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By Robert C. Edmiston

The measurement of temperatures in exploratory drill holes yields information on regional and local geothermal gradients and mean surface temperatures. This data may be beneficial to the mining geologist interested in the occurrence and oxidation of metallic sulfide minerals or to the mining engineer interested in subsurface temperatures or water movement. Additionally, the estimation of mean surface temperatures by the projection of thermal gradients to the ground surface provides data on which to evaluate infrared imagery as an exploration tool. Temperature measurements in 30 diamond drill holes in the Silver Bell mining district of Arizona show that a regional geothermal gradient of 2.45°C per 100 m increases to 3.03°C per 100 m near the ground surface. It is also found that an anomaly in the mean annual surface temperature of 0.5°C is associated with the shallow occurrence of disseminated sulfides. Changes in the geothermal gradient due to topography, water circulation, and formation changes also occur.

Jan 1, 1976

By Jack D. Webber

The successful use of oil well packers requires, in part: an understanding of the pressures which exist at the packer in various applications and an understanding of the characteristics of the various types of packers. It is with these pressures, the resultant forces, and the characteristics of packers. that this paper is primarily concerned. An oil well packer may be defined as a mechanical device for blocking the passage of fluids in an annular space. In the more usual case, the annular space is that between the tubing or drill pipe in a well and the casing, and packers which block such an annular space are broadly referred to as casing packers. In the other case. the annular space is that between the tubing or drill pipe and the walls of an open hole, and packers for blocking this space are generally called formation packers. While the hydraulics involved are essentially the same for casing and formation packers. a greater variety of conditions are encountered in the use of casing packers and only casing packers will be discussed. After a packer has been set and a pressure seal effected between tubing and casing, the packer is comparable to a piston in a cylinder. Pressures acting upon a piston result in forces which will move the piston unless some means is provided to prevent such movement. In the same manner, pressures acting upon a packer will move the packer unless there is present a sufficiently great restraining force. PACKER CLASSIFICATIONS Packers may be classified according to the pressure conditions under which they are capable of blocking the annular space between tubing and casing. Fig. 1 shows schematically two types of packers in common use. These packers are capable of blocking the annular space against the passage of fluids under a differential pressure of significant magnitude only when the pressure in the annular space above the packing element is greater than the pressure below. It may be seen that in Fig. l-a. slips with teeth which bite into the casing and prevent downward movement are provided. In Fig. 1-h. an anchor prevents downward movement. In each case, there i-only the tubing to prevent upward movement when differential pressures act to move the packers upwardly. Packers which hold only a significant differential pressure acting downwardly have been in use since the early days of the oil industry and will hereafter be referred to as conventional type packers. In many packer applications operating conditions will 1.crult in differential pressures across the packer which will at times act to move the packer upwardly, and at other times, act to move the packer downwardly. For these applications, designs are available which will block the annular space and resist movement in either direction. Fig. 2-a shows schematically a packer of this type which is designed to be run into a well and set, and removed when desired by merely pulling the tubing. It will be noted that two sets of slips are provided-— one set above the packing element to prevent upward movement, and another set below the packing element to prevent downward movement. This packer is built around a mandrel which is essentially a part of the tubing. and which is free to move longitudinally within certain limits through the set packer. Fig. 2-b shows schematically a permanent type packer which is capable of holding pressures from either direction. Here again, two sets of slips are provided to prevenl movement of the packer. This packer is designed to become virtuallv a part of the casing when set and it is made of drillable material so that it may be drilled out when its removal is desired. The seal nipple shown effects a pressure seal between the tubing and the packer. This seal nipple is a part of the the tubing, and the nipple and tubing may be withdrawn from the well without disturbing the packer. It should be noted that these figures are not representative of all available packers which are designed to hold pressures from both above and below. Packers which resist movement in either direction will hereafter be referred to as universal type packers. There is a third type of packer in general use and this type is designed to block the passage of fluids when the pressure below the packing element ii greater than that above. This type is provided with slips which prevent upward movement of the packer and is somewhat similar to a conventional type packer run upside-down. Packers designed to hold pressure only from below are made in a variety of designs and are usually owned and operated by service companies.

Jan 1, 1949

By Jack D. Webber

The successful use of oil well packers requires, in part: an understanding of the pressures which exist at the packer in various applications and an understanding of the characteristics of the various types of packers. It is with these pressures, the resultant forces, and the characteristics of packers. that this paper is primarily concerned. An oil well packer may be defined as a mechanical device for blocking the passage of fluids in an annular space. In the more usual case, the annular space is that between the tubing or drill pipe in a well and the casing, and packers which block such an annular space are broadly referred to as casing packers. In the other case. the annular space is that between the tubing or drill pipe and the walls of an open hole, and packers for blocking this space are generally called formation packers. While the hydraulics involved are essentially the same for casing and formation packers. a greater variety of conditions are encountered in the use of casing packers and only casing packers will be discussed. After a packer has been set and a pressure seal effected between tubing and casing, the packer is comparable to a piston in a cylinder. Pressures acting upon a piston result in forces which will move the piston unless some means is provided to prevent such movement. In the same manner, pressures acting upon a packer will move the packer unless there is present a sufficiently great restraining force. PACKER CLASSIFICATIONS Packers may be classified according to the pressure conditions under which they are capable of blocking the annular space between tubing and casing. Fig. 1 shows schematically two types of packers in common use. These packers are capable of blocking the annular space against the passage of fluids under a differential pressure of significant magnitude only when the pressure in the annular space above the packing element is greater than the pressure below. It may be seen that in Fig. l-a. slips with teeth which bite into the casing and prevent downward movement are provided. In Fig. 1-h. an anchor prevents downward movement. In each case, there i-only the tubing to prevent upward movement when differential pressures act to move the packers upwardly. Packers which hold only a significant differential pressure acting downwardly have been in use since the early days of the oil industry and will hereafter be referred to as conventional type packers. In many packer applications operating conditions will 1.crult in differential pressures across the packer which will at times act to move the packer upwardly, and at other times, act to move the packer downwardly. For these applications, designs are available which will block the annular space and resist movement in either direction. Fig. 2-a shows schematically a packer of this type which is designed to be run into a well and set, and removed when desired by merely pulling the tubing. It will be noted that two sets of slips are provided-— one set above the packing element to prevent upward movement, and another set below the packing element to prevent downward movement. This packer is built around a mandrel which is essentially a part of the tubing. and which is free to move longitudinally within certain limits through the set packer. Fig. 2-b shows schematically a permanent type packer which is capable of holding pressures from either direction. Here again, two sets of slips are provided to prevenl movement of the packer. This packer is designed to become virtuallv a part of the casing when set and it is made of drillable material so that it may be drilled out when its removal is desired. The seal nipple shown effects a pressure seal between the tubing and the packer. This seal nipple is a part of the the tubing, and the nipple and tubing may be withdrawn from the well without disturbing the packer. It should be noted that these figures are not representative of all available packers which are designed to hold pressures from both above and below. Packers which resist movement in either direction will hereafter be referred to as universal type packers. There is a third type of packer in general use and this type is designed to block the passage of fluids when the pressure below the packing element ii greater than that above. This type is provided with slips which prevent upward movement of the packer and is somewhat similar to a conventional type packer run upside-down. Packers designed to hold pressure only from below are made in a variety of designs and are usually owned and operated by service companies.

