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By D. W. Akins

The case history of a combination gas and water flood instituted early in the life of a field is described. It was recognized from the beginning that recovery would be low, under normal production methods, from the several separate, thin beds of porous limestone which had such poor native permeability that the wells would not produce without acidizing. It is thought that the combination flood gives excellent recovery efficiencies for this type of reservoir. The chief function of the gas flood now is to maintain bottom hole pressure in that part of the reservoir which will not be affected by the water injection program until later. Present estimates are that ultimate recovery will be approximately double the recovery expected under the original solution gas drive mechanism. Wide (80-acre) spacing has enhanced the economics of the over-all field program by the elimination of more than $5,000,000 worth of unnecessary wells. INTRODUCTION The Haynesville Pettit Field was discovered in November, 1941, with the completion of T. L. James Co.'s Callie Akin No. 1, located in the W 1/2 of the NE 1/4 Section 27-23N-8W, Claiborne Parish, La., at an approximate depth of 5,300 ft. The center of the field is about two miles north and a mile west of the town of Haynesville, La. A total of 189 producing wells have been drilled on 14,500 acres. An additional nine dry holes were drilled. The Louisiana-Arkansas state line divides the field so that 34 wells are in Arkansas and 155 are in Louisiana. Governmental sections are divided equally to contain eight production units making 80-acre spacing where the sections are regular. Along the state line in Louisiana there is an irregular tier of sections, each of which contains approximately 456 acres. When divided equally into eight production units the spacing is 57 acres per well for these three and a fraction productive sections. All Haynesville Pettit wells are identified by their section number followed by their position in the section as determined by numbering the production units counterclockwise beginning in the upper right corner of the section. All of the producing wells in the field except two are unit-ized and operated by the Haynesville Operators Committee. These two wells are located in the extreme northern part of the field in Arkansas. Efforts to bring them into the Unit are being continued. The Pettit operators organized the Haynesville Operators Committee and the field became a unit operation May 1: 1944. GEOLOGY The Pettit is Lower Cretaceous in age and is defined as the uppermost porosity in the Sligo formation. The unitized area known as the Haynesville Pettit Field is composed of two separate zones of porosity approximately 40 ft apart and without connection between the two, except in wells. These zones are known as the Upper Pettit and the Lower Pettit. The Upper Pettit is separated into two sections throughout most of its area by a relatively thin but quite impervious shale streak. These are called the "A" and "B" sections of the Upper Pettit. All of these lenticular zones are composed of coquina limestone and a small percentage of normal oolites. The large

Jan 1, 1951

By Walton J. Greer, System By John E. Owen

The guard electrode system measures the resistivity of formations by employing a thin disk of current which is caused to flow perpendicular to the bore hole. The control of this current disk is obtained in a brute force manner through the use of relatively long equipotential electrodes above and below the measuring electrode. The log obtained from the system is free of "lag," "plateau," "shadow," "reflection" and other distortions evident on conventional logs. The proportionate contributions of the hole size and invaded zone resistivity to the apparent resistivity reading are reduced when the mud and filtrate resistivities are lower. Thus, the guard system favors the use of conductive muds. The mathematical development of the theory is given in an appendix. Equations are derived to evaluate the effects of mud resistivity, hole size, invaded zone resistivity and depth, and the true formation resistivity. Sample logs from several provinces are reproduced and compared with conventional electric logs to illsutrate the much greater detailed lithology that can be presented by the guard electrode system. INTRODUCTION With increased ability of those in the petroleum industry to analyze formation characteristics from electrical resistivity data, there has become apparent the need for more precise measures of that parameter. The measurement of the resistivity of a homogeneous and isotropic material can be made simply when the body of the material is infinite in all dimensions and the measuring electrodes can be placed within the body. In such a case, the current leaving an electrode follows a spherical distribution and the mathematical expression for the potential level at any distance from that electrode can readily be derived.'.' If it is considered that the active electrodes are within a bore hole filled with mud of a resistivity different from that of the formation. the current does not flow in a spherical pattern near the current source or sink, and the calculations of potential levels become more difficult. The additional consideration of a section of formation invaded by mud filtrates, and thus having resistivity different from either that of the mud, the adjacent formations or of the undisturbed formation, makes the mathematical problem extremely complex. Should the vertical dimensions of the formations be considered as finite. the problem becomes so complex as to preclude reasonable solution. Yet, even these considerations have not described adequately the conditions encountered in a large proportion of the wells to be studied. In efforts to evaluate the effects of the various conditions. combinations of twn, three. and four electrode logging con- figurations of the conventional types have been used. The resulting logs have left much to be desired in some provinces. It has become apparent that the use of such configurations will not result in adequate measurements being made, particularly in cases where the formation is composed of thin sections. If all the current of a resistivity measuring circuit is made to flow through the formation opposite the exploring electrode, many of the shortcomings of the conventional measuring system are eliminated. In the guard electrode method of electrical well logging to be discussed in this paper, the current is so controlled by causing it to flow in a thin disk normal to the axis of the logging tool. EARLY HISTORY The guard electrode method of electrical well logging in its early years was a joint development by the Geophysical Research Corp. and the Amerada Petroleum Corp. The method was first experimentally investigated by means of model studies. The results of these studies indicated that current focusing systems properly applied to electrical well logging

