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By M. H. Gaskell, D. M. Kehn, G. T. Pyndus

A correlation of the bubble point pressure for black oil systems is developed using the standard physical-chemical equations of soiutions. The correlation is based on 158 experimentally measured bubble point pressures of 137 independent systems and is expressed in terins of the usually measured field pnrameters— flash separation gm-oil ratio, rank oil gravity, total gas gravity, and reservoir temperature. The data were obtained on systems produced in Canada, Western and Mid-Continent01 United States, and South America. The average error (algebraic) in the representation is 3.8 per cent, and the maximum error encountered is 14.7 per cent. INTRODUCTION In the absence of experimentally measured properties of reservoir fluids, it is often necessary for the field engineer to make estimates regarding the fluid properties based on the usually measured producing parameters. To aid in these estimations, various correlations have appeared in the literature in recent years. Among the pertinent properties of interest is the bubble point pressure. A correlation for this parameter has been reported by Standing'. However, this correlation was based essentially on California produced crudes and this limitation was pointed out with its presentation. The correlation presented in this paper utilized data on crude oil systems from Canada, Wes- tern and Mid-Continental United States, and South America. CORRELATION DEVELOPMENT The basic assumption used in this development is the same as employed by Standing', There is a wide variety of ways to combine these parameters; however, in this instance the combination was made on the basis of Henry's law2. Accordingly, the relationship proposed is Although Eq. 2 defines an individual system, it is of limited value since H' is a function of gas-phase composition and the system temperature. It was observed that for the systems where the bubble point was measured at several temperatures that the ratio of the bubble point pressures and the ratio of the corresponding absolute temperatures (R) were practically identical. Thus, for correlation purposes the bubble point pressure may be taken as a direct function of the absolute temperature. This relation is valid only for those systems that are not near the critical point. Accordingly, this correlation will be inadequate for systems in the region of the critical point. The solubility of the various hydrocarbons found in the gas phase increases with the molecular weight. Thus, the saturation pressure should be inversely related to the gas gravity. Applying these principles to Eq. 2 and rearranging terms gives: The variables 02 the left side of Eq. 3 were designated as the "hubble point pressure factor". The number of mols of tank oil per barrel is a function of the "mclecular weight" of the tank oil. Although the tank oil is a complex mixture, it was assumed for the purposes of this correlation that a unique molecular weight could be assigned to a given oil. This was designated as the "effective molecular weight", and was related to the oil gravity, This empirical relationship was developed simultaneously with the correlation by assuming values of M,. and working to obtain a smooth curve for both the correlation and the effective molecular weight. The relationship between the oil gravity and the effective molecular weight used in this correlation is shown in Fig. 1. The effective molecular weight is somewhat higher than the molecular weight of the C fraction. The difference between these values is largest for the low-gravity systems. It is noted that this effective molecular

By M. C. Miller, M. R. Tek, D. L. Katz

Previous studies have shown the influence of geometric variations on the drawdown and buildup behavior of a well completed in a homogeneous, porous medium containing a single-phase fluid. Other papers have shown the influence of leakage across caprocks on drawdown tests on water wells and aquifers. This paper presents two additional cases: the influence of an adjacent, expansible source of fluid, and the effect of caprock leakage on the measured in situ permeability and compressibility. Methods are developed for evaluating the influence of these two deviations from a uniform aquifer upon the in situ permeability and compre.ssibility indicated by pump tests. INTRODUCTION In relatively uniform porous media, saturated with a single-phase fluid, the effective reservoir permeability and compressibility of the water porous bed system may be obtained from drawdown and build-up data on wells, such as the initial wells drilled in aquifer storage reservoirs (Homers and Katz et al.7). In considering the drawdown and build-up behavior of wells adjacent to storage reservoirs, or of wells in an aquifer adjacent to an unknown gas field, questions arise as to the quantitative effect of the presence of compressible fluid on the measured permeability and compressibility of the formation. The solution to this problem is presented, using a constant pressure line source at some distance from two wells, one of which is pumped and the other used as the pressure observation well. The solution is presented in terms of the geometry of the wells and their relationship to the constant pressure line. It is known that caprock leakage can interfere with the determination of an aquifer in situ permeability and compressibility (Mantush4, Hantush and Jacob3 and Witherspoon and Muellerll). This paper presents an added case of the effect of leakage through a caprock of known thickness and permeability on well tests starting with a reservoir of constant pressure above the caprock and contributing to the aquifer as a result of the pump test. Again, both a pumping well and an observation well are postulated. These two cases are presented together since both a compressible fluid nearby and. caprock leakage show similar deviations from expected in situ permeability and compressibility results, and the solutions are similar in form. EFFECT OF A NEIGHBORING CONSTANT PRESSURE SOURCE ON IN SITU MEASUREMENTS Bixel, Larkin and van Poollenl presented a paper showing the influence of a discontinuity of the properties of a fluid formation system on drawdown and build-up performance. Their case is related to the present study but may be distinguished from it in that their numerical work and resulting graphs relate only to the performance of the pumping well itself. Incorrect values for in situ reservoir properties may be obtained from pump test data if the skin effect of the well and after-flow are not considered. Analysis of this problem by the authors indicated that the more reliable method of evaluating the influence of an adjacent gas field or expansible source was to use one well for pumping and another well at some distance from it for observing the aquifer pressure performance. An expansible source of hydrocarbon near a pumping well may be approximated by a line of constant pressure for a pump test. Fig. 1 illustrates a pumping well and an observation well near a line of constant pressure. Pressure behavior of an observation well during a drawdown pump test near a line of constant pressure is given by the diffusivity equation:

