.8 Pd alloy was etched with a solution of 25 ml HF, 40 ml glycerine, 35 ml methanol, and 18 g benzalkonium chloride. For X-ray examination, 1/2-in.-square speci- mens of sheet were mounted flat in a standard 1-in. metallographic mount and ground and polished as above. X-ray diffraction was performed using a Norelco type 12045 Diffractometer, employing CuKa radiation with a nickel filter at 40 kv and 20 ma. Specimens were rotated about the sheet normal during exposure. Although this procedure did not remove the effects of sheet texture from the relative intensities, it had the advantage that oxidation or contaminants entering during preparation of powder samples could not confuse the patterns obtained. RESULTS AND DISCUSSION Fig. 1 illustrates the Ti-Pd phase diagram according to Rudnitskii and Birunl with the work of the present authors superimposed. Both interpretations agree that the system is of the 0 -eutectoid type with an extensive 0-phase field, and that the eutectoid temperature is just below 1200°F. There is also agreement that the solubility of palladium in a titanium is restricted. Our work would indicate that the a solubility of palladium is low, probably less than 1 pct. However, whereas Rudnitskii and Birunl place the eutectoid composition at 41 wt pct Pd, this investigation shows it to be at about 24 wt pct Pd. Moreover, this investigation confirms the existence of compounds at Ti2Pd and Ti2Pd3, whereas Rudnitskii and Birun report only a single Berthol-lide phase covering the TiPd to TiPd, range. Laves et a1.' and Wallbaum, whose work was summarized by Maykuth , reported the existence of Ti2Pd3 and TiPd, in addition to Ti2Pd. More recently, Nevitt and Downe~' have reported the structure of

Jan 1, 1965

By R. H. Olds, B. H. Sage

The transient flow of gases in long pipe lines is a problem of industrial interest. The present discussion deals with the application of the conservation of momentum and material to the transient flow of gas in conduits which are long with respect to their diameter. Solutions of the resulting equations include consideration of variations in friction and specific volume of the fluid as functions of time and position along the conduit. The changes in state along the pipe line are established as a function of time. The methods proposed may be extended to other situations. The flow of compressible fluids under steady conditions' has been considered in detail. Primary emphasis was placed on the development of simple means of taking into account the non-uniform flow' realized in long conduits under such conditions. Binder2 discussed the essential differences between the flow of compressible and uoncompressible fluids. Bonilla" proposed direct methods of solution for equations describing isothermal flow in long pipes. Similar considerations limited to steady flow have been discussed by Ruth.' Palsgrove 5 sugrested a graphical means of solving specific problems relating to the flow of gases in conduits of uniform section. Some of the basic concepts of the flow of a compressible viscous fluid in straight tubes have been described by Kuo.6 Problems of this type require knowledge of the equation of state of the fluid. In many cases it liar been convenient to assume that the fluid follows the relationship ascribed to a perfect gas. The treatment of unsteady flow of compressible fluids is less complete. This state of affairs result* from the fact that the differential equations relating pressure and flow rate with time and position for unsteady flow are nonlinear in character.' Muskat and Wyckoff presented an excellent treatment of the situation in laminar Bow where inertia forces were not of controlling importance. Somewhat earlier Hurst9 discussed the uncteady flow of fluids in petroleum reservoirs. Helhering-ton. MarRoberts. and Huntington'" established experimentally the pressure distribution and accumulative flow rate of natural gas through an unconsolidated sand. Recently Joffe11,12 conhitlcretl the specific problem of the flow of natural gas in relatively long.,. pipe lines for unsteady conditions with emphasis upon the economic feusibility of the storage of gas in such a reservoir. These discussions were based upon approximations of the partial differential equations applying to the condititons of flow. The results were descriptive of the physical situation and indirated the effertiveness of large pipe lines as cyclic storage facilities for natural gas. The advent of analog computers" has increased materially the practicality of solving nonlinear partial differential expressions. Several iterative numerical and graphical methods14,15,16 have been developed to solve nonlinear equations. However, it appears that the pair of simultaneous nonlinear partial differential equations involved in problems of this nature are not directly susceptible to solution by presently available analog computer or formal iterative numerical techniques. Nevertheless. graphical analyses afford a means of obtaining data of engineering value without special equipment. MATHEMATICAL CONSIDERATIONS Since the length of the conduit is large in comparison to the cross section in the cases to be considered, it is possible to treat the characteristics of the flow as independent of position in the cross section of the conduit. This possibility follows since the energy- connected with the velocity profile is small compared to that required to overcome the friction associated with its movement throughout the length of the line. Average values of the pressure. velocity. kinetic energy. momentum, and specific volume may he assigned to the fluid at any particular cross section. From a mathematical viewpoint this may be expressed in the following way for velocity: µ = µ(?X)..........(1) The uncertainties introduced by such assumptions usually are negligible when the ratio of length to diameter is greater than the order of 1.000. On this basis a volume element ma!. be considered to occupy the entire cross section of the conduit. Such an element is presented in Fig. 1.