Jan 1, 1951

By D. W. Akins

The case history of a combination gas and water flood instituted early in the life of a field is described. It was recognized from the beginning that recovery would be low, under normal production methods, from the several separate, thin beds of porous limestone which had such poor native permeability that the wells would not produce without acidizing. It is thought that the combination flood gives excellent recovery efficiencies for this type of reservoir. The chief function of the gas flood now is to maintain bottom hole pressure in that part of the reservoir which will not be affected by the water injection program until later. Present estimates are that ultimate recovery will be approximately double the recovery expected under the original solution gas drive mechanism. Wide (80-acre) spacing has enhanced the economics of the over-all field program by the elimination of more than $5,000,000 worth of unnecessary wells. INTRODUCTION The Haynesville Pettit Field was discovered in November, 1941, with the completion of T. L. James Co.'s Callie Akin No. 1, located in the W 1/2 of the NE 1/4 Section 27-23N-8W, Claiborne Parish, La., at an approximate depth of 5,300 ft. The center of the field is about two miles north and a mile west of the town of Haynesville, La. A total of 189 producing wells have been drilled on 14,500 acres. An additional nine dry holes were drilled. The Louisiana-Arkansas state line divides the field so that 34 wells are in Arkansas and 155 are in Louisiana. Governmental sections are divided equally to contain eight production units making 80-acre spacing where the sections are regular. Along the state line in Louisiana there is an irregular tier of sections, each of which contains approximately 456 acres. When divided equally into eight production units the spacing is 57 acres per well for these three and a fraction productive sections. All Haynesville Pettit wells are identified by their section number followed by their position in the section as determined by numbering the production units counterclockwise beginning in the upper right corner of the section. All of the producing wells in the field except two are unit-ized and operated by the Haynesville Operators Committee. These two wells are located in the extreme northern part of the field in Arkansas. Efforts to bring them into the Unit are being continued. The Pettit operators organized the Haynesville Operators Committee and the field became a unit operation May 1: 1944. GEOLOGY The Pettit is Lower Cretaceous in age and is defined as the uppermost porosity in the Sligo formation. The unitized area known as the Haynesville Pettit Field is composed of two separate zones of porosity approximately 40 ft apart and without connection between the two, except in wells. These zones are known as the Upper Pettit and the Lower Pettit. The Upper Pettit is separated into two sections throughout most of its area by a relatively thin but quite impervious shale streak. These are called the "A" and "B" sections of the Upper Pettit. All of these lenticular zones are composed of coquina limestone and a small percentage of normal oolites. The large

Jan 1, 1951

By System By John E. Owen, Walton J. Greer

The guard electrode system measures the resistivity of formations by employing a thin disk of current which is caused to flow perpendicular to the bore hole. The control of this current disk is obtained in a brute force manner through the use of relatively long equipotential electrodes above and below the measuring electrode. The log obtained from the system is free of "lag," "plateau," "shadow," "reflection" and other distortions evident on conventional logs. The proportionate contributions of the hole size and invaded zone resistivity to the apparent resistivity reading are reduced when the mud and filtrate resistivities are lower. Thus, the guard system favors the use of conductive muds. The mathematical development of the theory is given in an appendix. Equations are derived to evaluate the effects of mud resistivity, hole size, invaded zone resistivity and depth, and the true formation resistivity. Sample logs from several provinces are reproduced and compared with conventional electric logs to illsutrate the much greater detailed lithology that can be presented by the guard electrode system. INTRODUCTION With increased ability of those in the petroleum industry to analyze formation characteristics from electrical resistivity data, there has become apparent the need for more precise measures of that parameter. The measurement of the resistivity of a homogeneous and isotropic material can be made simply when the body of the material is infinite in all dimensions and the measuring electrodes can be placed within the body. In such a case, the current leaving an electrode follows a spherical distribution and the mathematical expression for the potential level at any distance from that electrode can readily be derived.'.' If it is considered that the active electrodes are within a bore hole filled with mud of a resistivity different from that of the formation. the current does not flow in a spherical pattern near the current source or sink, and the calculations of potential levels become more difficult. The additional consideration of a section of formation invaded by mud filtrates, and thus having resistivity different from either that of the mud, the adjacent formations or of the undisturbed formation, makes the mathematical problem extremely complex. Should the vertical dimensions of the formations be considered as finite. the problem becomes so complex as to preclude reasonable solution. Yet, even these considerations have not described adequately the conditions encountered in a large proportion of the wells to be studied. In efforts to evaluate the effects of the various conditions. combinations of twn, three. and four electrode logging con- figurations of the conventional types have been used. The resulting logs have left much to be desired in some provinces. It has become apparent that the use of such configurations will not result in adequate measurements being made, particularly in cases where the formation is composed of thin sections. If all the current of a resistivity measuring circuit is made to flow through the formation opposite the exploring electrode, many of the shortcomings of the conventional measuring system are eliminated. In the guard electrode method of electrical well logging to be discussed in this paper, the current is so controlled by causing it to flow in a thin disk normal to the axis of the logging tool. EARLY HISTORY The guard electrode method of electrical well logging in its early years was a joint development by the Geophysical Research Corp. and the Amerada Petroleum Corp. The method was first experimentally investigated by means of model studies. The results of these studies indicated that current focusing systems properly applied to electrical well logging