Jan 1, 1967

By Raymond D. Sloan

Dropping from third position among the oil-producing states of the nation in 1942, Oklahoma ranked fourth in 1943 with a total output of 121,431,ooo bbl., a decline of 11.9 per cent from the previous year's total of 137,792,000 bbl. Production ranged from a maximum of 346,900 bbl. daily in February to a low of 322,800 bbl. daily in October, and at the close of the year was averaging 330,000 bbl. daily from 52,096 wells, or an average of 6.3 bbl. per well. The state's well, average at the close of 1942 amounted to 6.7 bbl. At the turn of the year, it appeared reasonable to assume that Oklahoma's producing rate would continue its downward trend during 1944 unless reversed by greater than normal discoveries. To Jan. I, 1944, Oklahoma has produced 5,188,466,-ooo bbl. of crude oil. Development and Exploration A total of 1287 wells was drilled in 1943, representing an increase of 77 wells, or 6.4 per cent over the preceding year's total of 1210. Of the wells completed, 587 (45.6 per cent) were oil wells with an average initial production of 319 bbl.; 127 (9.9 per cent) were gas wells with an average initial of 8,639,000 cu. ft.; and 573 (44.5 per cent) were dry. A total of 333 wildcats was drilled (25.9 per cent of all wells), an increase of 13 (4.1 per cent) over the 1942 total of 320. Of the*wildcats drilled, 46 (13.8 per cent) were oil wells with an average initial production of 235 bbl.; 27 (8.1 per cent) were gas wells with an average initial of 8,249,-ooo cu. ft.; and 260 (78.1 per cent) were recorded as failures. Reconditioning of wells throughout the state led to a total recompletion of 230 wells. Of these, 131 were oil wells with a combined initial production of 8360 bbl., 31 were gas wells with a total initial of 211,950,000 cu. ft., and 68 were abandoned. The 46 successful wildcats opened 33 new producing areas, one of which produced from three separate horizons, and led to the development of production in new horizons in 11 old pools. While none of the 1943 discoveries have as yet developed into what might be termed major pools, the West Moore pool, in Cleveland County, and the West Edmond pool, in Oklahoma County, are the two outstanding new areas opened to production. The West Moore pool, sec. 29, 10 N., 3 W., discovered in December 1943, was completed for an initial production of 248 bbl. of oil in 3 hr. through small tubing chokes in the second Wilcox sand from 8787 to 8800 ft. One well was drilling in this area at the close of the year. The West Edmond pool, an April discovery in sec. 32, 14 N 4 W., is producing from the Hunton lime at a depth of approximately 6950 ft., the world's deepest Hunton lime pool. To the end of the year, 15 oil wells had been completed, with no gas wells and no failures. Accumulated production to Jan. I, 1944, amounted to 474,300 bbl. of 41" gravity oil. There were 29 active operations in the field at the end of the year. The West Edmond and West Moore pool discoveries established the first commercial production west of the Granite Ridge,

Jan 1, 1944

By Raymond D. Sloan

Dropping from third position among the oil-producing states of the nation in 1942, Oklahoma ranked fourth in 1943 with a total output of 121,431,ooo bbl., a decline of 11.9 per cent from the previous year's total of 137,792,000 bbl. Production ranged from a maximum of 346,900 bbl. daily in February to a low of 322,800 bbl. daily in October, and at the close of the year was averaging 330,000 bbl. daily from 52,096 wells, or an average of 6.3 bbl. per well. The state's well, average at the close of 1942 amounted to 6.7 bbl. At the turn of the year, it appeared reasonable to assume that Oklahoma's producing rate would continue its downward trend during 1944 unless reversed by greater than normal discoveries. To Jan. I, 1944, Oklahoma has produced 5,188,466,-ooo bbl. of crude oil. Development and Exploration A total of 1287 wells was drilled in 1943, representing an increase of 77 wells, or 6.4 per cent over the preceding year's total of 1210. Of the wells completed, 587 (45.6 per cent) were oil wells with an average initial production of 319 bbl.; 127 (9.9 per cent) were gas wells with an average initial of 8,639,000 cu. ft.; and 573 (44.5 per cent) were dry. A total of 333 wildcats was drilled (25.9 per cent of all wells), an increase of 13 (4.1 per cent) over the 1942 total of 320. Of the*wildcats drilled, 46 (13.8 per cent) were oil wells with an average initial production of 235 bbl.; 27 (8.1 per cent) were gas wells with an average initial of 8,249,-ooo cu. ft.; and 260 (78.1 per cent) were recorded as failures. Reconditioning of wells throughout the state led to a total recompletion of 230 wells. Of these, 131 were oil wells with a combined initial production of 8360 bbl., 31 were gas wells with a total initial of 211,950,000 cu. ft., and 68 were abandoned. The 46 successful wildcats opened 33 new producing areas, one of which produced from three separate horizons, and led to the development of production in new horizons in 11 old pools. While none of the 1943 discoveries have as yet developed into what might be termed major pools, the West Moore pool, in Cleveland County, and the West Edmond pool, in Oklahoma County, are the two outstanding new areas opened to production. The West Moore pool, sec. 29, 10 N., 3 W., discovered in December 1943, was completed for an initial production of 248 bbl. of oil in 3 hr. through small tubing chokes in the second Wilcox sand from 8787 to 8800 ft. One well was drilling in this area at the close of the year. The West Edmond pool, an April discovery in sec. 32, 14 N 4 W., is producing from the Hunton lime at a depth of approximately 6950 ft., the world's deepest Hunton lime pool. To the end of the year, 15 oil wells had been completed, with no gas wells and no failures. Accumulated production to Jan. I, 1944, amounted to 474,300 bbl. of 41" gravity oil. There were 29 active operations in the field at the end of the year. The West Edmond and West Moore pool discoveries established the first commercial production west of the Granite Ridge,

Jan 1, 1944

By D. R. Parrish, W. E. Lamoreaux, W. W. Owens

Several methods are now being used by the industry for determining the gas-oil flow characteristics of reservoir rock samples. Most of the laboratory experirnerltal rlzethods can be classified either as steady-state, unsteady-state, or Hassler-type tests. Although the validity of the results obtained by any specific method is not questiorzed, in general, the complexity of these methods leaves much to be desired. This investigation dealt primarily with the development of a simplified unsteady-state (gas drive) laboratory test method for measuring kg/ko re1ationships of small core samples. A procedure for selecting uniform and representative sandstone rock samples was developetl since it was observed that the reliability of the test resu1ts was dependent upon having a sample which was uniform in porosity and permeability. The importance of factors known to influence the results of this type test, such as oil viscosity, gas expansion, and pressure differential were eva/uated. The method of calculating the test results was found to give valid data over a wide range of gas expansion. The limits of pressure differential and oil viscosity which would insure reliable results were defined. In cornparisorz with other presently used testing methods, the gar drive method requires considerably less apparatus, is less time consuming, and is more readily adaptable to a routine type core test. INTRODUCTION The detcrmination of the gas-oil flow characteristics of reservoir rocks has been given concentrated study by the oil industry for the past decade. Both analytical and experimental methods have been considered. The analytical methods have generally relied on a simplified characterization of porous materials in order that the fundamental laws of fluid flow and capillarity could be utilized. More direct experimental methods have been proposed by numerous production research laboratories with the primary goal being a simple and inexpensive, yet reliable method for measuring the gas-oil flow characteristics of reservoir rock samples. The experimental methods which have been reported in the literature generally can be grouped into one of the following classifications: 1. Steady state1,2,3,4 in which a fixed ratio of flowing fluids is forced through the test sample until equilibrium conditions of saturation and pressure gradient are established. 2. Hassler or stationary liquid method5,6,7 in which a uniform liquid saturation is attained, usually through capillary desaturation, then gas or oil is flowed through the sample at a pressure drop insufficient to disturb the pre-established saturation. :. Non-steady state method1,8,9,10 In which only the gas phase is injected into the sample, causing displacement of the oil phase and resulting in a system of continually changing average saturation and saturation gradient. The steady-state and Hassler methods have been most popular because, no doubt, of the simplicity of the actual relative permeability calculations. The problems involved in these methods were limited to apparatus design and measurement techniques. In the steady-state method, for instance, a constant flowing fluid ratio is established which, at equilibrium, results in an essentially uniform saturation over the entire length of the test sample. Therefore, the basic flow characteristics could be obtained by correlating the average saturation of the test sample with the kg/ko determined at various flowing gas-oil ratios.