Jan 1, 1951

By R. H. Olds, B. H. Sage

The transient flow of gases in long pipe lines is a problem of industrial interest. The present discussion deals with the application of the conservation of momentum and material to the transient flow of gas in conduits which are long with respect to their diameter. Solutions of the resulting equations include consideration of variations in friction and specific volume of the fluid as functions of time and position along the conduit. The changes in state along the pipe line are established as a function of time. The methods proposed may be extended to other situations. The flow of compressible fluids under steady conditions' has been considered in detail. Primary emphasis was placed on the development of simple means of taking into account the non-uniform flow' realized in long conduits under such conditions. Binder2 discussed the essential differences between the flow of compressible and uoncompressible fluids. Bonilla" proposed direct methods of solution for equations describing isothermal flow in long pipes. Similar considerations limited to steady flow have been discussed by Ruth.' Palsgrove 5 sugrested a graphical means of solving specific problems relating to the flow of gases in conduits of uniform section. Some of the basic concepts of the flow of a compressible viscous fluid in straight tubes have been described by Kuo.6 Problems of this type require knowledge of the equation of state of the fluid. In many cases it liar been convenient to assume that the fluid follows the relationship ascribed to a perfect gas. The treatment of unsteady flow of compressible fluids is less complete. This state of affairs result* from the fact that the differential equations relating pressure and flow rate with time and position for unsteady flow are nonlinear in character.' Muskat and Wyckoff presented an excellent treatment of the situation in laminar Bow where inertia forces were not of controlling importance. Somewhat earlier Hurst9 discussed the uncteady flow of fluids in petroleum reservoirs. Helhering-ton. MarRoberts. and Huntington'" established experimentally the pressure distribution and accumulative flow rate of natural gas through an unconsolidated sand. Recently Joffe11,12 conhitlcretl the specific problem of the flow of natural gas in relatively long.,. pipe lines for unsteady conditions with emphasis upon the economic feusibility of the storage of gas in such a reservoir. These discussions were based upon approximations of the partial differential equations applying to the condititons of flow. The results were descriptive of the physical situation and indirated the effertiveness of large pipe lines as cyclic storage facilities for natural gas. The advent of analog computers" has increased materially the practicality of solving nonlinear partial differential expressions. Several iterative numerical and graphical methods14,15,16 have been developed to solve nonlinear equations. However, it appears that the pair of simultaneous nonlinear partial differential equations involved in problems of this nature are not directly susceptible to solution by presently available analog computer or formal iterative numerical techniques. Nevertheless. graphical analyses afford a means of obtaining data of engineering value without special equipment. MATHEMATICAL CONSIDERATIONS Since the length of the conduit is large in comparison to the cross section in the cases to be considered, it is possible to treat the characteristics of the flow as independent of position in the cross section of the conduit. This possibility follows since the energy- connected with the velocity profile is small compared to that required to overcome the friction associated with its movement throughout the length of the line. Average values of the pressure. velocity. kinetic energy. momentum, and specific volume may he assigned to the fluid at any particular cross section. From a mathematical viewpoint this may be expressed in the following way for velocity: µ = µ(?X)..........(1) The uncertainties introduced by such assumptions usually are negligible when the ratio of length to diameter is greater than the order of 1.000. On this basis a volume element ma!. be considered to occupy the entire cross section of the conduit. Such an element is presented in Fig. 1.

Jan 1, 1951

By Reynold Q. Shotts

CHEMICAL methods, based on the relative rates of oxidation of fusain, bright coal, and dull coal by nitric acid, have been devised to determine these coal components.1-4 Results obtained by oxidation methods for fusain have been checked against results obtained from microscopic methods5, 6on duplicate samples of the same coals, but to the author's knowledge this has not been done for bright and dull coal components. For this reason it is not certain that the two methods of analysis identify essentially the same chemical or physical units. It would be highly desirable to see results of the application of both methods to duplicate samples, but in the absence of any such data the author has attacked the problem indirectly. From the U. S. Bureau of Mines samples were obtained of three Alabama coals which the USBM had analyzed optically and reported on over the past 30 years. These samples were subjected to analyses by oxidation rate methods. Results of this work, and comparisons with the USBM analyses, have been published." This was the first indirect approach to the problem. The present report attempts a second indirect approach by way of internal validation. By nitric oxidation samples of two whole coals were carefully analyzed for fusain, bright coal, and dull coal. One coal was analyzed in duplicate. Duplicate portions of each of the coals were divided into three density fractions by means of heavy liquids. A duplicate portion of one of the coals was divided by sieving into three size fractions. Each fraction was analyzed by oxidation and its percentage composition calculated in terms of fusain, bright coal, and dull coal. Because the weight percent of each fraction was known, a material balance calculation for the whole coal was also made. The resulting reconstituted analysis of the whole coal could be compared to that determined by direct analysis. In addition, specific reaction rate constants were determined for each component and for each whole coal or fraction. Arbitrary reactivity indexes were calculated by dividing by 100 the sum of the products of the percent of each component in the coal and its specific reaction rate constant. The resulting figure was an average reactivity index for each coal or fraction. Weighting the reactivity indexes for each fraction by the percent of the fraction in the coal gave a reactivity index for each whole coal which could be compared to that calculated directly from the whole coal analysis. If oxidation analyses really delineate definite physical entities within the coal, or even definite groups of similar entities, reconstituted analyses calculated from fraction analyses should check closely those made of the whole coal. It probably is true that optical methods identify and describe a greater variety of components than do chemical methods and that variations are wide in the appearance and quantity of those components identified optically. Chemical methods based upon differences in oxidation reaction rates would of necessity be less discriminating, as between similar components, than would optical methods. The procedures followed for oxidizing the samples, analyzing the residues, plotting and calculating the percentage of each component, and calculating its specific reaction rate constant have been fully described.'-' In brief the method originally proposed by Fuchs et al.1 for the determination of fusain consists of the oxidation of small samples of coal in boiling 8N nitric acid in a condenser-fitted flask. After boiling for periods of 1/2 to 4 hr, the unoxidized residue is filtered and washed. The washed residue is treated with normal sodium hydroxide, diluted, and allowed to stand for several hours. The resulting brown liquor is removed, and the filtered residue dried, weighed, ignited, and weighed again. The ash-free residue is expressed as a percent of original dry, ash-free coal. The percent residue is plotted against time, and the extrapolation of this line to zero time gives the percentage of dry ash-free fusain present in the original sample. The shape of the resulting time plots has been explained' by the assumption that they are the result of two different types of reaction, the first part representing a first order reaction with rate a func-

Jan 1, 1956

By N. Mungan

A study was made of the effects of wettability and interfacial tension on the immiscible displacement of a Iiquid by another Iiquid from porous media. The influence of viscosity ratio was also investigated. Porous media used were polytetrafluoroethylene (TFE) cores prepared by compressing TFE powder under different pressures. lt is shown that displacement of a wetting by a nonwetting Iiquid is always less efficient than the displacement of a nonwetting by a wetting fluid, all other things being equal. In the former case, the recovery efficiency can be increased substantially by either reducing the interfacial tension or increasing the viscosity of the displacing fluid. A qualitative discussion is given on the implications of this work to the recovery of crude oil by water flooding. INTRODUCTION The high cost of oil exploration and new recovery schemes makes it imperative that waterflooding be conducted under conditions favoring most efficient oil recovery. To improve oil recovery by waterflooding, it is essential that the role played by interfacial forces in the entrapment of residual oil be studied and understood. Interfacial phenomena in natural rock, connate water and crude oil systems are very complicated because of the complexity of the natural liquids found in petroleum reservoirs, because of our inability to adequately describe the geometrical structure of the porous media and because of a lack of understanding of physical and chemical interactions between the liquids and surface of the pores. The problem becomes further complicated when one tries to elucidate the role of interfacial phenomena in fluid flow. Numerous studies of the displacement of oil by water under different interfacial tension or wet-tability conditions have been made.lm3 These studies have been performed in silica, alundum or sandstone systems using water and paraffin oil and also some surface active material to control the interfacial tension s and the contact angle 0. Unfortunately, the high energies of various interfaces involved favor adsorption and orientation of the surface active material at the interfaces. Also the surface active material concentration at the interfaces exceeds that in the bulk of the liquid phases. Such surface excess may cause the surfactant distribution, the contact angle and the interfacial tension to differ from their measured static equilibrium values and makes interpretation of the displacement experiments difficult. Furthermore, as changes in s also lead to changes in cos 0, the role played individually by one of these parameters in the displacement becomes obscured by the effect of the other. To circumvent these difficulties, a low surface energy solid and true solutions or pure liquids should be used. Use of a low surface energy solid minimizes adsorption and orientation effects at the solid-liquid interfaces. By controlling s and cos 0 through use of selected pairs of pure liquids or true solutions rather than by surfactants, the adsorption effects at liquid-liquid interfaces are eliminated. In the present study TFE cores were used as the porous media. Liquids used were water, sucrose solutions, paraffin oils and benzyl, n-butyl and isobutyl alcohols. The interfacial tension was varied from 40 to 1.1 dynes/cm by suitably choosing the liquid pair. A surface active material was added to the water-oil system only in the case where interfacial tension of 0.5 dyne/ cm was desired. No precise changes of cos 0 were attempted. However, either the displaced or the displacing liquid could be made the one which preferentially wets the TFE surface. Using sucrose solutions and blends of paraffin oils proved to be a convenient way of changing the viscosity ratio between the displaced and displacing liquids. The present investigation examines the effect of interfacial tension, wettability and viscosity ratio on the immiscible liquid-liquid displacement from porous media. Observed data permit a