Jan 1, 1951

By R. D. Nelson, F. E. Bowman

Evidence has been found for a (010)a?(111)B[102]a /,11[341]/B crystallographic relationship between the monoclinic a and B phases of plutonium during the a?B transformation. The results of an X-ray diffraction study, where [010] fiber textured a samples were used in the absence of suitable single crystals indicate that the (OIO)a planes become (111)B planes upon transformation under near-equilibrium conditions. The transformation strain along the fiber axis, which was the [010] direction, was measured dila-tomekically; the measured 8.5 pct expansion compares favorably with the 8.44 pct expansion in the in-terplanar spacing represented by the (010)a?(111)B relationship. From plots of the atom positions in each of the related planes, a correspondence was deduced between the [102]a, direction and the [341]B direction. Further analysis of the two lattice structures in the light of this relationship revealed a rotation about the [102] direction of 1 deg 43 min and a slight shearing in this same direction of about 30 min. THIS paper discusses the (B crystal structure of plutonium and the orientation relationship existing between the monoclinic a and B phases during the a?ß transformation. The kinetics of the a?ß and (3 — a transformations have received extensive consideration, and because of the crystallographic complexity of these phases, the question of the mechanisms by which these transformations occur is especially intriguing. Nelson and Shyne1 evaluated the existing experimental evidence and concluded, from the indirect evidence available, that both the ß ? a and a ? ß transformations occur by a martensitic process. Their data reveal the anisotropic nature of these transformations which suggests the existence of specific crystallographic relationships between the parent and product phases. In this paper, we are concerned with the confirmation of the existence of such a relationship resulting from the a ? ß transformation and the derivation of the crystallographic details necessary to specify it. EXPERIMENTAL RESULTS X-ray diffraction and dilatometric data were obtained from samples of a plutonium having a [010] fiber texture. These cylindrical specimens, approximately 1 cm in diam, were prepared by transforming the ß phase to a under the influence of a uniaxially applied compressive load.' The [0l0] direction is parallel to the direction of applied stress; it is also perpendicular to the (010) planes. This correspondence between the plane normal and the direction having the same indices is, in the monoclinic a plutonium structure, restricted solely to this (010)[010] combination. Such a specimen was mounted in an evacuated, elevated temperature specimen holder on an X-ray dif-fractometer so that the diffracting surface was perpendicular to the fiber axis. The a diffraction pattern, Fig. 1, taken at about 115ºC, revealed the predominance of the (020) reflection. This monoclinic, P 21/rn space group yields no (0k0) reflections when k is odd. The temperature was raised slowly to 160°C to effect the complete transformation to the phase; then it was lowered to 120°C so that a diffraction pattern of the ß could be obtained near the a = ß equilibrium temperature for direct comparison with the a at the same temperature. The (3 diffraction pattern, Fig. 2, obtained under these conditions showed a (222) reflection relatively much more intense than in the random pattern. The other reflections appearing with sig-

Jan 1, 1970

By L. Yarborough, L. R. Smith

This paper presents results of a laboratory study of retrograde condensate recovery by revaporization into dry injection gas. Flow tests were performed in 10.6-ft long sand packs at 100F and 1,500 psi. In three runs methane revaporized the liquid from a n-pentane-methane mixture in the presence of immobile water. TWO of these tests were water-wet, and the third was totally oil-wet. In the three runs n-pentane recovery was complete after 2.5 hydrocarbon PV of injection. There was no significant performance difference between the two wettability extremes. In a fourth experiment, a methane-hydrogen sulfide mixture revaporized a synthetic light, sour condensate. No water saturation was present. Equilibrium compositions and volumetric data were obtained for the four-component condensate. The heavy component, n-beptane, was removed after 6 PV production. Comparison of the effluent fluid compositions with known equilibrium data shows that the flowing fluid was equilibrium vapor and that the mixing zone between equilibrium vapor and dry injection gas was short. Data indicated that complete recovery of retrograde liquid occurred after it was contacted by a sufficient quantity of dry gas. INTRODUCTION When pressure declines below the fluid dew point in a gas condensate reservoir, a liquid phase forms. In this process, referred to as retrograde condensation, the quantity of liquid formed is frequently small enough that the liquid is not a flowing phase. To prevent loss of valuable retrograde liquids, the process of dry gas cycling has been employed for several years as a more or less standard practice. In this procedure the reservoir pressure is maintained above the fluid dew point so that the liquid components may be produced as vapor and then separated at the surface. Although full pressure maintenance by gas cycling seems ideal in terms of preventing liquids loss, several factors can reduce the atuactiveness of such an operation. From a study of a condensate reservoir in Alberta, Canada, Havlena et a1.1 con-cluded that cycling under conditions of declining pressure leads to economic advantages and to a high recovery of hydrocarbon liquids. This study considered effects of volumetric sweep efficiency, retrograde behavior of the original wet gas and revaporization characteristics of the retrograde liquid when contacted by dry gas. The first major work concerning revaporization of liquid in a gas condensate system is that of Standing et a1.2 Calculations based upon the PVT behavior of a recombined gas condensate fluid indicated that all retrograde liquid can be recovered if it is contacted by a sufficient quantity of dry gas. The paper considered the effect of variable permeability upon the recovery of retrograde liquid. Standing et al. concluded that recovery of heavier components in the retrograde liquid is greatest if reservoir pressure is allowed to decline below the dew point prior to dry gas injection. Since the work of Standing et al., several laboratory studies have been reported which show that recovery of hydrocarbon liquids by vaporization into dry injected gas can contribute to increased recovery above that obtained by ordinary production practices. Vaporization from retrograde condensate,3 conventional oil4-7 and volatile oil8 reservoirs has been considered. There is little work that deals with revaporization recovery from condensate reservoirs. This study demonstrates that vapor-liquid equilibrium exists when a dry gas is injected into a porous medium containing retrograde condensate; investigates the effect of wettability on revaporization of retrograde condensate; and provides an indication of the amount of dry gas necessary to

Jan 1, 1969

By D. I. Bardos, Paul A. Beck

The 1100°c isothermal, sections of the V-Fe-Si, V-Co-Si, and V-Ni-Si systems were studied at silicon contents between 0 and 40 at. pct. The single-phase fields in the 30 and 50 at. pct Mn sections of the 1100°C tetrahedron of the V-'Wn-Fe-Si system were also determined. The direction of extension of the elongated O, R, D, and a-Mn Phase fields suggests that the stability of these phases is determined largely by the electron concentration. The peculiar shape of the above ternary a phase fields, as well as of the a phase fields in the V-;Mn-Si and Cr-MTZ-Si systems is accounted for on the assumption that in manganese-(iron-, coball-, nickel-) rich alloys silicon atoms do not exclude d electrons , while in alloys low in the above components they do. This assumption also leads to the expected electronconcentrations for q and ß-Mn phases formed by transition metals with aluminurn. In earlier work it was shown that in ternary alloy systems of transition elements the a a and certain other phases with complex structure, such as the p and R phases,3 form elongated phase fields extending in a direction corresponding to a constant electron concentration. Recently similar behavior was observed in manganese-rich ternary ß-Mn solid solutions with another transition element and with silicon, germanium, or tin,4 confirming earlier indications3 that ß-Mn is also an electron phase. The alloying behavior of silicon in these manganese-rich alloys sug- gested that the four outside electrons of silicon participate in the bonding and that the predominantly d-like bonding electrons are not excluded from the silicon sites. Presumably, some of the normally unoccupied 3d states associated with the silicon atoms are in these alloys lowered to the Fermi level;4 thus silicon behaves as if it, too, were a transition element. The manganese-rich boundary of the a phase in the V-Mn-Si system,4 as well as in the Cr-Mn-Si sys-tem,4,5 extends approximately parallel to the ß-Mn phase boundary, corresponding to the transition ele-mentlike behavior of silicon described above. However, at lower manganese contents (i.e., in the high-vanadium or -chromium region) the a phase field in both ternary systems mentioned extends in a direction roughly perpendicular to that of its manganese-rich boundary, a phenomenon that is apparently inconsistent with the behavior of silicon in the manganese-rich alloys. A similar, although somewhat less pronounced, extension of the a phase occurs also in the high-vanadium (low-iron) region of the V-Fe-Si system at 1175C, but reportedly not in the V-Co-Si or V-Ni-Si systems at the same temperature.5 The present work was undertaken to investigate in more detail the extension of the a phase (as well as of other electron phases that may be present) in the last three systems and to elucidate this phenomenon, which has not been satisfactorily explained previously. EXPERIMENTAL PROCEDURES Most of the alloys were melted in an arc furnace, using a water-cooled copper crucible under helium atmosphere. The transition metals were of better than 99.9 pct purity and the silicon used was 99.98 pct pure. Alloys containing less than 20 pct V were induction-melted in recrystallized alumina crucibles under argon atmosphere.