Jan 1, 1957

By C. A. Siebert, S. H. Bush

Isothermal temper-embrittlement studies were conducted on a 5140 steel at various temperatures for times as long as 3000 hr. Specimens from the embrittled steel were subjected to impact tests, metallographic examination, microhardness, and lattice-parameter measurements. SEVERAL of the steels in the low alloy group are subject to a pronounced decrease in impact energy if held within, or cooled slowly through, a range of temperatures below the lower critical. This phenomenon, known as temper embrittlement, is quite pronounced in the chromium steels of which AISI 5140 is typical. This study considered the response of one heat of 5140 steel when embrittled isothermally at various temperatures for times as long as 3000 hr. Excellent reviews of the work done in the field of temper embrittlement have been written by Hollomonl and Woodfine.' Both authors list the various theories which have been advanced to explain temper embrittlement. Some of the mechanisms considered were: 1—a transformation below 700°C; 2—an allotropic modification of iron; 3—precipitation from the ferrite of such compounds as carbides, nitrides, phosphides, or chromium oxides; 4—decomposition of retained austenite; 5—modification of special carbides; 6—grain-boundary segregation; and 7—selective distribution of carbides. The present study investigated the changes in hardness, Meyer's number, impact properties, micro-structure, and lattice parameter which occurred on embrittlement. Previous studies considered the influence of microstructure and of prior austenitic grain size3 on the response of 5140 steel to temper embrittlement. Equipment and Procedure All samples were taken from one heat of 5140 steel; the chemical composition of this steel was: 0.43 pct C, 0.86 pct Mn, 0.020 pct P, 0.019 pct S, 0.27 pct Si, 0.84 pct Cr, 0.10 pct Ni, 0.06 pct Mo, 0.10 pct Cu, and the remainder Fe. The material was received as % in. rounds. This stock was cut down to blanks measuring approximately 0.425~0.425~2.196 in. Heat Treatment: The rough blanks were normalized at 1600°F (870°C) for 1 hr, then austenitized at 1600°F (870°C) for 1 1/2 hr, and quenched into an agitated oil bath. The specimens were tempered at 1275°F (690°C) for 5 hr and water quenched. These tempered specimens were designated as the toughened state. Embrittling Treatments: The tempered bars were divided into sets and subjected to the various embrittling treatments listed in Table I. Temperatures from 750" to 1050°F were investigated for times of 1 to 3000 hr. Special tests to determine the effect of heating a short time at a higher temperature after long-time embrittlement at some lower temperature were also conducted. All specimens were water quenched at the end of the embrittling cycle, then ground and notched to obtain standard Charpy V-notch specimens. Impact Tests: The bars were fractured in a 260 ft-lb Charpy impact unit; specimens were fractured at temperatures ranging from —315°F to room temperature. Fixed temperatures used consisted of —315°F with liquid nitrogen, —115°F with dry ice and acetone, and 32°F with ice and water. Intermediate temperatures were obtained by suspending the bars in a jig over the liquid nitrogen, dry ice and acetone, or ice and water.

Jan 1, 1955

By H. B. Heller, T. J. LaChapelle

Phosphorus nitride has been used as a diffusant for introducing phosphorus into silicon under various conditions. It has a temperature -dependent rate of decomposition beginning in the 500°C range, increasing very rapidly above 1000 C, producing gas -eous phosphorus and nitrogen. Best control was obtained with a two-temperature arrangement, with silicon at the proper higher diffusion temperature. It is an easier compound to use than the usual P2O5 because it is nonhygroscopic and yields temperature-controlled surface concentrations together with excellent final surfaces. Surface doping nearly as high as that produced by phosphorus pentoxide has been observed for sources at 850" to 900°C. Reproducible high sheet resistances were obtained by using slow flow rates (1 linear in. per min) and staggered-baffle gas mixing with the nitride at 550°C. Both inert gas (argon, nitrogen) and oxidizing ambients have been examined. Oxygen reacts to produce anhydrous P2O5, consuming the source at a rapid rate. Nitrogen, except for short diffusion times, suppressed the dissociation reaction and sometimes produced inferior surfaces. Argon appears to be a more useful ambient. PHOSPHORUS is a common impurity atom which may be introduced into a semiconductor lattice to create a p-n junction or an nn contact region. Various investigators1-4 have described techniques which can be used with either elemental phosphorus or certain of its compounds. This paper discusses a newly available compound of phosphorus, phos- some processes silicon wafers are precoated with a phosphate glass which acts as the doping source. Although a nonoxidizing form like elemental phosphorus or a phosphine can be used, most diffusion methods usually involve the use of phosphorus pentoxide. Because of the rapid volatility of this compound, a two-step process is often used, combining a gaseous deposition to introduce a predetermined quantity of phosphorus into the silicon with a later redistribution to obtain the desired distribution and surface concentration. Such a process usually involves predepositing phosphorus at surface concentrations greater than 1020 cm-'. At such doping levels the phosphorus-diffusion coefficient appears to be strongly concentration-dependent.596 Distribution profiles5'9 for these high concentrations of phosphorus do not follow Fick's laws, having extended subsurface regions which appear electrically to be nearly uniformly doped with ionized impurity atoms. Radioactive-tracer experiments also show near-surface anomalies in the distribution profile. Additionally, it has been shown1' that the introduction of very high surface concentrations of impurity atoms into silicon (a step necessitated by the subsequent lowering of concentration during the redistribution) creates dislocations, even in material having no dislocations originally. For device fabrication the use of oxide masking introduces certain difficulties and limitations.7'8 The standard practice of using phosphorus pentoxide as an impurity source adds other problems to these because of the speed and ease with which this compound reacts with moisture present in any gas in contact with it. In fact, P2O5 is one of the fastest and most effective drying agents for gases. Because it is such an excellent desiccant, completely anhydrous phosphorus pentoxide is difficult to obtain and is even more difficult to keep dry. Adequately dry gloved boxes must be used for storage and transfer of the chemical. The presence of even traces of moisture will cause formation of phosphoric acids which, during the high-temperature diffusion, results in polyphosphoric acids of variable composition. Such reaction by-products end up as gradually accumulating viscous fluids in the cooler parts of the diffusion furnace. The calculation of the final solute distribution for