Jan 1, 1967

By C. D. Stahl, R. Sandrea

This investigation was made to evaluate the comparative effects of the viscosity and the phase behavior of the buffer fluid in the composite solvent displacement of Bradford crude from waterflooded sandstone cores. Buffer slugs of propane, naphtha and other refined hydrocarbons exbihiting increasingly favorable viscosity ratios and decreasing solubility relationships, respectively, with Bradford crude, were used in long Berea sandstone cores. The secondary slug was isopropyl alcohol. The results indicate that higher oil recoveries are obtained for increasingly favorable phase relationships even when these are accompanied by unfavorable viscosity ratios within the range studied. Moreover, when propane is used as a buffer slug with an adverse viscosity ratio of 36, it gives higher oil recoveries than at a similar size slug of an any1 alcohol having a viscosity ratio of 1.09. The investigation was extended to the study of the effect of flooding rate on oil recovery. Residual Bradford crude was displaced from a 6-ft Berea sandstone core at rates varying from 0.3 to 30 ft/ day. The results show that as flooding rates were increased above or decreased below a minimum range of 1 to 2 ft /day, displacement efficiency increased considerably. INTRODUCTION In recent years, the alcohol slug process as a means of tertiary recovery has been the subject of many investigations. Gatlin and Slobod showed the advantages of the combination solvent slugs over the previous single-slug process.1 The combination slugs require less total slug material to obtain similar oil recoveries. The basic combination process involves injecting a primary or buffer solvent which is preferentially oleophilic, followed in turn by a water-driven slug of isopropyl alcohol. This procedure ensures that the buffer slug, which is miscible only with the reservoir oil, displaces and replaces the oil and is in turn displaced, together with the water, by the isopropyl alcohol slug miscible with both fluids. Likewise, for those reservoir oils that show some degree of phase incompatibility with isopropyl alcohol, as does Bradford crude, a proper buffer solvent can artificially make the alcohol process technically feasible. From an economic standpoint, propane or LPG would be the most appropriate primary solvent to be used in the field; however, Taber, et a12 have indicated that the alcohol process becomes highly inefficient in the displacement of light hydrocarbons because of the entrapment of these hydrocarbons during the stabilized bank formation. Moreover, since materials such as propane have such low viscosities, adverse viscosity ratios with most reservoir oils would be penerated, thereby possibly further reducing the efficiency of the buffer solvent. This paper presents the results of an experimental study of the comparative effects of viscosity ratio and phase relationships on the displacement efficiency of Bradford crude by means of dual solvents. The work was extended to include the effect of flooding rate on oil recovery. Rates within the range of field and laboratory values were used. EXPERIMENTAL PROCEDURE APPARATUS The porous media used in this study consisted of two 10-ft and one 6-ft Berea sandstone cores, 3-in. in diameter. These were cast in galvanized steel pipe of 31/2-in. ID and the annulus was filled with Armstrong cement. The 10-ft cores were assembled by connecting two 5-ft units, which were joined together by 8-in. steel flanges fitted to the pipe. Intimate contact between the two sections was obtained by inserting a thin disk of the same sandstone between the core faces. The outlet and inlet ends of the cores were covered with threaded pipe caps. The injected fluid was gravity fed to two variable-rate positive-displacement pumps. The fluids were filtered before entering the core and the effluent was collected in an automatic fraction collector and

Jan 1, 1966

By M. H. Caron

BASIC U. S. Patent 1,487,145 on ammonia leaching of nickel ores was issued to the author on March 18, 1924. Equivalent patents in other countries were obtained later. The Dutch Syndicate Brikcarbo became interested in the process in 1935; and a couple of years later the late Dr. H. Foster Bain sent samples of Surigao laterite iron ore to Delft and witnessed tests made there on this material for the Philippines Commonwealth. As a result, the author was asked in April 1940 by Dr. Bain to go to the Philippines to erect and take charge of a pilot plant for the process. The World War prevented carrying out this proposal. The Dorr Co. also became interested in the process at about the same period. The investigations by the Freeport Sulphur Co. on the process as applied to the Cuban nickeliferous laterites, which resulted in the Nicaro enterprise, and the results of this operation have been well described elsewhere.1,²,³,4,5 This Nicaro plant was, in operation for almost two years, and during this period produced about 10 pct of the world nickel production from laterites containing 1.35 pct nickel. This plant and its operation were war measures and, in view of this, activities were suspended in April 1947. The results obtained fully demonstrated the technical feasibility of the process and its economical aspects on a commercial scale. In this respect, it should be understood that it is probable that improvements may be made by further development, and that there are possibilities for advantageous application of the process to garnierite and similar ores with higher values in nickel than the laterite iron ores at Nicaro. While the articles cited above have given a certain amount of information, no general article containing all the important process data has been pub- lished. Since the process is of more than local interest, a fuller knowledge of the fundamental and practical factors of the method may be welcome to those interested in this new field of metals technology. The author, accordingly, takes pleasure in submitting this article to the AIME as it represents in a condensed form the results of many years of research. The brief outlines of the fundamental and other factors and the explanation of observed phenomena are presented with as little discussion of details as possible, consistent with clarity. It is a special satisfaction to the author to make some contribution of his own in return for the benefits of the many valuable publications issued by the Institute during his thirty years of membership. Ores Adapted for Ammonia Leaching: All nickel and cobalt ores which originate from weathering of peridotites or similar basic rocks having sufficient values are suitable for treatment by the ammonia leaching process after a preliminary reduction under proper conditions. The formation of these deposits was probably as follows: In the course of time the basic rocks were attacked by atmospheric agencies; MgO and SiO2 were gradually leached out, and secondary nickel minerals formed, such as garnierite, a hydrated silicate of nickel and magnesia. These secondary products are, however, not stable. They decompose in a further stage of weathering and ultimately only a relatively small residue of insoluble oxides remains, known as laterite iron ore with a small nickel content and very little cobalt. Under these mantles of laterite, richer nickel values may be found, usually indicated by the occurrence of garnierite. The more the ore is disintegrated by nature, the higher the iron content and the better the nickel extractions that may be expected therefrom. Table I shows extractions that may be expected from different types of ores, assuming treatment of -200 mesh products and that all precautions have been taken for obtaining maximum extractions. As for the distribution of the various nickel minerals and compounds that may be present, great variations may occur from locality to locality as well as vertically in a deposit. From such "run of