Jan 1, 1967

"In 1899 the American Refining and Smelting Company obtained control of the East Helena Smelter, and have added improvements from time to time.The plant is four miles east of Helena, on the Northern Pacific and Great Northern railroads, with hourly street car service from Helena.Electric power is obtained from Canyon Ferry dam, twelve miles east on the Missouri river, and about 800 h-p. is used in the blowing engines, crushing machinery, cranes and locomotives.Besides the Montana ores convenient to the above railroads, a large part of the ore supply comes from the Coeur d'Alene district, Idaho, and is mainly lead ore and concentrates.A modern automatic sampling mill, with Vezin samplers and a capacity of 50 tons per hour, was completed in 1912.Three blast furnaces, each 48 inches by 136 inches, are now in continuous operation, and the monthly production of silver-lead bullion is six thousand tons.A part of the ore roasting is done in Godfrey furnaces, in connection with the Huntington-Heberlein process, 12 pots being in use, with a capacity of 300 tons per day.Four Dwight-Lloyd sintering furnaces, each 42 inches by 264 inches, and a smaller experimental machine, with a combined capacity of 440 tons per day, are in steady operation, and are successfully roasting ore as well as sintering flue dust. These machines are in great favor and results are being carefully watched.Three bag houses are used in connection with the 1,800 brick flue chamber, and each bag house contains 1,260 cotton bags, each 18 inches in diameter by 30 feet long, suspended on vertical roads. The product saved by the bags contains about 50 per cent lead and is retreated in the blast furnace after sintering.About 450 men are employed."

Jan 1, 1913

By Wesley G. Josephson

THE MINING PROPERTY of the Argonaut Mining Co., Jackson, Calif., is one of the oldest on the Mother Lode. A vein outcropping on a hill in this section could not long elude the eye of the forty-niner, so it was first discovered in 1850. From that time until 1893 the Pioneer mine, as it was then called, limped along under various poorly equipped and financed operators who tried tapping it by trenching and tunneling. Then the Argonaut Mining Co. took over the property and sank the present 65° inclined shaft in the hanging wall of the vein. The mine workings have now reached the 6000-ft. level, which is 5283 ft. vertically below the surface, or just 3 ft. over a mile. The total production of the mine is uncertain, because of lack of early records, but from 1893 to 1932 it is known to have produced in excess of $17,000,000.

Jan 1, 1932

By H. S. Cannon, F. N. Rhines

The application of a static load to a copper powder compact during sintering at an elevated temperature accelerates the rate of sintering in such a way that a given load induces the same proportional increase in rate for all times of sintering. It is shown that sintering under a load is like creep under a fixed load in that the stress required to accomplish a given degree of densification is proportional to the logarithm of the sintering time. VIRTUALLY all of the theories of sintering that have been put forward within recent years have contained the assumption that the chief driving force of the process is the surface tension resident in the exposed surfaces and internal pores of the compact, or powder mass. An externally applied load might be expected to provide a somewhat equivalent driving force for sintering. It is known that the application of a compressive load, during sintering, hastens densification, but it is by no means clear whether sintering under the influence of surface tension alone and sintering under an applied load are fundamentally similar processes. The present study was undertaken in an effort to obtain an answer to this question and with the hope that the answer may contribute to an understanding of the mechanism of sintering. It has been found that there is a close relationship between sintering and creep processes. Copper powder compacts were sintered in hydrogen at 1000 °C under dead loads of 0 to 165 psi and the progress of sintering was observed by means of density measurements. Using a commercial reduced oxide copper powder, see Table I, cylindrical compacts Yz in. x x in. high were made at a pressure of 12,500 psi. For sintering, these were placed in a cylindrical graphite container into which they fitted snugly. A compressive axial load was applied to the compact through a graphite rod of similar diameter, which rested upon the upper end face of the compact; iron weights, in suitable amount, were placed upon the graphite rod to provide the load. This assembly was encased in a vertical silica tube within a resistance-type furnace capable of maintaining a substantially constant temperature within the working zone. After various predetermined times at temperature, the samples were removed from the furnace and their density was measured by conventional means. The heating-up and cooling-down times have been included in the computed sintering time, using the assumption that the sintering rate doubles for each increase of 10 °C in temperature. The experimental results are presented in Table 11. Upon metallographic examination of the specimens, it was found that there was no apparent change in the shape of the pores as a result of loading, i.e, no flattening, Fig. 1. Substantial contraction away from the container walls was observed in all samples sintered with loads of 10.5 psi and less.