Jan 1, 1949

By C. W. Hazelett

This paper is a resume of some of the accomplishments in direct rolling of strip from molten metal, and a description of some experimental developments in recent years. In all the early developmental work, we used a pair of rolls with a bath of metal between them, maintained by flanges or plates at the ends of the rolls. These flanges produced an excess cooling of the metal and built up enormous pressures at this point as the metal went through the bight of the rolls. Many means were tried for compensating for this excess cooling, such as thickening the strip at the edges, heating the end dams directly or by flowing more of the molten metal against them, leaving an open crotch below the end dam and above the bight of the roll, where the excessive pressures built up could be relieved by some of the metal squeezing out at this point, and so forth. All of these helped somewhat to solve the problem, so that very large heats of many metals melting up to 200°F., having commercially uniform gauges, could be rolled up to 24 in. in width. The rolls were made by mounting heavy rings on heavy shafts, and pressures up to 75,000 lb. per inch in width were used. Cooling of the rolls was generally done by spraying water on the outside surface of the rolls that came in contact with the molten metal. Roll life was commercial with brass, barely satisfactory with copper, and totally impractical with steels. The greatest difficulty encountered in all this work was caused by lack of uniformity in the product, owing to a folding action in the mill. Those who are familiar with the operation of a rolling mill know that a bar entering a mill moves at a lower speed than the peripheral speed of the roll. However, the metal solidifying from a bath in a direct rolling mill is cast at exactly the peripheral speed of the roll. This results in irregular folding of the metal, some irregular remelting of the previously solidified sections, and it is difficult, if not impossible, in some cases to exert enough pressure to weld these folded sections sufficiently into a sound product. In addition to this melange of solid, semisolid and liquid metal in the bath, we know that pressure near the freezing point of any alloy in which the constituents have different melting points—and I believe all of them have—causes the lower-melling-point constituent to be squeezed back until it becomes cold enough to solidify and go through the mill. This segregates all alloys, the segregation increasing with the pressures and the freezing ranges of the metals. Add to these problems the excessive roll-maintenance costs with high-melting-point metals and then, the greatest difficulty of all, the vanity of homo sapiens where a matter of possibly large importance is being considered, and the problems seemed almost insuperable. It was long ago obvious to me that something much more than the size of a corporation's money and self-assuradce was necessary if this process was to be made commercial. I should like to show you first the performance of the only mill we ever really designed and built, to see what might be done with a well constructed mill. We accomplished something new in history with this prccess, first, by producing at Scovill Manufacturing Co. coils of brass

Jan 1, 1945

By J. A. Holmes

It is a fact that is coming to be more widely recognized by the general public, as well as by members of the medical fraternity, that the health of persons living in our hill-country depends in no small degree upon the drinking water obtained, just as it has been found that the* use of pure water in the lowlands and swamp-areas of the Southern States results in practical immunity from malarial diseases. Hence the problem, how to obtain supplies of wholesome water for the towns and manufacturing establishments in the hill-country or Piedmont plateau-region of the Southeastern States, becomes one of considerable interest, the importance of which will continue to increase, as the favorable conditions for manufactures and agriculture in this region will make it, in the near future, the most thickly populated portion of the South Atlantic States. Water-supplies from Surface-streams are unquestionably of the first importance; and in the mountain counties, where the region is still largely forest-covered and the streams are swift and continually aerated by rapids and cascades, the water is of superior purity and clearness. This statement is also applicable to the more elevated and sparsely settled portions of the Piedmont plateau; but in the less hilly and more thickly settled portions of this region the streams are more sluggish, and the waters more muddy and less pure, owing to the fact that a much larger proportion of the surface is under cultivation.

Jan 1, 1896

By J. Lyden

In the Picher field, structure made openings for the circulation of the mineralizing solutions by flexing, shearing, and fracturing the sedimentary beds. This structure is used with the spatial and genetic relationship of the ore minerals, sphalerite and galena, and the gangue minerals, dolomite and jasperoid, in prospecting for ore bodies. THE Picher Mining Field, fig. 1, which lies between Baxter Springs, Kansas, and Commerce, Okla., is the most intensely mineralized and the largest zinc-lead ore producing area in the Tri-State District of Missouri, Kansas, and Oklahoma. It has a vast lateral extent of underground workings that is unequaled for the observation of the geology of zinc-lead ore bodies in sedimentary horizons; and thousands of churn drill holes in the unmined areas supplement the underground observations with useful data for the interpretation of the geology. This paper is confined to the ore deposits of the Picher mining field. The reader is referred to the bibliography for the general geology of the Tri-State district which has been ably covered by many geologists. The writer was co-author of several publications on the Tri-State district.'-" This paper is necessarily a repetition of parts of those publications but contains a few changes and additions on the deposition of the minerals. The parts of this paper concerning mineralization maps and pipe slump-structures are not covered in the above publications. Geology The geology of the Picher mining field is similar to that of the entire Tri-State district because the sedimentary horizons that are found here are found throughout the district, and the ore bodies in the respective horizons have similar characteristics. The beds that contain the ore bodies in the Picher field are illustrated and described in fig. 2. The five unconformities found in the mines of the Picher field are indicated on the geologic section, fig. 2. The unconformity shown at the base of Meramec (B bed) is relatively unimportant since B bed was mostly eroded from the area of the Picher field before the Chester beds were deposited. B bed has been observed in the cuttings from only a few churn drill holes. The Pennsylvanian (Cherokee shale) formation is the top horizon found in the Picher mining field. It has been eroded from the southeastern part of the field, but because of the regional dip of the sedimentary beds to the west, it attains thicknesses of 100 ft to 200 ft along the west edge of the field. It is 200 ft to 300 ft thick in the Miami trough. It was deposited on the Boone limestone surface, which contained relatively few shallow erosion channels and very few depressions. Subsequent to the deposition of the shale, solution of limestone from underlying limestone horizons by circulating solutions caused the overlying beds, including the Cherokee shale, to slump into the larger openings formed by the solution and removal of the limestone. Chert The origin of the chert in the Tri-State district has been a controversial subject among geologists. Tarr7 advocated a syngenetic origin for the chert, postulating that it formed from colloidal silica deposited in the Mississippian seas. Leith, Dake and Leighton' argued in favor of silicification of erosion