Jan 1, 1951

By H. E. Cline, T. H. Alden

A study zvas made of rate-sensitive plastic deformation and superplasticity in alloys of lead and tin. These alloys (lead, PO-19 pct Sn, Sn-38 pct Pb, Sn-2 pct Pb, tin) were extruded, aged at room temperature, or melted and resolidified to produce a variety of ~nicrostrnctures. Flow stress us strain rate data were obtained frorn tension tests for strain rates between 10-6 and 1 min-1. The curve log o .us log £ was S-shaped jor fine-grained materials and approxinzately linear for coarse-grained nzaterials. At constant grain size, the behavior was relatively insensitive to conposition. High rate sensitivity (d log o/d log k) and superplasticity occurred at intermediate strain rates in fine-grained materials and are believed to be associated with a transition with strain rate in the mode of plastic flow. This transition was shifted to higher strain rates with increasing temperataire or decrensing grain size. The high rate rneclzanisrn is presunzed to be slip, while rnetallographic evidence sug-gests that the low rate lnechanism is pain boundary sliding. PEARSON' discovered that extruded eutectic alloys of Pb-Sn and Bi-Sn could be elongated as much as 2000 pct in tension. The ability for stretching decreased with aging time or annealing to increase the grain size. At high strain rates, or if the material was in the cast condition, normal ductility was observed. Following deformation of the extruded Pb-Sn eutectic at low rates, Pearson observed an equiaxed granular structure on an initially flat surface, while rapid straining produced elongated grains. He attributed the large deformation in the extruded alloys to the persistence of extremely small grains to a temperature sufficiently high for inter granular flow. Avery and backofen2 measured the strain rate sensitivity of the flow stress, m = d In old In 6, in the Pb-Sn eutectic and established a correlation between m and the tensile elongation. In the extruded eutectic alloy the strain rate sensitivity was 0.1 to 0.2 at rapid rates and the elongation was small, while at low rates m increased to 0.4 to 0.6 and superplastic elongation was observed. They also noted a grain size effect. In the case of the cast Pb-Sn eutectic the strain rate sensitivity remained at 0.1 over the range of strain rates of their experiment (3 x 10"3 to 2 min-I). These authors suggested that diffusional (Nabarro-Herring) creep was the mechanism by which deformation occurred at low strain rates, while climb-controlled creep occurred at high rates. Two predictions of this model are that, at low strain rates, the strain rate sensitivity approaches 1, i.e., Newtonian viscosity, and that the strain rate at constant stress varies as D/L2, where D is the coefficient of self-diffusion and L the grain size. More recently, a mechanical and microstructural investigation of the dilute superplastic alloy, Sn-5 pct Bi, has been done.3 The results show that the high strain rate sensitivity is associated with a transition with strain rate of the mechanism of plastic flow. At low strain rates, grain boundary sliding and its associated accommodation processes were evident, while at high strain rates quasi-uniform slip was concluded to be the dominant deformation process. The following experiments were performed to extend our knowledge of the phenomena of superplasticity to a larger range of strain rates, compositions, temperatures, and microstructures in the Pb-Sn alloy system. The question of why a cast structure does not exhibit viscous behavior although it appears to have a fine microstructure2 was investigated.

Jan 1, 1968

By G. Sachs, E. J. Riping

All ferrous alloys can be made brittle by straining at sufficiently low temperatures. However, the changes in mechanical properties for different ferrous materials with decreasing testing temperature do not appear to follow any universal law. In particular, complex effects of testing temperature have been observed if cold worked steels were subjected to tensile tests at low temperatures. EFFECTS OF PRESTRAINING AT A TEMPERATURE ABOVE THE TESTING TEMPERATURE ON THE FRACTURE CHARACTERISTICS‡ A considerable amount of data has been presented by a number of investigators on the fracture characteristics of various cold worked steels.' These data usually relate to a two-step procedure first used by Davidenkov,² consisting of stretching by tension to a certain strain or " prestraining" at room temperature and then completing the tensile test, or "testing" at the temperature of liquid air. On the basis of data of this type made available to date, ferrous alloys can be classified into two groups with respect to their fracture characteristics observed on testing at a low temperature after prestraining at room temperature. Very complex phenomena have been observed for all annealed steels. On the other hand, some observations indicate that steels in certain other conditions represent a fundamentally simpler relation. In considering the effect of prestraining at one temperature on the properties obtained at some lower temperature, it should be expected that any cold work reduces the ductility retained in proportion to the magnitude of the cold work. However, the test data presented to date indicate that only heat treated (quenched and tempered) steels appear to conform to this expectation, according to the very limited test data in Fig 1, presented by McAdam, Geil and Mebs. This series of tests, Fig 1, shows that the retained ductility became smaller the larger the prestrain. However, this decrease is less than the amount of prestrain or, in other words, less than the decrease in ductility at the prestraining temperature. These effects of prestraining are fundamentally identical with those observed by Bridgman3 when a steel was prestrained (in tension) under hydrostatic pressure and then subjected to a regular tension test. It appears, therefore, that the basic effect of prestraining under conditions which yield a higher ductility than the (subsequent) testing procedure, consists of gradually increasing the total ductility of the metal from the initial low value of testing to the higher value of prestraining. On the other hand, all annealed steels, if cold worked by tension at room temperature and then tested at a lower temperature, provided that some ductility is retained, showed a far more complex behavior than that discussed above. This relationship is exemplified by Fig 2, for three pearlitic steels.4,5 These particular steels were selected because of the various shapes of their ductility-prestrain curves. All three steels, and any other investigated so far, suffered a rapid decrease in retained (and consequently also in total) ductility when subjected to small pre-strains. Then, after exceeding a certain prestrain it was generally observed that the ductility recovered.* This rather complex behavior of annealed steels may be tentatively correlated with the presence of stretcher strains at small restrains. Heat treated steels do not exhibit stretcher strains. This fact might possibly explain their simpler prestrain-retained ductility relationship. The destructive effect of these stretcher strains may possibly be associated with the presence of triaxiality, which may occur in any highly non-uniform stress and strain state (and which is retained as residual stress after unloading). Even a small degree of triaxiality may then cause a reduction in ductility, or even embrittlement at a sufficiently low testing temperature. The discussion presented above deals with the effects of cold working at a high temperature on the fracturing