Jan 1, 1952

By G. W. Lester, T. J. Nowak

The paper presents a practical method of utilizing pressure fall-off data obtained when a water injection well is shut in for determination of: (I) the static reservoir pressure, (2) the potential water injective capacity (md-ft) of the formation, and (3) the formation damage (skin effect) surrounding the wellbore. In the development of the method, equations are presented which give The theoretical background for predicting the behavior of water injection wells. Certain physical factors which limit the application of the method are discussed. The procedure and the relevant precautions in obtaining the data are discussed. A sample analysis and computation from an actual pressure fall-off curve is illustrated. Fintrlly, general characteristics of pressure fall-off curve! obtained in several reservoirs are presented. INTRODUCTIO N Theoretically, in an injection well the flow of water into the formation will continue as long as the sand-face pressure is greater than the reservoir pressure. However, in practice, engineers have observed that upon stopping injection and opening the wellhead to atmospheric pressure, some wells backflow water for time intervals ranging from several seconds to several hours although the sand-face pressure, as calculated from the hydrostatic head, is considerably greater than the static reservoir pressure. Further, field observations indicated that upon shutting in a water input well, the wellhead pressure does not drop off immediately, but a pressure decline occurs lasting from several seconds to several days. These observations make it evident that when an input well is shut in, a residual pressure lingers in the vicinity of the wellbore which is greater than the average reservoir pressure. This residual pressure declines first rapidly, then more slowly, to the static reservoir pressure: therefore, it is called transient back-pressure or pressure fall-off. The first step in investigating the mechanism of pressure fall-off is to establish what general conditions are necessary for its occurrence, and to this end, Dickey and Andresen1 have presented a qualitative explanation describing the mechanism. They point out that the formation pressure gradient in the vicinity of the well does not disappear immediately when the input well is shut in, as if the system were filled with a totally incompressible fluid, but it is maintained by the expansion of the compressible fluids and by the elasticity of the formation. In such a compressible system the decrease in pressure is possible only to the extent that the water front continues to advance until the pressure is equalized. The principal aim of this paper is three-fold; namely. (1) to present a theoretical quantitative analysis of pressure fall-off data, (2) to present an application of the developed theory to field data, and (3) to discuss the general characteristics of actual pressure fall-off curves. Under (I), theoretical equations dealing with such factors as compressibility of the fluid-reservoir system, mobility of the fluids and certain physical restrictions that

Jan 1, 1956

By John Chipman, Helen Towers

DEVELOPMENT of a simple radioactive tracer technique for measurement of the diffusion coefficient of calcium ion in liquid slag has already been reported. The investigation was of a preliminary nature designed to explore the possibilities of using radioactive isotopes and to establish a method, and no great accuracy was claimed for the results. It was shown, however, that Ca15 could be used successfully, and the values obtained for the diffusion coefficient appeared to be of the right order of magnitude. However, it was considered that a better technique could be devised for carrying out the diffusion. The experiments were, therefore, continued to find a more accurate method, to check the calcium results, and to extend the investigation to include measurements of the diffusion coefficient of silicon in the same slag. There were two flaws in the original technique. Convection was the cause of too many failures, and the interface between the two slags in the diffusion cell was curved rather than plane, probably due to a surface tension effect caused by the addition of the tracer Ca45 in the form of chloride. Two methods of overcoming these defects were tried. Since it was planned to study diffusion of the short-lived isotope Si"' also, the development of methods was restricted to those which gave promise of being reasonably rapid. Method 1—The principle was identical to that previously used with respect to the diffusion conditions, but there were three differences in technique. Temperature control was more rigid, the tracer was added to the slag as Ca45O rather than the chloride and, finally, an effort was made to translate to high temperatures the elegant method developed by Cohen and BruinV or bringing together the two liquid layers and beginning the diffusion. A master slag was melted in graphite, ground to a fine powder, and analyzed (38.5 pct Ca0-20.9 pct Al2O3-40.5 pct SiO2). The tracer was received as Ca45C12 in an aqueous solution of CaC12 + HC1. From this, calcium oxalate was precipitated, ignited to calcium oxide, and added as such to the slag to give an activity of approximately 5 µc per g. The mixture was then melted into the form of a cylinder 3/16 in. diam and about 1 in. long. A solution identical to the tracer solution without Ca45 was given exactly the same treatment. The resulting Ca40O was mixed with that slag which was to form the tracer-free half of the diffusion cell, and this was likewise melted into a cylinder of the same size. Slag cylinders, two with and two without Ca15, were set in graphite blocks as shown in Fig. 1, and the crucible was lowered into position in the fur-

Jan 1, 1958

By T. A. Klinefelter

Lightweight concrete aggregates are materials weighing less than the usual aggregates of sand, gravel, and crushed rock. Concretes made with sand and gravel or crushed rock weigh 145 to 150 lb per cu ft, compared with 50 to 90 lb per cu ft for concretes made with lightweight aggregate. The ultra-lightweight concretes weigh much less than 50 lb per cu ft. Lightweight aggregates may be natural or manufactured materials, or byproducts from other commercial operations. Natural materials include pumice and pumicite, tuffs, breccia, scoria, diatomite, and vegetable products, such as peat, straw, and sawdust. Manufactured materials include expanded perlite, vermiculite, slag, clay, shale, and slate. Byproducts include cinders, aircooled slags, and coke breeze. Concretes made with lightweight aggregate were used first in construction of commercial buildings, later in homes. Present usage is general in multistory and other building construction, such as bridge decks, barges, jet-plane runways, piers and other structures. The industry has grown remarkably in the last decade. General Considerations The particular use to which the concrete may be put determines the importance of the various properties of the aggregates employed. Any given type of aggregate, however, should be reasonably uniform in composition and properties. It should be suitably graded and maintain proper weights, insulation values, and adequate strength to prevent breakdowns in mixing. It should bond properly with the cement, be inert to chemical reactions with cement and steel, and resist weathering, moisture, insects, and fungi. Some properties of any given type of lightweight aggregate from different suppliers may vary considerably because of differences in the source of raw material and the method of treatment. This statement applies particularly to expanded clays, shales and slates. All lightweight concretes have higher absorption of moisture and lower thermal conductivity, lower compressive strength, as well as lower unit weight as compared with standard concretes made with sand, gravel or crushed rock. Excepting cinders, the cost of lightweight aggregates is usually higher. Grading and unit weight requirements are given in ASTM standards: C 330-53T, Lightweight Aggregates for Structural Concrete; C 331-53T, Lightweight Aggregates for Concrete Masonry Units; C 332-54T, Lightweight Aggregates for Insulating Concrete. The production of masonry units shows the growth of the use and types of lightweight aggregates. In 1947 the total number of lightweight block was 460,000,000 units in 8 by 8 by 16-in. equivalents. By 1954 this had increased to 950,000,000 units. Of the 1954 production, 27 pct was of manufactured types, 43 pct of cinders, and 30 pct of remaining types. Raw Materials Used as Lightweight Aggregates It was stated above that a variety of products both natural and manufactured are used as lightweight aggregates. It is easy to understand that a bulky material of low unit value cannot be transported far and still remain a low cost product. Hence the product used in a particular market depends upon the availability of the possible raw materials. Thus it is