Jan 1, 1951

By J. Lyden

In the Picher field, structure made openings for the circulation of the mineralizing solutions by flexing, shearing, and fracturing the sedimentary beds. This structure is used with the spatial and genetic relationship of the ore minerals, sphalerite and galena, and the gangue minerals, dolomite and jasperoid, in prospecting for ore bodies. THE Picher Mining Field, fig. 1, which lies between Baxter Springs, Kansas, and Commerce, Okla., is the most intensely mineralized and the largest zinc-lead ore producing area in the Tri-State District of Missouri, Kansas, and Oklahoma. It has a vast lateral extent of underground workings that is unequaled for the observation of the geology of zinc-lead ore bodies in sedimentary horizons; and thousands of churn drill holes in the unmined areas supplement the underground observations with useful data for the interpretation of the geology. This paper is confined to the ore deposits of the Picher mining field. The reader is referred to the bibliography for the general geology of the Tri-State district which has been ably covered by many geologists. The writer was co-author of several publications on the Tri-State district.'-" This paper is necessarily a repetition of parts of those publications but contains a few changes and additions on the deposition of the minerals. The parts of this paper concerning mineralization maps and pipe slump-structures are not covered in the above publications. Geology The geology of the Picher mining field is similar to that of the entire Tri-State district because the sedimentary horizons that are found here are found throughout the district, and the ore bodies in the respective horizons have similar characteristics. The beds that contain the ore bodies in the Picher field are illustrated and described in fig. 2. The five unconformities found in the mines of the Picher field are indicated on the geologic section, fig. 2. The unconformity shown at the base of Meramec (B bed) is relatively unimportant since B bed was mostly eroded from the area of the Picher field before the Chester beds were deposited. B bed has been observed in the cuttings from only a few churn drill holes. The Pennsylvanian (Cherokee shale) formation is the top horizon found in the Picher mining field. It has been eroded from the southeastern part of the field, but because of the regional dip of the sedimentary beds to the west, it attains thicknesses of 100 ft to 200 ft along the west edge of the field. It is 200 ft to 300 ft thick in the Miami trough. It was deposited on the Boone limestone surface, which contained relatively few shallow erosion channels and very few depressions. Subsequent to the deposition of the shale, solution of limestone from underlying limestone horizons by circulating solutions caused the overlying beds, including the Cherokee shale, to slump into the larger openings formed by the solution and removal of the limestone. Chert The origin of the chert in the Tri-State district has been a controversial subject among geologists. Tarr7 advocated a syngenetic origin for the chert, postulating that it formed from colloidal silica deposited in the Mississippian seas. Leith, Dake and Leighton' argued in favor of silicification of erosion

Jan 1, 1951

By W. Bonfield

The temperature dependence of the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.) and the stress-plastic strain curve of polycrystalline Cu 1.9 wt pct Be have been measured for the solution treated condition, an intermediate condition containing G.P. zones and ?' precipitate and the overaged ? precipitate condition, in the range from -58° to 200° C. A transition in micro -yield behavior and a large temperature dependence were noted for the intermediate condition, which are interpreted in terms of the interaction of glide dislocations with two differently sized zones. In comparison the microscopic yield stresses of the solution treated and overaged conditions were less sensitive to temperature variations and are satisfied by the Mott-Nabarro and dislocation bowing theories, respectively. A determination of the temperature dependence of the yield stress of a precipitation hardening alloy has provided a powerful tool for evaluation of the operative deformation mechanism. There is a marked contrast between the effect of temperature on the yield behavior of a metal containing coherent zones or intermediate precipitates, which can be "cut through" by mobile dislocations, and a metal containing a dispersion of noncoherent particles, through which dislocation "bowing out" is the dominant role of deformation.' These studies have in general been confined to single crystals, as it was considered that similar experiments on polycrystalline material did not produce good data because of the lack of sensitivity with which the yield stress could be determined. However, this objection has been removed by the introduction of mi-crostrain techniques, with which the yield stress in polycrystalline materials can be measured to a strain sensitivity of 10-6. Such measurements have not only shown that the deformation of polycrystalline precipitation hardening alloys can be examined with the same detail as single crystals, but also that some unexpected results are obtained.' In this paper the results obtained from a study of the temperature dependence of the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.) and the stress-plastic strain curve of a polycrystalline Cu 1.9 wt pct Be precipitation hardening alloy (Berylco 25) are discussed. The temperature dependence of the alloy was measured for three different conditions: 1) The solution treated condition (a supersaturated solid solution of a containing ~12 at. pct Be3) which is obtained by water quenching the alloy from 800° C. 2) The condition of y' intermediate precipitate, to- gether with some G.P. zones,' which is produced after an aging treatment of 2 hr at 315°C from the solution treated condition. (The alloy was cold rolled to 40 pct reduction prior to aging to minimize grain boundary precipitation effects.)4 3) The condition with equilibrium ? precipitate structure2 which is developed after an aging treatment of 24 hr at 425° C. EXPERIMENTAL PROCEDURE Tensile specimens of gage length 1 in. and with rectangular cross section of 0.18 by 0.06 in. were prepared from the solution treated, cold rolled alloy and were either resolution treated for 1 hr at 800°C, followed by water quenching, or aged for 2 hr at 315°C and 24 hr at 425° C to produce the desired precipitate structures. The microstrain characteristics of the aged specimens were determined at temperatures from —58" to 200° C and those of the solution treated specimens from -58° to 30° C. Each temperature was controlled to ± 0.2°C, which was a level of stability sufficient to eliminate thermal expansion effects from the measurements (~1.2°C temperature increase produced an extension of 2 x 10-6 in.). The microplastic behavior of the specimens in the temperature range below 82" C was measured with a standard Tuckerman strain gage,5 while at temperatures above 82°C a modified Tuckerman gage with a reduced strain sensitivity (4 x10-6 in. per- in.) was used. A load-unload technique was used to establish values of the microscopic yield stress. The specimen was strained at a constant cross head speed of 2 x 10-2 in. per min to a given stress level, at which the total strain was measured. Then the specimen was immediately unloaded at the same rate and any residual plastic strain determined. This procedure was repeated for an increasing series of stress levels until the microscopic yield stress was established by a direct measure of the stress to produce a residual plastic strain of 2 x 10-6 in. per in. (It should be noted that, as reversible dislocation motion occurs at stresses less than the microscopic yield stress,2 the plastic strain rate at this level was not constant.) In an ideal test, the microscopic yield stress would be determined from a continuous stress-strain measurement, rather than from a load-unload sequence, in order to eliminate mechanical recovery effects.6 However, it was found experimentally that mechanical recovery was negligible in Cu 1.9 wt pct Be at small plastic strains for all the temperatures investigated, as the microscopic yield stress was independent of the number of load-unload cycles employed (i.e., the values measured for specimens subjected to different numbers of cycles was within the experimental scatter determined for specimens tested in an identical manner). Therefore, it is reasonable to consider the microscopic yield stress determined in the load-unload