Jan 1, 1950

By S. F. Frederick, W. A. Bailey

The relationship between microstructure and mechanical properties of cast 356-type aluminum alloys was studied to determine the cause of the variations in properties resulting from differences in solidification rate. It was found that variations in strength are a consequence of variations in ductility and that ductility is inversely proportional to the dendrite cell size. A mechanism is proposed to account for this correlation based on the fracture strain of the inter-dendritic silicon particles and the differential strain across dendrite cell boundaries. IT has long been assumed that permanent mold castings of aluminum are superior to sand castings because of their finer grain structure and reduced porosity.' A systematic variation of static properties was noted during unpublished studies of fatigue-strength variations with solidification rate of A356-T6. Of particular interest was the observation that for a given composition and heat-treatment, both ductility and the ultimate strength increased with higher solidification rate. Because the A1-Si system forms the basis of many alloys used for castings and welding wire, a study was initiated to determine the details of how higher cooling rates improved mechanical properties of these alloys. The results of this study are presented here. EXPERIMENTAL PROCEDURE Specimens were prepared from 356-T6 to supplement the A365-T6 alloy data from earlier studies. This allowed a comparison of behavior of alloys with substantially different strengths but with only small differences in alloy composition. The composition and heat treatment of both alloys are given in Table I. The specimens were cut from a chill plate casting,' which is a 6 by 9-in. plate, 1 in. thick, which has one end heavily chilled, and a large riser at the other so that solidification is essentially unidirectional from the chill end to the riser. Although not measured here, solidification times measured on similar specimens by embedded thermocouples are a few seconds at the chill end and up to 5 min near the riser. Specimens were obtained by cutting slabs from the plate, parallel to the chill; these represented different cooling rates, with essentially the same composition. For the tests, either 0.125 or 0.250-in. thick slabs were cut for standard 2-in. gage length specimens. The thicker specimens were tested to failure at 2000 lb per min while the thinner specimens were tested in an Instron machine at a constant cross-head speed of 0.02 in. per min. These thin specimens were intended for trans- mission electron microscopy. Some thin specimens were tested to failure while the remainder were given various amounts of prestrain. Dendrite cell sizes were measured by the linear intercept method on photomicrographs at either X100 or X50, depending on the cell size. It was assumed that the dendrite cells were outlined by the silicon particles. Determinations were made on two mutually perpendicular planes and an rms average taken. Electron fractographs of representative tensile specimens were made in the conventional manner using the two-stage replica technique.3 Samples for transmission electron microscopy were prepared by chemical milling followed by electropolishing. RESULTS AND DISCUSSION The results of the tensile tests and the dendrite cell-size determinations are given in Figs. 1 and 2. All data show the same trends, namely, a decrease in ultimate strength and elongation with increasing distance from the chill (and solidification time), and a corresponding increase in dendrite cell size. The yield strength remains essentially constant. The constancy of the yield strength was particularly significant since it indicated that variation in the solidification rate does not affect the stress required to initiate plastic flow. By plotting true stress-true strain curves as in Fig. 3, it can be seen that both

Jan 1, 1969

By J. W. Rutter, K. T. Aust

THE object of the experiments to be described in this report was to determine, first, which grains, out of a large number introduced into a sample in which their growth could proceed, were able to grow most successfully; and, second, the factors which control their growth selection. In an earlier study of grain boundary migration in high-purity lead,' it was found that, under some conditions, the most successful grain in an experiment of this type bears a special orientation relationship to the grain into which it is growing. The present work represents an extension of the previous study, directed at the determination of the orientation relationships which appear under a wider variety of conditions. Experiments of this general type have been done using commercial aluminum2 with somewhat conflicting results. In the present experiments, in contrast to the above,' the sample composition was a principal controlled variable, resulting in a considerable clarification of the phenomena observed. EXPERIMENTAL TECHNIQUE The experimental technique used in this investigation was essentially that employed previously in studies of grain boundary migration kinetics.1'3 The material used was zone-refined lead with various small amounts of tin or silver added to study the effect of varying the sample composition. The specimens were in the form of single crystals, about 1/4 in. 1/4 in cross section by 3 to 4 in. in length, grown from the melt in a horizontal graphite boat. A crystal grown in this way generally contained a lineage or "striation" substructure of the type shown in Fig. 1 of Ref. 1. This substructure consists of an array of low-angle boundaries which partition the crystal into regions misoriented from each other by a few degrees. The substructure constitutes a source of driving energy, estimated to be about 4000 ergs per cc, for the migration of a large-angle grain boundary into the striated crystal. New grains were introduced by plastic deformation in compression of a localized reglon at one end of the sample. Re-crystallization occurs at room temperature in the deformed region, introducing a large number of new, striation-free grains into the specimen. These grains are able to grow into the melt-grown crystal on annealing at a suitable temperature. The stria-tions are removed by passage of the grain boundary, as the substructure energy is utilized to produce the boundary migration. Usually, only one or two of the recrystallized grains persist after growth has occurred for about 1 cm out of the deformed region. Laue back-reflection X-ray photographs were obtained to determine the orientation relationship between the melt-grown crystal and the recrystallized grain or grains which grew most successfully in each specimen. EXPERIMENTAL OBSERVATIONS Fig. 1 shows the results obtained for a series of specimens to which had been added tin in the range from 0 to 5 ppm by weight. In this figure is plotted, in the standard stereographic triangle, the single axis about which the most successful recrystallized grain or grains are related to the starting, melt-grown crystal by the smallest rotation. The range of angular rotations observed about such axes is indicated beside each stereographic triangle. The results shown in the stereographic triangle on the left, Fig. l(a), were obtained by localized deformation at one end of each specimen at room temperature, followed by annealing in a furnace which had been preheated to 300°C. The furnace atmosphere was argon. It will be seen that the orientation relationships observed between the melt-grown and recrystallized grains are quite random. On the right, Fig. l(b), are shown results for samples in which the de-