Jan 1, 1960

By Carlton Beal

This paper presents useful charts for conversion of various viscosimeter units into centipoises and graphically summarizes published investigations of the viscosity of air, water and natural gas at high temperatures and pressures. Where possible, charts and correlations were constructed to cover a range of temperature (60°F. to 300°F.) and pressure (14.7 lb. per sq. in. abs. to 8000 lb. per sq. in. gauge) encountered in oil fields. Correlation charts, for the purpose of predicting crude oil viscosity and solubility behavior at oil field temperatures and pressures, were constructed from an analysis and correlation of 1332 viscosity and solubility observations from 953 crude oil samples taken from 747 oil fields. Of these fields, 501 are in the United States, including 75 in California. Of the 1332 observations, 1215 were viscosity values, including 786 of gas-free crude oil, 351 of oil saturated with gas, and 78 under-saturated with gas at pressures above the bubble point. Results show that crude oil viscosity at various reservoir conditions can be predicted with average deviations varying from 24.2 per cent for gas-free crude oil to as little as 2.7 per cent for undersaturated crude oil "above the bubble point." The solubility of crude oil may be predicted from oil gravity and saturation pressure with an average deviation of 22.0 per cent from observed values. In conclusion, it is shown that the viscosity of a gas and gas-saturated crude oil may be predicted within the accuracy of most reservoir computations. Viscosity is a measure of flow resistance; common units are in centipoises (cp.). The object of this report is to present conversion charts and simplified 'correlation charts showing the viscosity behavior of air, water, gas and crude oil and gas-saturated crude oil under oil field temperatures and pressures, which have been known to be as high as 300°F. and 8000 Ib. per sq. in. gauge under subsurface conditions. The viscosity of a liquid or gas is important because it is a measure of its fluidity, or its ability to flow through pipe lines or oil sands. Viscosity of air has become important because it is being used in secondaryl,2 recovery projects. The viscosity of natural gas and water at reservoir conditions is useful because they are almost universally associated and produced with crude oil. The viscosity of gas-saturated crude oil at reservoir pressures and tem peratures is of particular value in making estimates of oil reserves3 and rate of oil recovery from flush pools when production decline data are limited. Instruments Used to MeasuRe Viscosity There are many types of viscosimeters,4 and the instruments most commonly used to measure the atmospheric viscosity of liquids at moderate temperatures and their practical working ranges have been deScribed5,6 in detail. Fig. I and Fig. 2 are viscosity conversion charts which have

Jan 1, 1946

By Carlton Beal

This paper presents useful charts for conversion of various viscosimeter units into centipoises and graphically summarizes published investigations of the viscosity of air, water and natural gas at high temperatures and pressures. Where possible, charts and correlations were constructed to cover a range of temperature (60°F. to 300°F.) and pressure (14.7 lb. per sq. in. abs. to 8000 lb. per sq. in. gauge) encountered in oil fields. Correlation charts, for the purpose of predicting crude oil viscosity and solubility behavior at oil field temperatures and pressures, were constructed from an analysis and correlation of 1332 viscosity and solubility observations from 953 crude oil samples taken from 747 oil fields. Of these fields, 501 are in the United States, including 75 in California. Of the 1332 observations, 1215 were viscosity values, including 786 of gas-free crude oil, 351 of oil saturated with gas, and 78 under-saturated with gas at pressures above the bubble point. Results show that crude oil viscosity at various reservoir conditions can be predicted with average deviations varying from 24.2 per cent for gas-free crude oil to as little as 2.7 per cent for undersaturated crude oil "above the bubble point." The solubility of crude oil may be predicted from oil gravity and saturation pressure with an average deviation of 22.0 per cent from observed values. In conclusion, it is shown that the viscosity of a gas and gas-saturated crude oil may be predicted within the accuracy of most reservoir computations. Viscosity is a measure of flow resistance; common units are in centipoises (cp.). The object of this report is to present conversion charts and simplified 'correlation charts showing the viscosity behavior of air, water, gas and crude oil and gas-saturated crude oil under oil field temperatures and pressures, which have been known to be as high as 300°F. and 8000 Ib. per sq. in. gauge under subsurface conditions. The viscosity of a liquid or gas is important because it is a measure of its fluidity, or its ability to flow through pipe lines or oil sands. Viscosity of air has become important because it is being used in secondaryl,2 recovery projects. The viscosity of natural gas and water at reservoir conditions is useful because they are almost universally associated and produced with crude oil. The viscosity of gas-saturated crude oil at reservoir pressures and tem peratures is of particular value in making estimates of oil reserves3 and rate of oil recovery from flush pools when production decline data are limited. Instruments Used to MeasuRe Viscosity There are many types of viscosimeters,4 and the instruments most commonly used to measure the atmospheric viscosity of liquids at moderate temperatures and their practical working ranges have been deScribed5,6 in detail. Fig. I and Fig. 2 are viscosity conversion charts which have