Jan 1, 1969

By M. J. Blackburn

The phasal equilibria in TI':Al alloys has been studied Ry transmission electron microscopy, electron diffraction, and X-ray diffraction. It is shown that three-phase fields exist below the transformation, viz.: a disordered hexagonal solid solution a; an ordered hexagonal phase based on Ti3Al, aa; and a two-phase region. (a + (YZ) , occurring between the single-plzuse fields. The size. disiribution, and morphology of- the a, phase in the two-phase region is shown to be dependent upon the alloy composition and heat treatement. The ordering process in the a, phase leads to the formation of anliphase domain boundary networks; the contrast and stability of these networks is shown to be dependent on alloy composition. A new and relatively simple phase diagralil for the systemm is constructed. The phasal equilibrium at the titanium-rich end of the Ti:Al system has long been the subject of considerable controversy. crossleyl has recently reviewed the phase diagrams that have been advanced for the system and in his turn proposed yet another one. There would seem to be general agreement that a phase exists at a composition at or near Ti& with an ordered hexagonal DO,,-type structure. However, several other phases have been proposed; for instance, Ence and ~ar~olin's' diagram includes two phases, Ti2A1 and Ti3A1, in the region up to 25 at. pct Al. The position of the proposed phase boundaries varies over a considerable compositional and temperature range, a point graphically illustrated in Fig. 1 of Crossley's paper.' It is perhaps germane to briefly examine the techniques used by other workers in the establishment of the phase structure. These fall into three categories: 1) X-ray diffraction, the only limitation of which is the rather low intensity of superlattice reflections in this system.3 Thus, superlattice reflections become increasingly difficult to detect in the more dilute aluminum alloys. 2) A considerable amount of optical microscopy has been performed"2'4 and it will be shown in a later section that many of the obscure mi-crostructures that have been observed can be attributed to hydrogen contamination. It is concluded, therefore, that such observations should be interpreted with considerable care. 3) The variation of some physical property with aluminum content has been measured.5"7 These methods are a useful indication of the existence of a transformation, but are usually insufficient in themselves to identify the transformation. The results using these techniques will be considered in more detail in the discussion. In this paper, the phase structure of alloys containing up to 25 at. pct A1 has been studied by transmission electron microscopy and X-ray techniques, and the results are used to generate a new and relatively simple diagram for the titanium-rich end of the Ti:Al system. EXPERIMENTAL A series of alloys containing 5.05, 10.16, 13.39, 13.99, 14.40, 20.83, and 25.05 at. pct A1 were obtained in the form of hot-rolled sheet 0.02 in. thick. These alloys contained 0.10 to 0.15 pct 0. Thirty-gram arc-melted buttons were prepared from iodide titanium and 99.99 A1 which contained 16.1, 16.9, 18.2, 19.0, 21.6, 22.2, 23.0, and 23.9 at. pct A1 and had an average oxygen content of 0.03 pct 0. The differences in oxygen content did not appear to influence the nature of the phase transformations which were found. Oxygen content may affect the temperature of these transformations, but insufficient samples of the high-purity alloys were examined to answer this question. The heat treatment of alloys was performed in dynamic atmosphere and vacuum furnaces or in helium -filled silica capsules. A special vacuum furnace was constructed to provide a high quenching rate in which rates of 4000°C per sec were obtained using water as the quenching medium. As pointed out by Crossley,' it is important to avoid heat treatment in the a - [} phase field as the resultant segregation of the alloy into the two phases containing different amounts of aluminum can persist through subsequent treatments leading to ambiguous results. It will be demonstrated later that step cooling of specimens from the a phase region can also lead to anomalous effects. Thus, all solution treatments were carried out in either the a or 3 phase fields followed by water quenching and subsequent isothermal annealing at various temperatures. X-ray analyses were performed on a diffractometer on fine-grained bulk specimens. The value of long-range order parameter, S, wa_s calculated from the integrated intensity of the (1211) reflection. In general, the intensity of the (1011) superlattice reflection was compared with that of the (2021) fundamental reflection to correct for experimental differences between measurements. Thin foils for electron microscopical examination were produced by electropolishing using the technique described in an earlier paper.8 Dark-field techniques were employed to a large degree in this investigation using the gun-tilt method. Finally it should be noted that the lattice parameters of the D01,-type superlattice are approximately related to the disordered hexagonal phase parameters by Crf - c, and 2ad - a, where the subscripts s and d refer to the ordered and disordered unit cells, respectively.

Jan 1, 1968

By T. A. Pollard, C. R. Sandberg, E. B. Elfrink

This paper presents an evaluation of compressibility factor data and a discussion of their application to the estimation of gas reserves. A correlation is presented which provides compressibility factors for use in both two-phase and single-phase hydrocarbon systems. Accuracies comparable to those obtained previously for single-phase systems only can be expected. A simple means of predicting the presence or absence of a liquid phase in a condensate system of known composition is illustrated. The correlation is based on 1,030 compressibility determinations from 21 hydrocarbon samples taken from eight oil fields. Of the data used, 75 per cent were from California, 15 per cent were from the Mid-Continent area, and 10 per cent were from South America. The average numerical deviation of the experimental data from this compressibility chart is 1.22 per cent. Charts and tables are included and discussed which illustrate the errors involved through the misuse or nonuse of compressibility factors in estimates of gas-in-place. INTRODUCTION The compressibility factor is a coefficient which expresses the deviation of a gas of given composition from the Perfect Gas Laws. A factor such as this is necessary in any calculation involving volumes of gaseous mixtures, and finds extensive application in the estimation of natural gas and condensate reserves. It is used in the decline curve, the volumetric, and the material balance methods of gas reserves estimation. The behavior of gases at high pressures has been investigated extensively in recent years and considerable data have been assembled on the compressibility characteristics of a number of gases. Notable among the investigators of high pressure gas relationships are Kvalnes and Caddya, Kay" Sage and Laceys, and Brown, Standing" and Katz4. Other contributors are Smith and Watson, Roland and Kaveler', and Stevens and Vance". The data on compressibility factors assembled by these investigators have been presented and correlated in numerous ways; particularly noteworthy is the method first presented by Kay5 which relates compressibility factor "Z" to pseudo-reduced temperature and Pseudo-reduced pressure. Other investigators have used this empirical relationship successfully and numerous charts covering a large number of gases have been constructed on this basis. It is the purpose of this paper to evaluate compressibility factor data and to illustrate the importance of their proper use in the estimation of gas-in-place for both gas and condensate reservoirs. EVALUATION OF COMPRESSIBILITY FACTOR DATA The compressibility chart presented by Standing, Katz, Brown and Holcomb in 1941 is probably the most recent and reliable chart for natural gases. The reliability of the Katz chart has been investigated by the writers for a fairly large number of gases (single-phase) in the pressure range from 500 to 10,000 psia and temperature range from 80 to 400°F. A summary of this comparison is presented in Table I. The numerical average deviation of the chart compressibility factors from the experimental compressibility factors is 1.05 per cent, and the algebraic deviation is -0.28 per cent. The Katz correlation appears to be quite accurate for single-phase hydrocarbon systems. It was based on single-phase systems and does not necessarily provide a means of accurately predicting the behavior of two-phase systems which might be encountered in condensate work. Data published recently by Sage and Oldsl' have enlarged the knowledge of phase behavior in condensate systems by covering extensively the Compressibilities of systems in the two-phase as well as single-phase regions for a wide range of temperatures, pressures and gas-oil ratios. An evaluation of these data indicates that conditions can arise, especially in condensate systems having fairly low gas-oil ratios, in which two phases occur and the usual gaseous compressibility factors do not accurately apply. The measured PVT data of Sage and Olds covering two-phase systems have been correlated with additional such data from the Mid-Continent area and South America; these are presented in Fig. 1. This chart is the result of 1,030 compressibility* determinations from 21 hydrocarbon samples taken from eight oil and condensate fields. Of the data used, 74.75 per cent were from California, 15.45 per cent were from the Mid-Continent area, and 9.80 per cent were from South America. The chart construction is based on the original