Jan 1, 1964

By Richard B. Reese, George R. St. Pierre, Robert A. Rapp

The vapor pressures of pure iron and pure chromium have been measured using a Knudsen cell coupled with a mass spectrometer. The experimental results agree well with some previously reported data; heats of sublimation and vaporization have been calculated. From vapor pressure rr~easurernents, the activities of iron and chromium in their binary alloys have been determined for NcY = 0.10 to 0.65 over a 1400" to 1700~ temperature range. The activity of chromium in the liquid alloys was found to exhibit positive deviation from ideal behavior when referred to solid chromium as the standard state; however, for the activity of chromium referred to nonequilibrium undercooled liquid chromium as standard state, the activity behavior is almost ideal. ALTHOUGH the Fe-Cr system is important as the basic system of alloy steels, the thermodynamic properties of this system have not been thoroughly investigated at elevated temperatures. In view of the potential practical applications of such data as well as their contribution to alloy theory, further study of the Fe-Cr system was undertaken. In addition, further development of experimental techniques for equilibrium measurements at high temperature is required. The present research involved an application of the Knudsen effusion method in conjunction with a time-of-flight mass spectrometer. Belton and ~ruehan' have measured the activities in Fe-Ni and Fe-Co alloys by a similar method. Speiser, Johnston, and lackbburn' have determined the vapor pressure of pure solid chromium between 1283" and 1561°K by a Langmuir free evaporation technique. The vapor pressure of chromium was described by the expression: over the temperature range 1283" to 1561°K. McCabe, Hudson, and paxton3 have measured the vapor pressures of pure iron and pure chromium by the Knudsen cell technique around 1500°K. The vapor pressure and heat of sublimation at O°K, AH,", for pure chromium agreed within experimental error with the measurements of Speiser et al. at 1200°C. Kubaschewski and HeYmer~ determined the vapor pressure of pure solid chromium in the temperature range 1170" to 1400°C by the Knudsen effusion technique combined with a radioactive tracer analysis of crS1. Their results agreed with the work of previous investigators. Edwards, Johnston, and Ditmars5 have measured the vapor pressure of pure solid iron by the Langmuir technique between 1356" and 1519°K. The vapor pressure of solid iron in the temperature range studied was given by: The data of McCabe, Hudson, and paxton3 on the vapor pressure of pure iron around 1500°K by the Knudsen effusion technique were in good agreement with those obtained by Edwards et a~.~ Hultgren, Orr, Anderson, and Kelley give the selected values for the AH: of pure iron and pure chromium as 98,990 *200 and 94,340 * 500 cal per mole, respectively. These values are the average values determined in the several investigations by different methods. The Fe-Cr phase diagram7 is shown in Fig. 1. Previous determinations of activities in this system have been carried out by several investigators, but most of the work has been done on solid alloys. Using a Knudsen effusion method with cr5', Kubaschewski and Heymer4 reported that the Fe-Cr system exhibits positive deviation from the ideal behavior for compositions ranging from NCr = 0.0398 to 0.699 at 1170"

Jan 1, 1969

By D. A. Thomas, E. S. Meieran

Tungsten wires were examined by transmission electron microscopy after drawing and after high-temperature annealing. Drawn wire consists of highly elongated grains called fibers, whose long axis is parallel to [110]. Each fiber is ribbon-shaped, with the wide dimension of the ribbon parallel to (001) and the narrow dimension parallel to (110). Furthermore, most fibers are bent about [I10] and twisted along their length. The fibers are divided into cells, which in some cases contain a platelet substructure lying on (110) planes. The misorien-tations of these platelets accumulate to allow the macroscopic twist of the fibers. During annealing, several competing reactions occur, starting at different temperatures and progressing at different rates. Among these processes are fiber-boz~ndary migration, polygonization, dislocation rearrangement, and possibly impurity segregation. The fiber-boundary migration accompanied by the formation of transverse boundaries during polygonization leads to an equiaxed grain structure although recrystal-lization does not occur. There is a relationship between the flow stress of the wires and their average subgrain width in the form sy = s0 + kyd-1/2 . Also, there appears to be a relatio'nship between wire ductility and the formation of transverse boundaries during annealing at about 800°C. THERE have been many investigations of the structures and properties of tungsten wires1-4 due to their commercial importance for use as lamp filaments. The structural studies have so far been limited to optical microscope and replica electron-microscope studies. due to the difficulty of .-me- paring from wires thin foils which can be examined by transmission electron microscopy. However, this difficulty has been recently overcome,5 and it is now possible to examine tungsten wires by transmission electron microscopy as well as by other techniques. In this paper, the structure of drawn tungsten wire is described, as are the changes in the structure during high-temperature annealing. Some discussion of the relationship between structures and properties is also given. EXPERIMENTAL MATERIALS AND PROCEDURES Commercial 0.030-in.-diam doped tungsten wires drawn at progressively decreasing temperatures between about 1400° and about 800°C were examined. The composition, mechanical properties, and optical microstructures are described in detail elsewhere.' All experimental materials were vacuum-annealed for 10 ot 30 min at temperatures at 100°C intervals between 700° and 2000°C. Specimens were thinned for examination in the Siemens Elmiskop I electron microscope by the method of Meieran and Thomas.5 STRUCTURE OF AS-DRAWN WIRE The optical microstructure of as-drawn tungsten wire has been described by Peck and Thomas.7 They observed that wire in longitudinal section consists of highly elongated grains called fibers whose width varies between 1 and 10 µ, while in transverse section the fibers appear to be elliptical in cross section and bent about their common [110] wire axis. They explained this unusual appearance as being due to the drawing of a bcc material with a [110] texture, and predicted that the wide and narrow planes of the fiber cross section would be parallel to (001) and (110), respectively. The fibers apparently bend about the [110] axis during drawing to maintain grain boundary continuity during drawing. Transmission electron microscopy offers a way of checking these predictions as well as providing a more detailed picture of the wire structure. Figs. 1, 2, and 3 are typical electron micrographs of