Jan 1, 1961

By C. R. Masson, M. L. Pearce

The nitrogen contents of seven specimens of iron and steel were determined by the three methods. Good agreement won generally observed between the results of the isotope -dilution and Kjeldahl determinations, tltzts establishing the reliability of the isotope -dilutzon technique. For some specimens, the vacuum-fusion values at 1650 °C were lower than the corresponding Kjeldahl values by up to 0.0015 pct absolute. These differences were eliminated for a specimen of "pure" iron by performing the vacuum-fusion analyses at 2100 ° to 2240 °C. The reason for this relatively high temperature required m the vaczium-fusion analyses is discussed. ThE determination of nitrogen in iron and steel has been the subject of numerous investigations and a concise review of the extensive literature in this field has recently appeared.' Two methods of analysis are most commonly employed, the vacuum -fusion and the chemical or Kjeldahl method. Except in special cases where the presence of certain alloying elements may present difficulties, both methods are generally regarded as applicable, although the vacuum-fusion method is more sensitive and is often preferred for samples of very low-nitrogen content. The method of isotope dilution, first employed for the determination of gases in metals by Kirshenbaum and Grosse,2 has recently been applied to the determination of nitrogen in iron and steel.3,4 The method is attractive in that it does not require the quantitative extraction of gas from the metal specimen. Staley and Svec3 modified the standard Kjeldahlpro-cedure by introducing, along with the steel sample, a measured amount of ammonium sulfate enriched in the isotope 15N. The nitrogen content was obtained by measuring the isotopic ratio 15N/14N in the resultant solution. The technique involved the distillation of nitrogen as ammonia from alkaline solution and subsequent oxidation of NH4+ in the distillate to gaseous nitrogen. The results for iron and steel samples of commercial origin were often in reasonable agreement with values quoted by the suppliers, although occasional marked discrepancies were observed, particularly with the results of vacuum-fusion analyses. Preliminary work in this laboratory4 on the determination of nitrogen by isotope-dilution in the gas phase yielded results for three samples which were significantly higher than the values obtained by vacuum-fusion. The present paper describes an extension of this work to a wider variety of samples. Analytical results by the Kjeldahl method are also reported. EXPERIMENTAL The technique employed for the isotope-dilution determinations was similar to that described elsewhere.4 Several minor modifications were made to the apparatus. These included the use of molybdenum instead of platinum-rhodium suspending wires when crucibles were degassed at temperatures above 1600°C. The circulatory system used previously for converting CO to CO2 was replaced by a single chamber, the walls of which were cooled directly in liquid nitrogen. Temperatures were measured with an optical pyrometer which had been recently calibrated and, as in the previous study, were minimum values obtained by sighting on the center bottom of the crucible. Temperatures obtained by sighting on the interior walls were always higher by 100' to 130°C with the design of crucible employed. Flat-bottomed crucibles exhibited an even larger temperature difference. To check the efficiency with which crucibles were degassed in the isotope-dilution apparatus, several experiments were done in the vacuum-fusion apparatus, suitably modified4 for isotope-dilution studies. Faster pumping speeds and higher degassing temperatures were possible, the latter due to the use of a generator with a higher power output (10 Kva at 398 kc per sec). In these experiments the combustion of CO was omitted and a correction4 was made for the contribution of CO to the ion current at m/e 28, used in determining the isotopic ratio R = l5NP4N. This correction did not seriously influence the re-

Jan 1, 1962

By A. E. Powers, J. F. Libsch

THE simultaneous influence of time and temperature upon the tempering process in steel is well known. Hollomon and Jaffe¹ have expressed the effect of time and temperature upon the progress of tempering by a single parameter, T (c + log t); where T is the absolute temperature; t, the tempering time; and c, a constant characteristic of the steel and treatment. It was found that when hardness data for plain carbon and low alloy steels were plotted vs. this parameter, a master tempering curve was obtained which satisfied all the data for a given steel and a given hardening treatment. Roberts, Grobe, and Moersch² successfully applied the tempering parameter to various tool steels, including high speed steel for tempering times ranging from 6 min to 100 hr. The influence of tempering time and temperature upon the physical properties of high speed steel has also been extensively investigated.'" Recently, the use of induction heating for very rapid tempering treatments has received attention. The authors% have shown that tempering treatments of only a few seconds duration may be successfully applied to plain carbon and low alloy steel. However, the influence of such short tempering treatments in high speed steel has not been explored. Since high speed steel is a highly alloyed steel exhibiting physical reactions during tempering that are often relatively slow and large in magnitude, it is an interesting steel for the study of tempering reactions. It was the purpose of the present investigation, therefore, to study the early progress of reactions leading to secondary hardness in high speed steel, type 6-5-4-2, and to determine if induction-tempering treatments of a few seconds duration are able to produce results equal to those of more conventional long-time tempering cycles. Experimental Details The chemical compositions for two different heats of W-Mo high speed steel used in this study are given in Table I. Table II summarizes the heat treatment given various groups of specimens cut 21/2 in. long and centerless ground to ¼ in. diam. Hardening treatments consisted of preheating to 1600°F (870°C) for V2 hr and then oil quenching from 2250°F (1230°C). Heat I was subjected to the high temperature in a salt bath for 3 min, while specimens of heat II were austenitized in a carbon-block muffle furnace for 10 min. Specimens of series E were immediately refrigerated to — 318°F (— 195°C) in liquid nitrogen following the hardening treatment to transform the major portion of the retained aus-tenite. Specimens of series F and G were subzero cooled to — 100°F (-75°C) in a dry ice-alcohol mixture. Induction tempering was performed with a Lepel high frequency converter operating at a frequency of approximately 300,000 cycles per sec. Heating cycles were controlled and recorded for each specimen using a chromel-alumel thermocouple, percussion welded to the surface of the specimen, and a modified high speed instrument with a timer previously used and described.' Temperature oscillation of the specimens, while being held at the tempering temperature, was ± 15°F (8°C). Tempering Treatments: After hardening, specimens were tempered between 900" and 1500°F (480" and 815°C) to study the progress of retained austenite decomposition and secondary hardening. The specimens tempered in salt for 1 hr (series C, G, and I) were considered to represent conventional treatment and are used for comparison with rapid tempering treatments. Several induction-tempering cycles were employed: 1—flash tempering, i.e., induction heating to the tempering temperature and immediately cooling (series A, E, and F); 2—induction heating for 60 sec at temperature (series B); and 3—double-induction tempering by two successive heating and cooling cycles (series D). All specimens tempered by induction were heated at an initial rate of 450°F (250°C) per sec except those of series E, which were heated at an initial rate of 1300 °F