Jan 1, 1946

By R. M. Waterstrat

The phases occurring in the V-Mn system were studied by means of X-yay diffraction and metallo-paphic techniques, using are-melted alloy specimens annealed in the temperature range 800° to 1150°C and quenched. The bcc solid solution extends at 1250°C all the way from vanadium to 6-manganese. Below 1050°C the a-phase is formed, and the terminal a-manganese phase is stabilized up to about 900°C by vanadium in solid solution. IN the only previous general survey of the V-Mn system Cornelius, Bungardt and Schiedtl reported the existence of three intermediate phases corresponding to the approximate compositions VMn,, VMn, and V5Mn. The phase VMn8 has recently been identified as a o phase2 but the alloy VMn was found to have a bcc structure2 corresponding apparently to the vanadium solid solution rather than to the large cubic unit cell reported by Cornelius et al. 1 Subsequent work by Rostoker and Yamamoto3 has shown that the vanadium-base bcc solid solution extends to at least 15 pct Mn at 900°C. An alloy corresponding to the composition VMn, was examined by Elliott,4 who reported that the as-cast sample as well as samples annealed at 1200o and 1300°C had bcc structures, but that annealing at 1000°, 800") and 600°C produced two phases. One of these phases was apparently the bcc solid solution and the other resembled the o phase structure. Hellawell and Hume-Rothery5 established the phase relationships in manganese-rich alloys above 1000°C, and showed that the o phase in this system is replaced by the 6 Mn (bcc) solid solution at temperatures above 1050°C. These results suggest that a continuous bcc solid solution may exist above 1050°C between vanadium and 6 Mn. The present investigation was undertaken in order to develop more complete information in regard to this system. EXPERIMENTAL METHODS The alloys used in the present work were prepared by arc-melting electrolytic manganese having a minimum purity of 99.9 pct and vanadium lumps with a purity of 99.7 pct. The major impurities present in these metals were carbon, nitrogen, and oxygen and this would account for the small percentage of nonmetallic inclusions observed metal-lographically. The arc-melting was at first performed under a helium atmosphere and it was necessary to keep the melting times as short as possible in order to minimize the loss of manganese by vaporization. It was later found that the evaporation of manganese was considerably reduced when the melting was done under argon atmosphere. The final composition of each alloy was calculated by assuming that the total weight loss during melting was due to evaporation of manganese. Compositions which were calculated in this manner agreed reasonably well with the results of chemical analysis, as shown in Table I. Spectrographic analysis revealed the presence of contamination by tungsten, but in no case was the percentage of tungsten greater then 0.4 at. pct. The specimens were in each case broken in half and the fractured section was examined visually and microscopically for evidence of inhomogeneity. Each specimen was homogenized at temperatures near l100°C, as shown in Table I. After this treatment most specimens consisted of large columnar grains of the bcc vanadium solid solution. The etchant used in most of the metallographic work consisted of 20 pct nitric acid, 20 pct hydro-flouric acid, and 60 pct glycerine. It was found that this etchant would clearly delineate the phases present in these alloys although it does not produce any striking contrast between the phases. For certain manganese-rich alloys, a 1 pct aqueous solution of nitric acid was used. This etchant gave a brown color to the a-manganese phase, whereas the o phase was virtually unattacked and appeared very light as shown in Fig. 1. The etchants used by Cornelius et a1.l were found to produce spurious effects in some of these alloys. In particular, the vanadium-rich alloys etched in hot sulfuric acid often appeared to consist of two phases when both X-ray diffraction and etching with the glycerine-acid mixture indicated the presence of single phase bcc solid solution. A few percent of what appears to be an oxide or nitride phase was found at the grain boundaries and in the interior of the grains, especially in the vanadium-rich alloys. All alloys were annealed in sealed silica tubes containing 1 atm of pure argon and these tubes were then quenched in cold water. Although some manganese loss occurred during annealing, the loss seemed to be confined to the surface of the speci-

Jan 1, 1962

By S. D. Baumer, P. M. Hulme

IN the late thirties, the National Carbide Co. cooperated with C. E. Wood, of the U. S. Bureau of Mines, in his investigation of the relative merits of various desulphurizers, including soda ash, caustic soda, and calcium carbide. Laboratory tests showed that carbide, when it could be made to react, is an excellent desulphurizing agent for molten iron. Sulphur content can be driven to lower levels and higher extractions obtained with carbide than with actionsany of the more common reagents. Wood's results1 are shown in Table I. Unfortunately, as the Handbook of Cupola Operation puts it, the chemical fact that carbide is a good desulphurizer was of only academic interest because it was found to be extremely difficult to devise a practical means to make it react with molten iron. Calcium carbide is formed in the electric furnace at 4000°F and above, and its softening point is probably at least 500 °F above the usual working temperatures encountered in iron and steel practice. Consequently, carbide does not form a true slag but floats as a dry powder on top of the metal and only a very small portion of it ever comes in actual contact with the iron. Stirring with a rabble, or pouring the metal over the carbide, increases the efficiency only slightly. Extractions of 20 to 30 pct can be obtained in this manner, but conventional soda slag treatment can do better than this and do it more cheaply. All attempts to lower the melting point of carbide in order to obtain a reactive, liquid slag have so far proved fruitless. Directly under the arc in a metallurgical electric furnace, carbide becomes highly reactive. Excellent sulphur removal can be obtained without any slag other than a thin layer of carbide." imilarly, good results are obtained by adding small amounts of carbide to the finishing slag in double-slag arc furnace practice. To react a liquid with a solid, it is axiomatic that the liquid has to wet the solid before anything can happen. If the solid is heavier than the liquid, the problem is easy, but it becomes more difficult when the solid is much lighter than the liquid, as in the case of carbide and liquid iron. Wood recognized this problem and solved it in a unique fashion. The results shown in Table I were obtained by spinning the carbide beneath the surface of the molten iron by means of a refractory centrifuge. This technique allowed each particle of the finely divided carbide to come into intimate contact with the metal and to be wetted thereby. Wood's centrifuge technique was successful in the laboratory where it achieved excellent and consistent results. Some attempts were made to expand this method to commercial practice, but serious difficulty was encountered in obtaining a refractory centrifuge head that would be economically feasible. About this time the war intervened and the project lay dormant for several years. In 1944, it was revived. It was suggested that the carbide could be blown into the metal with a carrier gas in an attempt to eliminate the necessity for the expensive and brittle centrifuge. The idea was first tried out in a fairly large ladle of iron using natural gas as the carrier. Considerable sulphur was removed, but it was quite obvious that the use of natural gas was not practical. Attempts then were made to blow carbide into molten iron using, in turn, nitrogen, argon, carbon dioxide, air, and oxygen. The latter two gases proved unsatisfactory. Calcium evidently prefers oxygen to sulphur because in the tests calcium oxide and carbon dioxide were produced, the sulphur still being untouched in the iron. Nitrogen, argon, and carbon dioxide gave much better results, although the efficiencies and extractions were erratic, and only a few isolated tests approached the results obtained by Wood. Table II shows typical results obtained with these gases. The sulphur removals were interesting, sometimes even encouraging, but it is evident that such erratic behavior could not be tolerated in commercial practice. A number of different types of equipment, such as sand blasting machines, refractory guns, and the like can used to blow the solid into the metal. All types required relatively large quantities of gas in order to maintain the flow of solid carbide through the system and into the metal. It was observed that the bubbles of gas breaking through the surface of the metal contained quantities of unreacted carbide. The liquid metal never came in contact with these particles and if it cannot wet them it cannot react with them. The initial work had shown that carbide had great possibilities as a desulphurizer. In practice