Jan 1, 1965

By N. J. Grant, C. F. Flo, F. B. Cuff

An investigation of the Ti-Cr system has shown the presence of a complete series of solid solutions in the ß phase, with a minimum in the solid us near 50 pct Cr. An intermetallic compound, TiCr2, forms during cooling from the ß solid solution. There is a eutectoid reaction at the low chromium side of the system. IN view of the recognition of the potentialities of titanium and its alloys as important structural materials there has arisen a need for a systematic investigation of various titanium binary diagrams. Of these, the Ti-Cr system was of particular interest because of the improved properties imparted to titanium by small chromium additions. A literature survey disclosed a partial constitution diagram that had been suggested by Vogel and Wenderott,¹ This diagram, shown in Fig. 1, is the result of work done on the Fe-Cr-Ti ternary system. Alloys containing less than 43 pct Cr were not investigated. In addition to this, a study of alloys in the Ti-Cr system was reported by McPherson and Fontana.² Adenstedt3 furnished a number of dilato-meter curves obtained from specimens containing 5, 10, and 15 pct Cr. Very recently, McQuillan4 submitted a proposed diagram covering the complete range of compositions between titanium and chromium. This diagram was in general agreement with the one described here. Experimental Procedure Sponge titanium (99.7 pct) and electrolytic chromium (Bureau of Mines analysis: 99.03 pct Cr, 0.40 pct Fe, 0.53 pct O2) were used for the initial determination of the system. Subsequent refinement of points, particularly for the low chromium side of the diagram, was accomplished by using iodide titanium and high purity chromium (National Research Corp. analysis: 0.050 pct C, 0.045 pct O2). The Ti-Cr alloys were prepared by melting 25 g charges in an enclosed, water-cooled copper crucible using a movable tungsten electrode. The atmosphere was helium, prepurified by first passing it through a drying agent and then through sponge titanium heated to 850°C. Particular care was taken to avoid any large scale segregation resulting from insufficient mixing of the components. Each charge was melted and kept molten for approximately 1 min, allowed to cool, inverted, remelted, and kept molten for an additional minute. In order to ascertain the amount of impurity pickup (oxygen and nitrogen) during the melting procedure, three iodide titanium specimens were melted in sequence and then checked for increased hardness. The specimens in the as-cast condition showed a relatively large hardness increase over the hardness of the as-received iodide titanium. The scattering on these readings was large. However, after the specimens had been homogenized at 840 °C for 2 hr and slowly cooled, the measured increase in hardness over the as-received titanium was small with a corresponding decrease in scatter. The reason for this hardness change is that in heat treating these specimens below the transformation temperature (885°C) there was a conversion from the as-cast structure to the more nearly equilibrium structure of the annealed specimen. The alloys were analyzed for chromium content and although the actual percentage was invariably low the deviation from the nominal composition never exceeded 0.6 pct Cr.

Jan 1, 1953

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 G. F. Sager, B. J. Nelson

Magnesium alloy forgings offer higher and more uniform mechanical properties than heat treated magnesium alloy castings and are used principally for light weight parts that may be stressed in fatigue or subject to impact loads, or where space limitations do not permit the use of the necessarily bulkier magnesium alloy castings. Compositions and Properties of Magnesium Forging Alloys The nominal compositions and properties of the principal commercial magnesium forging alloys are given in Table 1. The two that are most commonly used are AMC58S and AM65S. The former has the highest strength and is, therefore, employed for heavy duty applications. However, the forging of this alloy and of AMC57S ordinarily requires the use of slow speed hydraulic presses. The forging alloy AM65S combines good, although somewhat lower, mechanical properties with excellent forging characteristics. This alloy can be forged on hammers, upsetters, rolls, and mechanical presses, as well as on hydraulic presses. These characteristics make it particularly useful for many applications. Manganese Segregation in AM65S The alloy AM65S contains 5 pct tin, 3 1/2 pct aluminum, and a small amount of manganese, the manganese being added to insure satisfactory resistance to corrosion. Some manganese segregation was occasionally encountered in this alloy. In many applications, such segregation is of no particular consequence, but when forgings are acid dipped prior to the application of various chemical coatings, the segregated particles of manganese constituent may stand in relief. The resultant surface roughening may impair appearance and is undesirable in forgings employed in the textile industry, where very smooth surfaces are essential to avoid the catching and breaking of fine threads. An effort was therefore made to determine the cause of manganese segregation in this alloy and find a method for its elimination. Radiographic examination of a series of cast ingot sections and extruded samples of the AM65S type having manganese contents ranging from zero to about 0.7 pct revealed no appreciable manganese segregation when the manganese was less than about 0.4 pct. A small amount was observed with a manganese content of 0.46 pct and considerable with manganese contents of 0.6 pct or higher. Attempts to eliminate the manganese segregation by variations in the melting and casting conditions were unsuccessful and it soon became apparent that the trouble was attributable to the fact that the manganese contents that caused segregation were in excess of the amounts that would remain in solution at temperatures encountered in the melting and/or casting operations prior to the complete solidification of the ingots. A knowledge of the amounts of manganese that would be soluble in molten alloys of the AM65S type at various temperatures was obviously desirable. The liquid solubilities of manganese in binary Mg-Mn alloys and in Mg-Al-Mn and Mg-Zn-Mn alloys have been determined by Tiner and others,* but no data on the solubility of manganese in molten magnesium alloys containing tin and aluminum are given in the literature. For this reason, an investigation to determine the solubility of manganese in a magnesium alloy containing 5 pct tin and 3.5 pct aluminum (AM65S type) was undertaken.

Jan 1, 1950

By J. Geertsma

In order to obtain a better insight into the pressure-volume relationship of reservoir rocks a theory of pore and rock bulk volume variations is presented. The theory is independent of the shape of the pores but is restricted to isotropic porous media built up of continuous homogeneous matrix material. The main conclusion obtained from this theory is that only three elastic constants and three viscous constants are required for describing pore and rock bulk volume variations if the porosity is explicitly introduced into the treatment. In addition, reasonable approximations are introduced for various types of reservoir rock, e.g., sandstones, limestones, and shales, which lead to further simplifications of the basic formulas. In consequence there is then a further reduction in the number of deformation constants which have to be determined experimentally. It is shown how measurements of these remaining deformation constants can be performed most conveniently. Finally the application of the theory to reservoir studies is discussed and the translation of experimental results obtained in the laboratory into reservoir behavior is considered. INTRODUCTION The decline of fluid pressure in connection with the withdrawal of fluid from an underground reservoir gives rise to a change in volume of both reservoir fluids and reservoir rock. The volume variation of the reservoir rock results in a decrease of both the pore volume and the total volume of the fluid-filled formation. Whereas the variation in volume of the reservoir fluids with pressure is usually known from PVT analysis, that in the volume of the porous medium is rarely measured, as it is considered of minor importance in reservoir engineering. Nevertheless, certain experimental results' suggest that in a number of cases the neglection of the variation in pore volume may introduce errors into material balance calculations of reservoirs producing above the bubble point. Only a few experimental results on the compressibility of porous rocks have been published. The compressibility of pure quartz and of calcite can be found in a paper by Adams and Williamson'. Botset and Reed' carried out some experiments on the compressibility of loose sands, while Carpenter and Spencer' measured the compressibility of a number of consolidated sandstones, which data were supplemented by Hughes and Cooke5. Hall' finally reported a number of experiments designed to study the influence of the porosity on the compressibility of oil-bearing formations, from which it appeared that, particularly in the low porosity range, the compressibility of the pore volume is important enough to be taken into account. Difficulties, however, arise in applying these experimental results to field cases. This is partly due to the fragmentary nature of the published data. Yet even if more complete data were available, the need for a theoretical background would be strongly felt. Such a background can be partially found in studies carried out by Biot,6,7 who published a theory of elastic deformations of porous materials and their influence on fluid displacement within the pores, by Lubinski8, who studied the stress distribution in an elastic porous medium neglecting pore compressibility, and by Gass-mann" who mathematically analysed the elasticity of packings of spheres. The contributions of Biot intro-duce a number of deformation constants which are impractical for reservoir rocks from an aspect of experi-mental determination. The theory developed by dass-mann is correct but difficult to read. It appeared, how-