Jan 1, 1952

By P. S. Kotval, H. Hahell

PRECIPITATION of M23C6 carbides at grain boundaries in austenitic steels and nickel base superalloys has received considerable attention. Hatwell and Berghezan,1 in a study using carbon extraction replicas, observed that dendritic growth of the M23C6 carbide phase occurred at grain boundaries in austenitic steels. Merrick and Nicholson2 have observed that in thin foils of "Nimonic 75" alloy the precipitation of M23C6 carbide was discontinuous at grain boundaries. Lewis and Hattersley3 have suggested that the type of M23C6 precipitation observed in Ni-Cr austenites represented the early stages of discontinuous precipitation. In a more recent study, Singhal and Martin4 have concluded that grain boundary M23C6 precipitation involves the migration of an austenite grain boundary by a mechanism very similar to that proposed by Tu and Turnbull.5 Tu and Turnbull's suggestion essentially involves grain boundary migration under the driving force arising from the difference between the surface free energies of the opposite sides of the plate. Thus, Singhal and Martin's observation4 implies that the first stage of discontinuous precipitation has taken place and that the grain boundary has provided a diffusion short circuit for the sub-stitutional solute atoms (principally chromium) which assist the preferential growth of the M23C6 plate in contact with the grain boundary. However, no evidence of the characteristic cellular morphology typical of discontinuous precipitation was found in Singhal and Martin's studies. Presumably, this is due to the low volume fraction (i.e., low supersaturation of solute) of the precipitating carbide reported by Singhal and Martin.4 Recently, Raymond6 has studied precipitation of the M23C6 carbide in Incoloy alloy 825 and shown that the growth of this phase is perpendicular to grain boundaries at 1400°F and in the plane of the grain boundary at 1700°F. The former aging condition resulting in discontinuous or "cellular" precipitation. Raymond has suggested an explanation for this behavior based on the relative rates of chromium diffusion by volume and grain boundary diffusion at the two different aging temperatures. In the course of a recent investigation on precipitation behavior in several ' strengthened superalloys, precipitation of M23C6 carbide at grain boundaries was studied. Under conditions of a high degree of supersaturation, the M23C6 carbide precipitates in the discontinuous or cellular morphology in Waspalloy (Ni-18.51 Cr-2.0 Fe-3.53 Mo-1.16 Al-2.78 Ti-0.09 C). This note presents electron microscopy observations of this mode of precipitation and its effect on mechanical properties. Specimens of Waspalloy after "solution" heat treatment at 1950°F show essentially single phase matrix with a few residual particles of "primary" MC carbide. In normal commercial heat treatments, precipitation of Ni3(Al,Ti) ordered fcc r' phase occurs throughout the matrix and M23C6 precipitates as globular particles at the grain boundaries. In these commercial heat treatments the degree of supersaturation during precipitation is low. However, if specimens of Waspalloy are quenched from the solution heat treatment temperature of 1950°F and then aged at an aging temperature where the degree of supersaturation is high, discontinuous precipitation of M23C6 occurs. Figs. 1 and 2 show thin foil micrographs of Waspalloy, solution heat treated at 1950°F, water quenched, and aged at 1292° and 1598°F, respectively, for 500 Fig. 1—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 500 hr at 1292°F. Magnification 15,500 times. Fig. 2—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 114 hr at 1598° F. Magnification 13,000 times.

Jan 1, 1970

By J. Chipman, N. J. Grant, E. C. Roberts

An equilibrium study was made of the distribution of chromium and oxygen between liquid iron, containing less than 1 pct Cr, and simple slags of the CaO(MgO)-Si02-FeO-Cr& type in the temperature range 1526' to 1734OC. The effects of slag oxidation, temperature, and basicity were observed. IN spite of the fact that chromium is one of the most important alloying elements in steel, and exists in almost all steels as a significant residual element, little research has been done to determine its behavior in basic steelmaking processes. Considerably more work has been done under silica-saturated acid slag conditions. Korber and Oelsen,' Herasymenko,' and others have generally agreed that in acid steelmaking practice the chromium in the slag behaved as if it were present as the chrom-ous ion (CrO). Work by Hilty- ir, high chromium slags also indicated that chromium may exist as CrO. In basic slag systems no equilibrium data exist. Based on individual studies of basic open hearth and electric furnace practice, Bardenheuer," Rock-rohr,% nd HauckQ oncluded that: 1—chromium recovery increased with decreasing basicity, and 2— chromium recovery increased with increasing temperature, although the effect was small. In similar studies Yavioskii and Dzemyen' concluded that: 1— slag FeO is the most important variable, 2—the basicity of the slag has no effect on chromium recovery, and 3—slag viscosity is not high even when 20 pct Cr,O, is present. Lapitskii\ oncluded that chromium recovery improved as the basicity of the slag decreased and increased with increasing manganese in the metal. Regarding the effectiveness of CrZ08 as a base or acid in basic slags, both Kristofferseno and Trojer" reported that Cr,08 was an acidic component requiring neutralization as 2CaO-Cr,O,. Experimental Procedure The experimental apparatus and procedure used for the present research were similar in most details to those used by Winkler and Chipman" and were described in detail by them. A magnesia crucible was used, holding 60 to 80 lb of Armco iron which was decarburized with hydrogen to about 0.010 pct C. Since all the metal samples solidified without gas evolution, this carbon level was assumed not to be significant. Synthetic slags made by mixing pure oxides were used throughout the study. Temperatures were measured by means of calibrated W-Mo thermocouples and were checked by Pt-Pt-Rh thermocouples. The range of temperatures covered in this study was from 1526" to 1734°C. The chromium content of the iron was in the range 0.032 to 0.82 pct, although the bulk of the tests showed 0.04 to 0.2 pct. The slags were of the CaO(MgO)-SiO,-FeO-Cr,O, type in which the Cr,O, content was from about 2 to 20 pct, although most of the slags showed from about 2 to 10 pct. The FeO range was from about 10 to 65 pct. CaO and SiO, were in the range of about 5 to 45 pct each, yielding a rather wide range of basicity values. The first 12 heats were made without a sulphur addition, and with only 30 min allowed for slag-metal equilibrium to be reached. In previous research it had been shown that less than 30 min was adequate to achieve equilibrium in slags free of Cr2O8.11,14.15 A study of the present data indicated that some of the tests may not have reached equilibrium in this time; accordingly four additional heats were made in which at least 1 hr was permitted for equilibrium to be reached. For reaching