Jan 1, 1952

By N. J. Grant, C. C. Wang

The Ti-Cr-O ternary system has been studied in detail near the titanium-rich corner within the limits of 10 wt pct 0, and 20 wt pct Cr. Studies were extended, but not in detail, to the region beyond 25 wt pct 0, (50 atomic pct) and 62 wt pct Cr (60 atomic pct). Four isothermal sections at 1400°, 1200°, 1000°, and 800°C are presented as well as two vertical sections at 1 and 2 wt pct 02. DURING the last decade much interest has been shown in the development of high strength titanium alloys for high temperature and corrosion resistant applications. Extensive research is being carried out at present, as the current literature indicates, in order to study the properties of titanium and to develop improved alloys. Two of the important alloying elements in commercial titanium alloys are chromium and oxygen and it would be desirable to know their combined influence upon titanium. For this purpose the present work was carried out to investigate the titanium-rich corner of the ternary system TiICr-0. The binary systems Ti-Cr and Ti-0 have been published recently. The Ti-Cr system was studied by several investigators " and their results are in close agreement. The eutectoid decomposition of the B phase has been shown to be extremely sluggish. TiCr, was the only intermetallic compound found in this binary system and was formed at 1350°C by a transformation from the p phase. TiCr? was established as the cubic C 15 (MgCu,) type of structure with 24 atoms per unit cell and was designated as the y phase. This terminology will be adopted in the present work. There was disagreement about the actual composition of this compound among the several investigators, although it is evident from their data that the compound probably has a solubility range of about 2 to 3 pct and is in the vicinity of 65 pct Cr. It has been indicated recently that a high temperature modification of this y phase (TiCr,) existed at a temperature above 1300°C." ' This high temperature modification was identified as a hexagonal C 14 (MgZn,) type of structure with 12 atoms per unit cell. The exact transformation temperature from the high temperature phase to the low temperature phase has not been established. A considerable hysteresis was observed and, due to the sluggishness of this transformation, the high temperature phase often co-existed with the low temperature phase at temperatures below 1300°C. A preliminary study of several Ti-0 compounds and the Ti-0 system had been carried out by Ehr-1ich."-"' The most complete binary Ti-0 system was the one reported recently by Bumps, Kessler, and Hansen." The first intermediate phase found in the system was the 8 phase which formed by a peritec-toid reaction of the phases a and Ti0 at temperatures below 925 °C. This reaction is extremely sluggish. The structure of this 8 phase was tentatively identified by these authors as being tetragonal and the lattice constants were found as c,, - 6.645A, a,, = 5.333A and c/a = 1.246A. Experimental Procedure The raw materials used for this investigation were TiO,, electrolytic chromium, iodide titanium, and sponge titanium. The TiO, was in the form of powder of chemically pure grade (99.8 pct pure). The chemical analysis of the electrolytic chromium was: 0, 0.50 pct; Fe, 0.07; Cu, N, and C, 0.01; and Pb, 0.001. The oxygen in the chromium was calculated as part of the final oxygen content of the alloys. The alloys were prepared by the cold crucible method using a tungsten arc. The entire system was evacuated and flushed with purified helium three times and then filled with helium. Each alloy was melted, turned over, and remelted at least four times to insure homogeneity. The total melting time was generally from 6 to 10 min. A master alloy of 25 pct 0,-75 pct Ti was prepared to facilitate alloying by melting compacts of TiOl powder with either iodide or sponge titanium, yielding the compound TiO. It was found necessary to bake the TiO, powder compact at about 150°C to remove adsorbed moisture. This was done to prevent the disintegration and spattering of the compact when the arc was struck. TiO, powder dissolved quite readily into the melt and no other trouble was encountered.

Jan 1, 1955

By E. H. Crabtree, T. G. Chapman, V. W. Winters

This paper traces the experimental and pilot plant work completed by the authors since 1939 including the various methods which have been developed in applying coarse activated carbon to cyanidation. The methods and results developed by the authors in desorbing gold and silver from carbons are given and the possibilities for the re-use of the desorbed carbons are discussed.

Jan 2, 1950

By John A. Church

AT a time when the treatment of gold and silver ores by fusion, in opposition to the mill-process, is attracting so much attention in this country, it may be useful to consider what is done in a well-conducted foreign work. For this purpose I will ask the reader to accompany me to Lend, in Austria, a small but thoroughly organized

Jan 1, 1873