Jan 1, 1949

By J. B. Stubbins, R. A. Blais

Extensive geological work was initiated — and continues — when operations of the Iron Ore Co. of Canada commenced in the Labrador-New Quebec area. Such geological operations include: mapping, test pitting, drilling, underground workings, volume factor and structure tests, and the calculation of ore grades and tonnages. Details of such work are given. Development is carried sufficiently ahead of mining to provide reliable tonnage and grade estimates and allow final mine planning. In order to make full use of geology in mining operations, the pit engineer combines the duties of geologist and mining engineer. The iron deposits of the Knob Lake range are located in the central part of the Labrador peninsula, a territory nearly twice the size of Texas, which is bounded by Hudson Bay on the west, Hudson Strait on the north, the Atlantic Ocean on the east and the Gulf of St. Lawrence on the south. The mining district proper is about 1000 miles northeast of Toronto. A 360-mile railroad links this mining area to the port of Sept-Iles on the Gulf of St. Lawrence. Schef-ferville, which is only a few miles from the open-pit mines, is the center of operations of the Iron Ore Co. of Canada. It has a population of nearly 5000. The nearest settlement is Labrador City, some 120 miles to the south, where this company is erecting a large plant for beneficiating its huge reserves of local low-grade iron ores. HISTORY The mineral possibilities of the area were recognized as early as the end of the last century, when A.P. LOW' of the Geological Survey of Canada made his famous trek across the Labrador Peninsula. After mapping several belts of iron formation, Lovr recommended that the area be thoroughly prospected for iron. In 1929, two well known Canadian geologists, J.E. Gill and U'.F. James, led a private expedition in central Labrador and discovered the first deposit of high-grade iron ore near what is now the Ruth Lake Mine. In 1936 the Labrador Mining and Exploration Co. was formed to 11ake over a prospecting concession of over 20,000 sq miles in central Labrador. An adjoining concession of 3900 sq miles in New Quebec was obtained in 1942 by Hollinger Consolidated Gold Mines, which had just Purchased the Labrador Co. The same year the M.A. Hanna Co. Purchased an interest in both exploration companies. From 1942 to 1950 extensive exploration was conducted by the Hollinger-Hanna technical staff to systematically appraise these vast concessions. More than 40 deposits of high grade ore were found and, by the end of 1950, the total ore reserves reached 418 million tons. In 1949 five American steel companies joined the Hollinger-Hanna interests and formed the Iron Ore Co. of Canada. Financing and full-scale construction were decided upon in 1950. This included the construction of a 360-mile railroad through very difficult terrain, the erection of two hydroelectric plants, the installation of terminal port facilities at Sept-IIes, the building of a modern town-site at Schefferville, the construction of crushing and screening plants, and the preparation of deposits for mining. Ore was first shipped in July 1954. Total open-pit mine production to date is 66 million long tons of direct-shipping ore. GEOLOGICAL ENGINEERING The above achievements would not have been possible without irtegrated teamwork of people of diverse skills and extensive use of geology. In their paper on the role of geologists in the development of this iron ore field, (Gustafson and Moss1 rightly emphasized the difficulties facing the early workers in the area. In an uninhabited land with no roads or railroads and no navigable rivers leading to the interior, everything had to be flown in. It was not until 1948 that aerial photographs and adequate base maps became available. In spite of these and other difficulties, an impressive amount of field work has been done since 1942. Nearly all this work has been directed by geological engineers and geologists. About 15,000 :sq miles have been geologically

Jan 1, 1962

By C. P. Walker

Determining the distance to remote objects by observing the time required for sound to traverse the intervening space is an old practice. Attempts have been made to use this method for determining the fluid level in oil wells but as far as the writer is aware it was not found to be practicable, because vibrations in gas in the audible frequency range do not travel as well and as far as low-frequency pressure waves, which are capable of transmitting a greater amount of energy than can be transmitted by audible waves. Wood, in his book "Sound," states that in a given medium the range of sound transmission will vary inversely as the square of the frequency. The fact that the sound from a whistle having a low tone has a much lower attenuation rate than that from a whistle of high pitch is well known. Also, the pressure waves caused by cannon fire often rattle windows at points so distant that no sound of the cannon is heard. In 1932 P. E. Lehr and H. T. Wyatt, of the Shell Oil Co., experimented with the principle of the concussion, or pressure-wave echo, method of determining fluid levels in oil wells. They released compressed gas into the top of the casing, thereby creating a pressure wave, which traveled down the well and back again. Their experiments proved conclusively that, with the proper apparatus for recording the echoes and determining the velocities at which the waves travel, the method could be used successfully for determining fluid levels in oil wells. Wells are often equipped with from one to three tubing catchers and these together with the top of the liner are frequently above the fluid. Each of these obstructions reflects a part of the pressure wave. In such wells there may be, therefore, as many as five pressure-wave reflections. Thus it is obvious that in order to identify the various reflections and to determine therefrom the fluid level in a well it is necessary to obtain a graphic record of these reflections.

Jan 1, 1937

By F. Garofalo

It has been shown by various investigators that during constant stress creep the dependence of minimum creep rate, 6,, on stress, o, is given by em = A onat low stress levels, md by 6, = A' exp [ß s] at high stress levels. In these relations A, n, A', and ß are constant at constant temperature. A single relation has been found which satisfies conditions for both high and low stresses and agrees well with experimental results. This relation is 2, = AN (sinh a s)n, where A" is a constant at constunt temperature and a = p/n. This relation also satisfies the linear relation, 6, = k s, found at temperatures near the melting point at low stresses. EXPERIMENTAL creep results have led to a number of empirical relationships between minimum creep rate, 6,, and the applied stress, s. Under conditions of constant stress it is generally found that at low-stress levels,'-' the dependence of minimum creep rate is given by 6, = Asn. At high-stress levels'74 the experimental results fit the relation, 6, = A' exp [po l. In these relations A, n, A' and ß are constant at constant temperature. A model based on climb-of-edge dislocations from a pile-up array leads to a relation similar to that found experimentally at low stresses.' On the other hand. theories based on chemical-reaction rate,5 nonconservatively moving dislocation jogs, and jog migration and climb-of-edge dislocations4 lead to a relation similar to that found experimentally at high stresses. No difference in mechanism between low and high stress levels has been clearly defined; it is questionable whether such a difference really exists. In any event, the major argument usually given in substantiation of a change in mechanism from low to high stresses is that no single relation exists for defining the stress dependence of the creep rate over wide ranges in stress. However, such a relation has been found and is of the form, dm = A" (sinh a s)n, where A" is a constant at con- stant temperature and a = ß/n. This relation agrees well with experimental results over wide ranges in stress and temperature for copper, aluminum, an A1-3.1 pct Mg alloy, and an austenitic stainless steel. STRESS DEPENDENCE OF MINIMUM CREEP RATE At low stress levels the minimum creep rate, gm, depends on the stress, 0, under conditions of constant stress creep through the relation em=Aon [1] The quantities A and n have been defined previously. In the range in which this relation applies, a linear dependence is found in a log em,-log o plot. Above the stress range of application of relation [I], the minimum creep rate increases much mar; rapidly than predicted by relation [I]. This behavior is shown in Fig. 1 for a series of creep tests on copper4 at various temperatures ranging from 673 o to 973°K. Relation [I] is satisfied at the lower stresses, although the results at 973°K are quite limited. In all cases the transition beyond the applicable range of relation [I] is a gradual one indicating no abrupt change in mechanism. For all test temperatures, values of n have been determined from the results in Fig. 1. These are reported in Table I under Alog tm/hlog o. At high stress levels the stress dependence of minimum creep rate under conditions of constant stress is given by im = A' exp [ß a] 2] All factors have been defined previously. In a log em-0 plot, relation [2] predicts a linear function. Experimentally, a pronounced deviation from the prediction of relation [2] is found at lower stresses. As the stress is lowered, the minimum creep rate decreases more rapidly than predicted by relation [2]. This shown for copper in Fig. 2. Again it is found that the transition from high to low stresses is gradual and no really sharp change is found. Values of p determined from the high stress results are given in Table I. The dependence of minimum creep rate on stress at constant temperature for all ranges in stress