Jan 1, 1958

By R. H. Hopkins, R. W. Kraft

X-ray and metallographic analysis reveal that the preferred cryslallograPhic relationships in direc-tionally solid~fied Pb-Sn eutectic specimens can be stated: interface growth direction, Experiments in which tin single-crystal seeds were used to nucleate the eutectic demonstrate that the normal lamellar structure observed at steady state can be forced to break down initially to a semide-generate structure when the crystallograPhic direction of the tin seed does not lie within the preferred eutectic interface plane. A normal structure eventually develops by preferred grain growth. X-ray topo-graphs and rocking curves substantiate that the perfection of eutectic samples increases as growth proceeds until steady-state conditions prevail. RECENT years have seen substantial progress made in the understanding of eutectic solidification through both intensive theoretical1'' and experimental investigations (see Ref. 7 for a review and extensive bibliography of both aspects). Several important observations concerning the nucleation and growth aspects of binary eutectic solidification have been brought to light. Briefly some of these include the nonrecipro-cal nucleation of one phase upon another,'j9 the tendency for a specific low-index direction of one or both phases of the eutectic to be aligned in the growth direction during unidirectional solidification,'0711 and the production of lamellar microstructures having a preferred interface plane between "11-13 phases. Questions quite naturally arise as to the mechanism by which preferred grain growth evolves during eutectic solidification and what relationships (if any) connect the initial nucleation of one phase upon another with the preferred growth directions and interface planes observed after a few centimeters of growth in many systems. This study was initiated in an attempt to answer these questions. An experiment was devised in which both the nucleation and growth steps in the crystallization of a binary eutectic, Pb-Sn, could be correlated with subsequently developed eutectic morphology and crystallography. This was accomplished by nucleating the eutectic upon a tin single crystal seed and then causing the eutectic to grow from the seed by directional freezing. The morphology of the structures produced in this manner was then monitored metallographically and the orientation relationships and substructural perfection determined by X-ray analysis. The information thus ob- tained was correlated to the growth history of the samples. EXPERIMENTAL DETAILS The eutectic of composition 38.1 wt pct Pb and 61.9 wt pct sn14 was prepared by accurately weighing lead and tin of 99.999+ (from ASARCO and Lytess Metals and Chemicals, respectively), melting in a clean Pyrex beaker under an argon blanket, and casting into the proper crucible for resolidification as described below. Tin seeds were grown by the method of ~halmers," saw-cut, oriented by the Laue method, and soldered to the pull rod of the Czochralski puller. All seeds were given a final electropolishing (to assure the removal of any deformed material from the cutting operation) and acetone degreasing immediately prior to the nucleation experiment in which they were to be used. Eutectic samples were unidirectionally solidified in a horizontal graphite boat1' or by pulling from the melt16 with tin (or graphite) seeds. A flowing argon atmosphere was employed in all experiments and growth rates and temperature gradients, constant for a given run, varied from 2 to 4 cm per hr and 8" to 15°C per cm over the course of all the experi-

Jan 1, 1969

By K. P. Gupta

In ternary systems containing silicon and transition elements, silicon was found to stabilize the a phase.1 At 1000°C a broad a-phase region was found in the Cr-Mn-Si system,1 which extends very close to the Mn-Si binary line (within about 3 at. pct Cr). Later investigation showed that, if chromium was replaced by small amounts (3 to 5 at. pct) of v,1 Ti, Nb, Ta, Mo, or w,1 the a phase or the R phase was again stabilized. Whether stabilization of complex crystal structures is possible by small additions of iron, cobalt, or nickel to Mn-Si is not known. Investigation of the Co-Mn-Si system4 shows the presence of several ternary phases, but at cobalt concentrations higher than 10 at. pct. In the present work the ternary systems Fe-Mn-Si and Co-Mn-Si were investigated at low iron and cobalt concentrations (< 7 at. pct Fe or Co) in search of phases of complex crystal structure. Experimental Procedure. The alloys were pre-pared by induction melting Co (99.8 pct), Si (99.9 pct), electrolytic Fe (99.88 pct), and Mn (99.9 pct) in recrystallized alumina crucibles under an inert atmosphere of argon gas. The alloy specimens were wrapped in molybdenum foil, sealed in argon-filled (at 1/2 atm) silica capsules and annealed for 72 hr at 1000" 1°C, and water-quenched. The use of argon-filled capsules was found to reduce the losses during annealing and the molybdenum foil prevented reaction of the manganese with silica. The total weight loss due to annealing and melting was found to be less than 1 pct for each alloy. The alloys were not analyzed chemically. A part of each annealed specimen was polished and examined metal-lographically using etching solutions, a) 0.1 to 0.5 pct oxalic acid solution in water, or b) 0.5 pct HNOs in methyl alcohol. Even though the etching solutions were quite dilute, the specimens were heavily etched and stained if the etching time exceeded more than 5 sec. Etching times found suitable were usually 1 to 3 sec. For X-ray diffraction work, a part of each annealed specimen was powdered by crushing after the exposed surface was ground off. X-ray diffraction patterns were taken with powder specimens using a 20-cm-diam asymmetrical focusing camera and Fe K radiation. These powder patterns were found quite satisfactory for the purpose of phase identification. However, X-ray diffraction patterns of single-phase alloy powder specimens were also taken using a Siemens diffractometer and filtered Cr-Ka radiation for greater resolution of the diffraction lines. Results and Discussion. In the Fe-Mn-Si system a new ternary phase was found at 1000°C between the p manganese and the MnsSi phase regions. The approximate phase relationships in this region of the 1000°C isothermal section are shown in Fig. 1. The new ternary phase, designated as the K phase, was found to occupy a narrow region about 1 at. pct in width and extending from Fee.oMn74.5Silg.5 to Fe.Mn.Silg.. At the high-iron content region, the K phase was found in equilibrium with the p manganese and the MnsSi phases but, at the low-iron content end of the K-phase region, the phases in equilibrium with the K phase were the p manganese phase, the MnsSi phase, and another new phase, designated in Fig. 1 as the v phase. The v