Jan 1, 1955

By J. J. Gilman

RECENT experiments have shown that the mar-tensite reaction in a standard tool steel is influenced by the history of the reacting austenite. The martensite reaction proceeds to a given extent at a higher temperature in austenite formed from an annealed spheroidal structure than it does in austenite formed from tempered martensite: that is to say, a prequench lowers the temperature range of the martensite reaction in this steel. Furthermore, a prequench alters the appearance of the martensite as compared to martensite formed from "virgin" austenite. The steel used for this work was a manganese nondeforming tool steel of the following composition: C, 0.85 pct; Mn, 1.43; Si, 0.23; Ni, 0.12; Cr, 0.59; and W, 0.59. A piece from a rolled bar was forged to Vz in. sq and annealed to a spheroidal structure. Disks 1/8 in. thick were used in the experiments. Several sets of the specimens were prepared and austenitized in lead at 1475°F. Three sets were held at 1475°F for 15 min, quenched in water, and immediately reheated to 1475°F. After this quench the three sets were held for 5 min, 30 min, and 3 hr, respectively, at 1475°F and then the individual specimens in each set were quenched in molten baths to 325", 300°, and 275ºF, respectively, and held for 15 sec. Immediately after the quenching treatments? the specimens were tempered at 600°F for 30 sec to darken the martensite and then were quenched in water. The holding times were short enough to avoid isothermal transformation. Three other sets of specimens were given the same final quenching treatments as the first three, but they were austenitized at 1475°F for 20 min, 35 min, and 3 hr and 15 min, respectively, without an intermediate water quench. The two individual specimens from each set were quenched together in order to eliminate quenching errors. Several experiments were run in this way but only the six sets referred to are described in detail because they all yielded essentially the same results. By means of the stated heat treatments the martensite reaction was investigated for: 1—austenite formed from an annealed structure, and 2— austenite formed from tempered martensite. The martensite reactions of the two types of austenite differed significantly. This is shown by Figs. 1 and 2. Comparison of the photographs on the left in Figs. 1 and 2 with those on the right shows that less martensite was formed by a quench to a given temperature from prequenched austenite than from austenite formed from an annealed structure, that is, the prequench suppressed the martensite reaction. The effect was observed for specimens austenitized 20 min, 35 min, and 3 hr and 15 min. A comparison of Figs. 1 and 2 shows that the martensite reactions in both sets of specimens occurred at lower temperatures with increased austenitization time. This was caused by the increased dissolution of residual carbides with time at 1475°F. However, the difference in amount of martensite formed in prequenched austenite as compared to virgin austenite was approximately the same for all three austenitization times. One further observation should be noted. The needles of the martensite formed from virgin austenite are somewhat longer on the average and show less of a tendency to cluster than those of martensite formed from prequenched austenite. This causes the martensite on the right in Figs. 1 and 2 to have a more acicular appearance than the martensite on the left. Since the sets of specimens used in this work were austenitized for identical total lengths of time and the effect of a prequench on the martensite reaction existed for specimens held at the austenitizing tem-

Jan 1, 1953

By G. B. Thomas

Several methods of analyzing pressure build-up data in wells have been presented by various authors. This paper reviews the theory and method of D. R. Horner and presents example calculations performed on data obtained by testing several different types of wells. These calculations include, (1) graphical estimation of final static pressure, (2) determination of the productive capacity of the pay away from the well bore and. (3) the degree to which the formation adjacent to the well bore has been damaged by completion or other causes. The methods of testing and precautions which should be taken to assure the best data possible are discussed. Limitations and reliability of calculated results are also treated. INTRODUCTION Pressure testing of wells is generally limited to the determination of producing and static mean formation pressures. The so-called "static" pressure determination.. along with PVT, electric log and production data, enable the reservoir engineer to determine, within reasonable limits, the drive mechanism of the reservoir and in some cases. the amount of edge water encroachment. Producing pressure tests enable calculation of productivity indices and allow the engineer to plan the systematic production of a pool for optimum conservation of suhsurface energy. The radial flow formula advanced by Muskat' has been based on the assumption of incompressible radial fluid flow. It has been known that reservoir fluids do not behave in an ideally incompressible manner. For example, incompressible flow theory indicates a simple logarithmic relationship between the difference of the instantaneous and static well pressures when plotted against time. 'The latter stages of this type of plot of pressure build-up data generally show a marked devia-, tion from the earlier straight line trend. which deviation may be shown to be due to the compressible flow of fluids toward the well bore. Shut-in times of 24, 48. 72. or at most 96 hours are currently in wide use for determining so-called "static" reservoir pressure. Due to the continuation of compressible flow of fluids into the well bore long after this arbitrarily taken shut-in time, the determination of static pressures has almost invariably resulted in lower than equilibrium values. Materials balance calculations made early in the life of a reservoir often result in a calculated reserve which later observations prove to be too low. Failure to obtain reliable "static" reservoir pressures within the prescribed 24 or 48-hour build-up period has undoubtedly been a major factor in obtaining these low estimates. Comparison of theoretical and actual productivity performance has indicated that formation damage and not being able to attain true static pressures have been partially responsible for the observed discrepancies. Research into the theory of compressible flow behavior has resulted in methods of applying these theories to the testing of wells. Application of the developed theories to pressure build-up performance indicates that in many cases the following can be estimated. 1. The static reservoir pressure. 2. The in-place effective formation permeability away from the well bore. 3. The degree or extent by which the formation has been damaged adjacent to the well bore, either through completion methods or subsequent damage due to fluid entry. REVIEW OF THEORY Horner2 has shown that the pressure build-up within a "point source" well is approximated by the following formula: Equation (1) is the approximate "point source" solution to the radial compressible flow equation advanced by Muskat. The solution assumes the following: 1. A point source well is producing at constant rate from the center of an infinite reservoir with a constant pressure at its external boundary. 2. The fluid flowing is present in one phase only. 3. The compressibility and absolute viscosity of the fluid remain essentially constant over the range of temperature and pressure variation encountered. 4. The well i.; shut-in at the sand face arid there is 110 after production into the well bore. 5. The formation permeability is homogeneous in the direction of flow. From Equation (1) it can be seen that if an ideal well were shut-in while producing from a reservoir under the conditions assumed, the pressure build-up would be a logarithmic func-

Jan 1, 1953