Jan 1, 1963

By R. Stickler, A. Vinckier

An optical and electron microscope study was made on a commercial 302 stainless steel heat treated for massive carbide precipitation. Convincirg evidence was obtained that the grain boundary precipitate does not grow away from the grain boundary into the matrix, but grows as a network of large thin dendrites in between the grains. IN austenitic stainless steels the carbon in supersaturated solution precipitates when the steel is heated in the temperature range 450" to 1000°C. During such heat treatments the chromium-rich carbide occurs primarily at the grain boundaries and has adverse effects on the corrosion resistance and low-temperature ductility of the material. It has been shown that the morphology of the precipitated particles differs widely depending on the time and temperature of the heat treatment, the nature of the boundary, the misfit between the grains, and so forth.1"5 It was assumed by Mahla et al.,' Streicher,' and Mc Nutt' that the carbide particles which nucleate in the grain boundary grow in various geometric or dendritic forms away from the boundary into the matrix. However, Kinzel,' Hatwell et a, and Plateau et aL4 found that the particles nucleate in the grain boundary and grow as a network of thin dendrites in the grain boundary interface. We have made a comprehensive studyg of the precipitation occurring in a commercial 302 austenitic stainless steel heat treated for times ranging from 0.15 to 1500 hr at various temperatures from 480" to 1065"~. This study was made to elucidate the influence of heat treatments on both the mechanical and the corrosion properties of this steel. Part of this investigation which is pertinent to the morphology of the grain boundary carbides referred to above is separately reported here. We found that the particles which nucleated in the boundaries grew in the interface of these boundaries, thus supporting the viewpoints of Kinzel,' Hatwell et al.,3 and Plateau et al.4 Furthermore, when carbide particles nucleated in the matrix very close to the boundaries, they possessed a morphology distinctively different from the particles growing in the grain boundaries. MATERIAL A study of metallographic samples and of fracture surfaces of a 302 stainless steel is reported in this paper. The composition and heat treatments are listed in Table I. Polished and etched samples were examined und813r the optical microscope, and carbon extraction replicas of etched micrographic samples and various fracture surfaces3'8'9 were examined under the electron microscope. RESULTS AND DISCUSSION A representative optical micrograph of the 302 steel, condition A, is shown in Fig. l(a). Particles can be seen on the grain boundaries but no traces can be found of particles which grow from the grain boundaries into the matrix. A carbon extraction replica of this sample shows numerous large thin dendrites, Fig. l(b). The lateral dimension of such carbide particles vary up to 100 p, and their thickness estimated from the amoun! of electron penetration i:; between 500 and 1000A. Such large dendrites are extracted from almost all grain boundaries and, if they had grown into the grains, they would definitely be revealed by etching traces in the matrix, Fig. l(a). The reason why these large dendrites on the extraction replica appear to be grown into the grain is due to the mechanism of the extraction replica process. Thus, these dendrites are supported by the carbon replica film only at the edges originally along the grain boundary trace A-A, Fig. l(b), in the polished metal section and have subsequently fallen over onto the carbon replica film during handling. Although such dendrites generally fall only to one particular side of the grain boundary trace, one finds occasionally that parts of a dendrite have fallen to both sides, as shown in Fig. l(b). Further evidence for the growth of carbide in the grain boundary can be obtained from the appearance of fracture surfaces. A small impact specimen of the 302 steel, condition A, was broken at liquid nitrogen temperature. The fracture path follows the

Jan 1, 1962

By C. R. Sandberg, T. A. Pollard, E. B. Elfrink

This paper presents an evaluation of compressibility factor data and a discussion of their application to the estimation of gas reserves. A correlation is presented which provides compressibility factors for use in both two-phase and single-phase hydrocarbon systems. Accuracies comparable to those obtained previously for single-phase systems only can be expected. A simple means of predicting the presence or absence of a liquid phase in a condensate system of known composition is illustrated. The correlation is based on 1,030 compressibility determinations from 21 hydrocarbon samples taken from eight oil fields. Of the data used, 75 per cent were from California, 15 per cent were from the Mid-Continent area, and 10 per cent were from South America. The average numerical deviation of the experimental data from this compressibility chart is 1.22 per cent. Charts and tables are included and discussed which illustrate the errors involved through the misuse or nonuse of compressibility factors in estimates of gas-in-place. INTRODUCTION The compressibility factor is a coefficient which expresses the deviation of a gas of given composition from the Perfect Gas Laws. A factor such as this is necessary in any calculation involving volumes of gaseous mixtures, and finds extensive application in the estimation of natural gas and condensate reserves. It is used in the decline curve, the volumetric, and the material balance methods of gas reserves estimation. The behavior of gases at high pressures has been investigated extensively in recent years and considerable data have been assembled on the compressibility characteristics of a number of gases. Notable among the investigators of high pressure gas relationships are Kvalnes and Caddya, Kay" Sage and Laceys, and Brown, Standing" and Katz4. Other contributors are Smith and Watson, Roland and Kaveler', and Stevens and Vance". The data on compressibility factors assembled by these investigators have been presented and correlated in numerous ways; particularly noteworthy is the method first presented by Kay5 which relates compressibility factor "Z" to pseudo-reduced temperature and Pseudo-reduced pressure. Other investigators have used this empirical relationship successfully and numerous charts covering a large number of gases have been constructed on this basis. It is the purpose of this paper to evaluate compressibility factor data and to illustrate the importance of their proper use in the estimation of gas-in-place for both gas and condensate reservoirs. EVALUATION OF COMPRESSIBILITY FACTOR DATA The compressibility chart presented by Standing, Katz, Brown and Holcomb in 1941 is probably the most recent and reliable chart for natural gases. The reliability of the Katz chart has been investigated by the writers for a fairly large number of gases (single-phase) in the pressure range from 500 to 10,000 psia and temperature range from 80 to 400°F. A summary of this comparison is presented in Table I. The numerical average deviation of the chart compressibility factors from the experimental compressibility factors is 1.05 per cent, and the algebraic deviation is -0.28 per cent. The Katz correlation appears to be quite accurate for single-phase hydrocarbon systems. It was based on single-phase systems and does not necessarily provide a means of accurately predicting the behavior of two-phase systems which might be encountered in condensate work. Data published recently by Sage and Oldsl' have enlarged the knowledge of phase behavior in condensate systems by covering extensively the Compressibilities of systems in the two-phase as well as single-phase regions for a wide range of temperatures, pressures and gas-oil ratios. An evaluation of these data indicates that conditions can arise, especially in condensate systems having fairly low gas-oil ratios, in which two phases occur and the usual gaseous compressibility factors do not accurately apply. The measured PVT data of Sage and Olds covering two-phase systems have been correlated with additional such data from the Mid-Continent area and South America; these are presented in Fig. 1. This chart is the result of 1,030 compressibility* determinations from 21 hydrocarbon samples taken from eight oil and condensate fields. Of the data used, 74.75 per cent were from California, 15.45 per cent were from the Mid-Continent area, and 9.80 per cent were from South America. The chart construction is based on the original