Jan 1, 1964

By J. M. Campbell, T. S. Buxton

The most widely used methods of predicting the volumetric properties of gas are based on the principle of corresponding states, which asserts that the compressibility factor is a universal function of reduced temperature and pressure. Previous studies have shown that the acentric factor, as proposed by Pitzer, l is an important addition to reduced pressure and reduced temperature as factors affecting the compressibility factor. Results of this study indicate that, if the pseudocritical temperature and pressure used to determine the reduced conditions are adequately predicted, characterization of natural gas-carbon dioxide mixtures with the acentric factor will allow reliable determination of the compressibility factor. Comparisons of predicted and experimental compressibility factors have shown that the pseudo-critical constant rules of Stewart, Burkhardt and Voo 2 are satisfactory for hydrocarbon mixtures. However, these rules fail to predict the pseduo-critical constants for hydrocarbon-carbon dioxide mixtures. Based on graphically determined pseudocritical temperatures for binary hydrocarbon-carbon dioxide mixtures, a correlation which gives the required correction to the Stewart, Burkhardt and Voo rules was prepared and a compressibility factor prediction technique was proposed. To test the proposed technique, compressibility factors for live mixtures of methane, carbon dioxide and either ethne or propane were experimentally determined at 100, 130 and 160F and pressures up to 7,026 psia. The predicted and experimental compressibility factors for these live mixtures had an average absolute deviation of 0.55 percent. INTRODUCTION Two-parameter generalized correlations based on the principle of corresponding states (PCS) are presently available for reliably predicting the compressibility factor of lean natural gas, i.e., natural gas with low concentrations of hydrocarbons heavier than methane. When these same correlations are used for mixtures of natural gas and carbon dioxide, large deviations between actual and predicted compressibility factors are observed. This study was undertaken to provide a means for accurately predicting the compressibility factor for such mixtures. In the past, two avenues of approach have been employed to extend the applicability of the PCS. The first has been to introduce additional parameters. The second has been to develop combination rules for predicting pseudocritical constants which do not suffer from the limitations of the commonly used molal average constants. In this study, both of these approaches have been considered and employed to arrive at a method for predicting the compressibility factor of mixtures of hydrocarbons and carbon dioxide. SELECTION OF A THIRD PARAMETER Failure of the original PCS to predict the compressibility factor for all pure gases, regardless of their mass, shape or polar moment, has led to the introduction of additional parameters into the PCS. Parameters have been introduced to correct for quantum deviations,3-5 non-spherical or globular shapes6-9 and for polar moments.8-12 In addition to these parameters which are based on some microscopic property and intended to correct for some specific cause of deviation, more general parameters based on some bulk property have also been introduced.1913-16 To use additional parameters to correct for each of the possible causes of deviation among the individual constituents of a gas mixture would require a rather complex form of the PCS. To maintain the PCS in as simple a form as possible, it is more desirable to have a single third parameter which is based on some bulk property influenced by several of the factors causing deviations. The third parameter selected for use in this study is a factor originally proposed by Pitzer.9

By John B. Myers

Vermiculite is the commercial name used to describe a micaceous mineral that expands appreciably when heated. This process, called exfoliation, results in a light weight material. The light weight material is also called vermiculite, or more exactly, expanded vermiculite. Practically all uses of vermiculite are for the expanded material. Composition and Properties Vermiculite, in its natural state, has the characteristic micaceous habit and a perfect basal cleavage and readily splits into thin laminae, which are soft, pliable, and inelastic. The monoclinic crystal faces are often marked by triangular lines at 60° and 120°. The hardness varies from 1.5 to 2 or more, depending on the composition. The specific gravity varies from 2.2 to 2.7; specific heat 0.2; fusion temperature 2,000° to 2,500°F; luster pearly to greasy; color amber, bronze, brown, dark green, and black. Feel is like talc and sometimes soapy when wet. When heated quickly at elevated temperatures, vermiculite exfoliates by expanding at right angles to the cleavage into long wormlike pieces (the name vermiculite is from the Latin vermiculari, to breed worms). This important characteristic of expansion is believed to be a mechanical separation of the layers when the contained water is converted to steam. The increase in bulk volume of commercially prepared material is 8 to 12 times, but individual flakes may expand as much as 30 times. There is no expansion parallel to the cleavage. Vermiculite may also be expanded by several chemical processes such as soaking in hydrogen peroxide, weak acids and other electrolytes. The color changes during expansion. Heat-treated material changes to a light golden bronze or cream color depending on composition. The conditions of heating affect color. Heating in an oxidizing atmosphere produces reddish colors and heating in a reducing atmosphere produces dull gray colors. The iron is generally not oxidized during chemical expansion. Vermiculite is hydrated magnesium-aluminum silicate. Although there has been much research on the chemical and structural composition, there is not yet complete agreement on the exact formula and composition. This is to be expected since vermiculite is not a mineral of fixed composition and different workers have examined different varieties. It has been proposed that vermiculite is not a single species but a family of related minerals. This has also resulted in many names for the particular vermiculite found in a certain deposit. All of this difficulty arises from the very nature of its crystal chemistry. Unlike most minerals, certain crystal structure properties and the chemical composition can be changed by the ordinary forces of nature or in the laboratory. This would suggest that vermiculite be thought of more as a variable mineral rather than a group of related species. It was stated on page 261 of this volume in the chapter on Clay Minerals by H. H. Murray of the Georgia Clay Co., that vermiculite is an equidimensional, expandable clay mineral. Gruner (ref. 14, Chap. 12) showed that the structure consists of a layer made up of two silica tetrahedral sheets with a central magnesium, iron octahedral sheet separated by two layers of water molecules and adsorbed magnesium and calcium ions. Mathieson and Walker,2a in a recent publication, agree that vermiculite must be regarded as a true clay mineral. The characteristic properties of the mineral, such as high cation ex-

Jan 1, 1960

By G. G. Priest, B. E. Morgan

The production of oil and gas from wells is often seriously hindered by the compaction of solids in the perforations during the perforating process. To realize the full productive capacity of a well, it is necessary either to remove the plugging material from the perforations or to perforate in a manner which does not cause plugging of the perforations. The latter method can be accomplished by having a non-plugging fluid in the casing at the time the well is perforated. This paper describes the results of laboratory tests, perforating tests, and experimental field tests which demonstrate that certain emulsions serve effectively as non-plugging perforating fluids. The principal components of these emulsions are two liquids: an aqueous phase consisting of a solution of either sodium chloride or calcium chloride, and an oil phase consisting of diesel oil, tetrachloroethylene, or a combination of both. Small amounts of other agents which serve to stubilize the emulsions, to reduce the fluid loss, and to inhibit corrosion are also present. The density of the emulsions is controllable within the range of 7.5 to 12.5 lb/gal; no insoluble solids are present, the filtration rate is low, and the thermal stability is satisfactory at temperatures as high as 200°F. The corrosion of steel by these emulsions is negligible. Tests conducted under conditions which simulate the temperature and the pressure in an actual well demonstrate that these emulsions fulfill the requirements of a non-plugging perforating fluid. In addition, lirnited field experience furnishes evidence that these emulsions remain in position after they are spotted, that they are retained in the casing after the perforations are made, and that they are easily removed from the perforations when the well is opened for production. When the pressure in the borehole is greater than the formation pressure at the time a well is perforated, plugging of the perforations can be avoided by spotting an emulsion adjacent the interval to be perforated. This procedure should eliminate low well productivity caused by plugging the perforations. INTRODUCTION Nature of Problem The most widely used method for the completion of oil and gas wells is to set and cement casing through productive horizons, and then to obtain production by gun-perforating the section of casing opposite the desired interval. This method is gen- erally successful and it was thought at one time that those failures which did occur were due to insufficient penetration by the perforator. Despite recent improvements in perforators which assure ample penetration, unsatisfactory fluid production continues to be a problem. Evidently, the trouble comes from some other source. Recent results obtained by Allen and Worzel1 demonstrated that low fluid productivity may be caused by the perforating process and/or by the fluid in the wellbore at the time of shooting. They found that perforations are often completely plugged by debris from the perforator, pulverized sand from the formation, and compacted solids from the drilling mud when the pressure in the wellbore is greater than the pressure in the formation at the time of perforation. In some cases a differential pressure in excess of 400 psi was required to initiate flow into the well through these plugged perforations. The plugging of perforations by solids not only causes low productivity from wells, but it creates simultaneously other problems in the production of oil and gas. For example, when most of the perforations are plugged, high rates of flow must occur through the few perforations that are open. The resulting high pressure drop may cause production