Jan 1, 1949

By J. C. Shyne, T. D. Gulden

The steady-state creep behavior, in compression, of indium containing a dispersion of atomized glass particles was studzed over a range of temperature, stress, and composition. The observed behavior was not consistent with a simple model of dislocation climb over dispersed particles. From room temperature to about 100°C the temperature dependence could be described by an activation energy about one and a half times that of self-dijfusion in indium while at higher temperatures a much higher ternperature dependence was observed. THE value of dispersion-hardened and precipitation-hardened alloys has long been recognized. The mechanism of hardening, however, is not completely understood, especially at elevated temperatures where dispersed particles increase creep resistance. Following the suggestion of Schoeck1 that the rate of creep in dispersion-hardened materials is controlled by dislocation climb over second-phase particles, Ansel and weertman2 derived steady-state creep equations for dispersion-hardened materials. Their derivation was based on dislocation climb over non-deformable spherical particles in a metallic matrix. For low stresses they predicted a linear relation between applied stress and steady-state creep rate. For stresses large enough to cause dislocations to pinch off around the precipitate particles, the theoretical creep rate was shown to be proportional to the fourth power of stress. For very high stresses an exponential stress dependence was predicted. In all cases the theoretical creep rate is linearly proportional to the diffusion coefficient. This provided the primary temperature-dependent factor. Subsequently, Ansel and Lenel3 reported some experimental data on SAP, a composite of aluminum and aluminum oxide, that was in good qualitative agreement with the above theories. Their experimental creep rates, however, were four orders of magnitude less than the theory predicts. This was attributed to a low density of active dislocation sources in the material; somehow the dispersed particles inactivated the dislocation sources instead of merely interferring with dislocation motion. Meyers and sherby4 have recently reported on the creep behavior of SAP. Their results were inconsistent with a simple dispersion-strengthening model and led them to conclude that a continuous network of oxide controls the high-temperature mechanical characteristics of SAP. Because of the rather complex mechanical behavior of SAP and the lack of agreement about the morphology of its oxide phase, it appeared desirable to study the creep of a dispersion-strengthened material of controlled morphology. For the present work a dispersion of spherical glass particles imbedded in a matrix of indium was chosen. The microstructure of this material was similar to the idealized uniform dispersion of hard spheres in a deforming matrix assumed by Ansel and Weertman in their theoretical treatment. SPECIMEN PREPARATION For experimental convenience, it was decided to use a low melting-point metal in this investigation. It was necessary that the metal not be oxidized readily up to its melting temperature and that it wet the second-phase particles. It was desired that the material chosen for the dispersed phase be available as a fine powder with closely controlled size and shape. The material chosen to satisfy these requirements consisted of a matrix of indium metal containing a dispersion of atomized particles of a soft soda-lime-silica glass ranging from 5 to 30 µ in diam. The glass particles had a highly regular spherical shape. The composite was made by stirring the glass powder into liquid indium maintained at a temperature just above the melting point of indium, 156°C. The creep specimens were prepared by a hot pressing operation. Five to ten g of the mixture were placed in a steel die and pressed at 125°C for 5 min under a pressure of 30,000 psi. The resulting specimens were cylinders about 3/8 in. in diam and ranged from 0.4 to 0.7 in. high. By following this procedure a uniform dispersion was obtained in the creep specimens. Typical microstructures of specimens containing twenty and forty volume percent glass powder are shown in Figs. 1 and 2. Unfortunately, grain size could not be determined by the metallo-graphic techniques used. CREEP TESTING PROCEDURE Creep tests were performed in compression under constant stress. The specimens were placed in

Jan 1, 1963

By G. Y. Chin, M. T. Dolan, W. L. Mammel

We have obtained by computer methods the solutions of the Taylor analysis1 for axisymmetric flow in bcc metals. Four modes of slip have been treated in detail:2-4 (111), {112}(111), {123}( 111), and a mixture of all three. In addition to obtaining anisotropy of strength data for randomly oriented or textured polycrystalline material,4 we have also obtained the lattice rotation resulting from slip on the predicted systems. The patterns of lattice rotation are essential to an improved understanding of texture development during deformation. The present note shows the results of lattice rotation for 5 pct axisymmetric compression, for fifty-two axial orientations distributed at 5-deg intervals throughout the standard stereographic triangle. The data are presented in Figs. 1 to 4 for the four modes of slip. The lattice rotation is indicated by a vector, the ends of which correspond to the positions before and after the deformation. The different vectors emanated from a given orientation represent different combinations of five slip systems that satisfy Taylor&apos;s minimum shear criterion.&apos; Fig. 1 shows the results for {110}< 111> slip. They are similar to those obtained by Bishop5 for the case of (111 )(110) slip in axisymrnetric tension, since in axisymmetric flow the sense of lattice rotation for {111)( 110) in tension is the same as that for (110) (111) in compression. The pattern of lattice rotation may be divided into three regions: region A in which the rotation is toward [100]; region B, toward [lll]; and region C, toward either [ loo] or L lll]. Although some slip combinations in region C lead to [1101, the latter is not stable as continued activity of the same combinations will eventually move the axis toward [loo] or Llll]. It may also be noted that [loo] is itself not stable. However, close inspection of the vectors in region A shows that it is impossible for an axial orientation within A to rotate outside its boundary. Hence after heavy compression, all orientations from A and some from C are expected to form a diffuse band in the [100] vicinity. By far the largest region is B. Here all orientations rotate to [lll], which is a truly stable position. Thus the [111] texture component is expected to be rather sharp. For the case of (112 }( 111) slip, Fig. 2, region C is enlarged at the expense of A, with B about the same as for {110}( 111) slip. A significant difference, however, is that [loo], as well as [Ill], is now truly stable. Fig. 3 shows the results of slip on {123}( 111) systems. Region B is substantially enlarged at the expense of C, with A being intermediate in size between the {110}(111) and {112}(111) cases. Like the case of {110)( 111) slip, [100] is itself unstable. However, the lattice rotations here are confined to less than 5 deg; hence it may be considered "stable" for practical purposes. Finally, Fig. 4 shows the results of mixed slip. Here region B is the largest, and C the smallest, of all the cases considered. Both [loo] and [ill] are stable. The behavior of the three corner positions is, in fact, identical to the case of {112)( 111) slip, Fig. 2; it turns out that in these positions for the mixed slip case, all the active slip systems (based on Taylor&apos;s criterion) belong to pure {112}( 111) .4 In summing up the results for the four modes of

Jan 1, 1968

By E. S. Tankins, G. R. Belton

A simple solution model, based upon the formation of molecular species, is developed for strongly electronegative dilute solutes in liquid binary-metallic solvents. Two approximations are considered for the relative concentrations of the species: the random and the quasi-chemical. Equations are presented for the partial molar free energy, enthalpy, and entropy of mixing of the solute. An experimental study has been made of equilibrium in the reaction H2 6) +0 (dissolved) = H2O(g))for the liquid Cu-Co alloys. The standard free energy of solution of oxygen is presented as a function of composition for the alloys at 1550°C and as a function of temperature for five of the alloys. The experimental results for these alloys and also for Cu-Ni alloys are shown to be in reasonable agreernent with the theory in the random approximation. A knowledge of the thermodynamic behavior of dilute solutes in liquid metals and alloys is of importance in understanding and designing refining and alloy-making processes. Accordingly, several attempts have been made to derive suitable solution models to forecast the effect of a third component on the activity coefficient of such a solute in a metal. Alcock and Richardson&apos; reviewed the literature prior to 1958 and also showed that a regular solution model gave a reasonable description in the case of metallic solutes but failed to account for the behavior of the more electronegative solutes sulfur and oxygen. These same authors2 later modified their model by using the quasi-chemical approximation3 to calculate the average composition of the first coordination shell surrounding each solute atom. This modified model was shown to lead to a better qualitative description of the behavior of the electronegative solutes; however, quantitative agreement with experimental data for oxygen in alloys could only be achieved by assuming a very small coordination number. The authors concluded that the major source of error in the model was the assumption that pairwise interaction energies were independent of composition. Substitutional and interstitial random solution models by Wada and saito4 are essentially similar to the first model except that the required interchange energies were derived from the modified solubility parameter equation of Mott, instead of from experimental binary data. Most recently Hoch5 has presented a statistical model for interstitial solutions and has applied the model to the Fe-C-O system. However, as the various interaction energies needed in the model had to be derived from the ternary data, the model does not promise well as a means of forecasting ternary behavior. Each of the above models carries the assumption that the strongly electronegative solutes have the same configurational environment as metallic solutes; i.e., the solute can be treated as a substitutional or interstitial atom in a quasi-crystalline lattice and is surrounded by a normal coordination shell of solvent atoms. There are, however, a number of facts which suggest that this is unlikely. First, the heats of solution are large, being more typical of molecule formation rather than alloying. For example, the heats of solution of monatomic oxygen and sulfur in liquid iron are -90 kea16,8 and -74 kea1,7, 8 respectively. These are to be compared with maximum heats of solution of metallic solutes in liquid iron of about -13 keal (silicon is an exception with -28.5 kea17). The large depression of the surface tension of liquid iron by trace amounts of the electronegative solutes oxygen, sulfur, and selenium9 suggests, by analogy with aqueous systems, the possible existence of polar molecules in the liquid. The effect of these solutes is at least three orders of magnitude greater than normal metal solutes.10 As has been pointed out by Richardson,11 the electron affinities and ionization potentials of oxygen and sulfur are such that it is likely that they exist in metallic solution as negatively charged ions. If this is so, and it is assumed that electrostatic forces play an important role in determining the configuration, it is unlikely that the stable configuration will be that of an isolated ion surrounded by a symmetrical coordination shell of solvent ions. It is more likely that the energy of the system would be lowered by the formation of solute-solvent screened dipoles. The above arguments suggest the formation of "molecular species" between solute and solvent atoms. The idea of the existence of molecular species in such solutions is not new, however&apos;, for Marshall and chipman12 have explained in a semi-quantitative manner the C-O equilibrium in liquid iron by postulating the species CO. Chen and Chip-man13 interpreted their measurements on the Cr-O equilibrium in iron in terms of the species CrO. Zapffe and sims14 have also postulated the existence of such species in liquid-iron alloys.

Jan 1, 1965

By W. D. Robertson, J. -P. Briant, M. Gell

The distribulion of dislocatiorls genevnted during the propagalion of hydrogen-induced cracks in Fe-Si cryslcrls was studied as a funclion of temperature f-110o lo 243°C) and silicorz conlenl (3.1 and 4.2 pct). It zoas found that the clislocntiotl densily and the size of the plctslic zone increased with increasing tempevalnre and decreasing silicon conlent. Furtheruvzove, there was a correlcrtion in the dislocalion patterns formed around cracks that propagated at different tempevattrt-es in cvyslals of diffevent silicon contents such that a 1 pcl itlcverise in silicon content was equivalent to a lemperaluore redziclion of approximately 120°C. The experimenlal YeSnllS were compaved with the results of an elastic-plastic wodel that relates the size of the pluslic .zone to the cvack length, internal pressure, and yield stress. it was found that the clzunges in the dislocctlion cryrays with lemperature and combosition can be e-kplaincd by the lemperatrnre and composilion dependence of the yield stress. An wmtsual feature of this study was the observation of low -temperature noncrystrrllogruphic cracks. PLASTIC relaxation can occur at the edge of a moving crack by the operation of pre-existing dislocation sources or by the creation of new sources in a region of perfect 1attice.l&apos;2 The amount of relaxation in a given crystal depends on the crack velocity and the temperature, and can determine whether a crack propagates in a brittle or a ductile manner.1-3 Tetelman and Robertson4 observed microcracks m Fe-3 pct Si single crystals that formed on (100) planes by the precipitation of hydrogen gas during electrolytic charging at 23°C. The plastic deformation accompanying crack propagation was observed in the form of dislocation etch pits and an extensive analysis has been made of the size, shape, and crystallography of the dislocation arrays5-7 This paper describes the effect of temperature on the plastic deformation generated around hydrogen-induced cracks in Fe-3.1 pct Si and Fe-4.2 pct Si single crystals. The observations are compared with the results of an elastic-plastic model for yielding around a crack containing an internal pressure. 1) EXPERIMENTAL PROCEDURES The composition of the materials used in this study are given in Table I. Single crystals of alloy A and the 4.2 pct Si alloy were grown by the strain-anneal method; crystals of alloy B and the 5.1 pct Si alloy were cut from an ingot grown from the liquid. he ~ingle-cr~stal metallographic specimens had a Cross section of 0.100 by 0.050 in. with a length of at least 3/8 in. Specimens were annealed for 3 hr at

Jan 1, 1968

By E. W. McAllister

The decision of the California Oil Umpire&apos;s&apos; office to accept well potentials established from subsurface-pressure data has brought to the attention of many operators for the first time the application of such data to production problems. This paper reviews the development and application of subsurface-pressure data in kettleman Hills, where these data have been used in production work since 1932. The Kettleman Hills field was discovered in October 1928. The first subsurface-pressure surveys were made early in 1932 and by the middle of 1933 the two major operators in the field were making routine pressure runs in thcir respective wells. Shortly therefter, these companies agreed to exchange pressure data, and later a third company entered into the agreement. This made it possible to analyze the effects upon the reservoir pressure of past production practices, which are discussed in the latter part of the report. It is interesting that many of the applications of subsurface-pressure data discussed herein were anticipated by C. L. Clark and C. B. Kimberlint in a report2 dated March 1933. PRODUCTIVITY Index In the majority of individual well problems involving the use of subsurface- pressure data, it is necessary to use a factor known as the "productivity index," which indicates the ability of a well to produce and represents the number of barrels of oil or oil and water per day that will enter the well bore for each pound per square inch pressure drop made opposite the producing interval of the well. The productivity index may be determined from pressure and production data for one or more rates of flow and a static or shut-in pressure survey or from production and pressure data for two or more rates of flow. Productivity indices may be based upon either net oil or total fluid production. All indices referred to in this report are based upon net oil. The value of the productivity index for Kettlcman Hills wells decreases generally with time and it is not uncommon for the index to vary in value at any specific time fur various rates of flow. The decline of the productivity index may be attributed partly to the loss of reservoir pressure. As the reservoir pressure decreases, gas originally in solution is released from the oil, congesting the flow of fluids through the formation and increasing the viscosity and surface tension of the oil; thus the flow resistance of the fluids through the formation is increased, resulting in a decrease of the productivity index. For convenient reference, the productivity indices for each well are plotted against time and a curve is drawn through the points showing the trend of the average index value. Plotted on Fig. I are index values for five

Jan 1, 1941