Jan 1, 1958

air-lift and equipped with tapered tubing of proper design, we would have a gas input consumption of about 2500 cu. ft. per bbl., which at 3 to 4c. per 1000 cu. ft. would be 7 1/2 to l0c, per bbl., and there would be very infrequent loss of production due to stoppages. It has been demonstrated that with efficient design of air-gas lift, the production of wells can be increased much beyond that obtained with the former type of air-lift employed; also that small wells can be operated by air-lift with tapered tubing at a cost that places this method in competition with beam pumps in many fields. The next step in conservation that the writer expects to have an opportunity to demonstrate is that of restoring the pressure in a pool and producing by air-gas lift all of the oil possible to lift economically. This combined operation is probably the method toward which we shall eventually be working in recovering the maximum quantity of oil from pools where the oil is recovered through bore holes. General Discussion on the Air-gas Lift H. P. Porter, Tulsa, 0kla.—The papers presented at this meeting contain a great amount of valuable information. Wonderful progress has been shown in the development of air and gas-lifts. There has been nearly everything brought out that touches upon the subject. The real point that is lacking is exact knowledge of the velocity with in the flow column which will produce the best effect—that is the thing we must know more about. Velocity in Gas-lift Flow In other lines of industry the matter of velocity of fluids in pipe lines has been well analyzed and there are known laws by which to calculate velocity of flow; for instance, in irrigation work large pumps are designed with intake pipos to employ an intake velocity of 4 ft. per scc. By reduced cross-sect&apos;ion the velocity is increased rapidly as it enters the pump and the discharge rate is at 12 ft. per src., which in turn is reduced in the discharge column to 4 ft. per sec. Crushed coal, grain and granular material is found to be best conveyed by air when a pneumatic conveyor is employed at 100 ft. per sec. As in the design of a pumping plant or a pneumatic conveyor, the velocity at the lower end of the column in the flowing well must be controlled within certain limits for best results. Mr. Griswold, I believe, stated that they had velocity as low as 15 it. per scc. and from that up to 78 ft. per sec. Mr. Pierce and Mr. Lewis showed an ideal flow column showing how the velocity increased as the fluid was carried up the column, hut did not give any figures as to the velocity. It would be well to take that sort of a diagram to establish an ideal velocity at the lower or intake end, and then calculate the velocity from expansion of the gas as it goes up. It may be that the, ideal intake velocity would vary, depending on the depth of the well, the quantity of liquid to be handled or the pressure which it may be desired to hold. The subject is one that might be worth much research.

Jan 1, 1928

By J. E. Hanlon, S. R. Butler, R. J. Wasilewski

It is known that stoichiometric NiTi transforms to a structure of lower symmetry near room temperature. The present investigation deals primarily with the changes in the electrical and magnetic properties which occur at the transformation. The effects of composition and various heat treatments on electrical properties are also discussed. In recent investigations by Purdy and Parr,&apos; Wang et a1.,2 Dautovich and Purdy,~ Dautovich et a1.,4 and the authors, ~,&apos; NiTi has been observed to undergo a martensitic phase transformation from the ordered CsCl (B2) structure to one of lower symmetry. The crystal structure of the low-temperature modification is still not completely worked out. This transformation occurs near room temperature for the stoichiometric composition. The thermodynamic, elastic, crystallographic, and microstructural characteristics of this transformation for some compositions have been previously reported.&apos;-= In the present investigation, the changes in the electrical transport properties and magnetic susceptibility of NiTi when it undergoes the martensitic phase transformation have been measured. The approximate composition range covered is 48 to 52 pct Ti.* *All compositions are given in atomic percent._____________________ EXPERIMENTAL PROCEDURES AND RESULTS 1) Sample Preparation. The NiTi alloys were prepared from iodide titanium (>99.92 pct Ti) and vacuum-premelted carbonyl nickel (>99.95 pct Ni) by repeated arc melting under gettered argon and casting in a water-cooled copper mold. After the cast buttons were hot-forged at 800" to 950°C, the oxidized surface was removed by grinding and etching. Samples were cut from the worked polycrystalline buttons. After fabrication, the samples were annealed 1 hr at 900°C and water-quenched. The composition of the alloys was assumed to be the same as in the initial feed. This assumption was supported by material balance checks on 100-g arc-melted buttons which demonstrated quantitative recovery to within k0.02 pct. The oxygen content of the alloys was &apos;150 ppma (weight) and the carbon content was 30 to 50 ppm. 2) Electrical Resistivity and Hall Effect. The electrical resistivity was measured over the composition range 48 to 52 pct Ti for temperatures varying from 4.2"K to 900°C. The high-temperature and many of the low-temperature experiments were carried out using conventional 4-probe dc techniques.7 The Hall coefficient and ac resistivity were measured at 20 cps using the apparatus shown schematically in Fig. 1. The equipment is basically an ac potentiometer: The resistive or Hall voltage of the sample is balanced by a comparison voltage provided by a dividing network across a standard series resistance. The off-balance signal is amplified by a Tektronix 122 amplifier and detected by a Princeton Applied Research (PAR) phase-sensitive detector. The precision of the resistivity and Hall coefficient measurements is i0.1 and i3 pct, respectively. The uncertainty in the data is increased by i2 pct from the precision limits because of uncertainty in dimensions and possible end effects. The temperature dependence of the electrical resistivity and Hall effect for a stoichiometric (50.0 pct Ti) NiTi sample are illustrated in Fig. 2. Above 75"C, this sample has essentially the B2 structure, while below about 0°C it is completely in the low-tempera-

Jan 1, 1968