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By R. Floyd Farris

A method is presented for determining minimum waiting-on-cement time, which takes into account the differences that exist between types and brands of cements and such individual well conditions as depth, temperature, and pressure. The basis for the method was determined by laboratory tests. Being a laboratory development, several steps were required to prove its merit. The first step consisted of laboratory tests designed to determine the minimum cement strength required in wells. Basis was found for setting a minimum value of 8 Ib. per sq. in. tensile strength. Next, it was shown by laboratory tests that the time to 8 Ib. per sq. in. tensile strength may be expressed as a function of consistometer stirring time to loo "poises," the approximate relation being "the time to 8 Ib. per sq. in. tensile strength equals the time to I00 'poises' times three." Next, it was shown that the time of maximum temperature development in cement slurries, due to heat of hydration, is also related to consistometer stirring time to loo poises, but only by a factor of approximately two. It was shown also that the shut-in casing pressure will build up after cement is placed and register a maximum pressure at approximately the same time the slurry down the hole attains maximum temperature. From this and the relationships listed above, the general rule was established that minimum waiting-on-cement time (time to 8 Ib. per sq. in.) after casing cement jobs in any well is equal to the time when the shut-in casing pressure reaches a maximum, as measured from the initial mixing of cement, times a factor of 1.5. Cement plugs drilled in the field at the time prescribed by this formula were found to drill "firm to hard," thus confirming the laboratory tests. These tests prove that many of the present regulations for waiting on cement require a longer time than is absolutely necessary. Use of the method herein proposed offers the possibility of a saving of $1200 per well. Introduction The length of time allowed for cement to set after casing is determined either by state-wide rules, field rules, or self-imposed rules written into drilling contracts. In general, the time is dictated by experience and common practice. However, owing to differences in opinion and in experience of the various groups involved, waiting-on-cement time often varies from one area to the next. For example, an operator in an area where no rules exist may drill out of surface pipe at 24 to 36 hr., while another operator in another area may wait 48 hr. or more to comply with state or field rules, although the depth of the well, hole size, type of cement, and other data are identical. An even greater difference in practices will be found by making similar comparisons with respect to oil-string cement jobs. Differences in waiting-on-cement times of 36 to 48 hr. are common. Further complicating the picture is the rather common practice of allowing more waiting time for cement to set at the greater depths than is allowed at the shallow depths. This practice has existed for years in spite of the common knowl-edge1,2,3 that the temperature of the earth at the usual setting depths of surface

Jan 1, 1946

By Spencer S. Shannon

The lanthanide elements from lanthanum (atomic number 57) to lutetium (71) plus yttrium (39) are called the rare-earth elements; scandium (21) is chemically similar to yttrium and the lanthanides, but differs in occurrence. The rare-earth metals were divided into three categories by the chemist, Berzelius, in the early 1800s; however, modern usage defines only two groups. The cerium group is named after the most abundant -element and comprises lanthanum (57), cerium (58), praseodymium (59), neodymium (60), promethium (61), samarium (62), europium (63), and gadolinium (64). Traces of natural promethium were discovered in apatite in Finland (Erametsa, 1965). The yttrium group, also named after its most abundant representative, comprises terbium (65), dysprosium (66), holmium (67), erbium (68), thulium (69), ytterbium (70), and lutetium (71). Yttrium most closely resembles holmium in chemical properties, and occurs most commonly with the heavy lanthanides. The rare-earth minerals may be divided into cerium-group, yttrium-group, or mixed-group classes. A number of rare-earth minerals contain thorium and uranium, but these are variable in content and are not essential to the composition of the minerals. In monazite, a mineral that is a principal source of rare earths, the worldwide average content of thorium oxide is 7.2 % ; however, varieties of monazite contain as little as 0.001% and as much as 31.5% thoria. Monazite is the chief ore of thorium and, until recently, thorium has been the main product; the rare-earth metals were in fact byproducts. However, because of the great demand for rare-earth metals by the petroleum refining and the iron and steel industries since the early 1970s, the roles have been reversed so that thorium is now the byproduct. Uses A 9 to 1 mixture of yttrium and thorium oxides is used for high-intensity incandescent lamps and for high-temperature-resistant windows and lenses. Yttrium oxysulfide and orthovanadate, doped with europium oxide, are used in color television tube phosphors. Yttrium, as well as cerium, praseodymium, and samarium, is alloyed with cobalt to form strong permanent magnets. It hardens magnesium alloys and retards the oxidation of iron-chromium alloys. Yttrium-iron garnets are used for transmitting low microwave frequencies. Yttrium-aluminum garnets are used as host crystals for lasers and as artificial gems. Yttria also forms strong, stable, high-temperature refractories. Gadolinium-gallium garnets are used in substrate wafers on which bubble-memory films are deposited. Rare-earth chlorides, particularly of lanthanum, neodymium, and praseodymium, are used as catalysts for petroleum cracking. Mischmetal is used for lighter flints and to improve the ductility and impact strength of iron and steel alloys. Mischmetal also reduces the fatigue resistance of magnesium and aluminum alloys. Rare-earth oxides are used for polishing glasses and lenses. Individual or specific combinations of high-purity oxides are used as additives in glass to maintain or change its color, dispersion, or refractive index. High-purity oxide combinations are also used to color tile and to opacify porcelain enamel. Rare-earth fluorides and oxides are used in carbon-arc electrodes to provide incandescent white light. Lanthanum or gadolinium oxysulfide phosphors, activated with terbium, are used as x-ray screen intensifiers. Hydrogen can be stored by sorption on lanthanum-nickel alloys (Anon., 1979). Thorium232 is bombarded with slow neutrons in breeder reactors to create fissionable thorium233 for nuclear fuel cells. The 330-MW, high-temperature gas-cooled reactor at Fort St.

Jan 1, 1983

By J. Charles Miller

NATURAL carbon dioxide has recently been exploited in the United States in consequence of oil and gas developments in the Western States and the growing demand by transcontinental and transoceanic shippers for solid carbon dioxide. The discovery by drilling of commercial deposits resulted in consideration of its geographic and geologic distribution and occurrence. Its wide distribution in nature is evidenced by its occurrence in the atmosphere, hydrosphere and lithosphere. The question of origin of carbon dioxide involves consideration of theories similar to those concerning natural hydrocarbons, although available evidence favors an inorganic rather than an organic source. Areas favorable to development of commercial production appear to be those in proximity to igneous rocks or in the vicinity of decadent volcanic activity, where, it has long been known, the gas is evolved either free or dissolved in the waters of fumaroles, geysers or mud pots. Structure contour maps are presented showing the Wagon Mound anticline in New Mexico and the Farnham anticline, Utah. A well drilled on the latter supplies gas to a 20-ton plant manufacturing solid carbon dioxide at Wellington, Utah, on the Denver and Rio Grande R.R., whence it is shipped to surrounding territory and to the West Coast. Before funds are invested in a plant for the manufacture of liquid or solid carbon dioxide, whether supplied by wells or springs, an effort to ascertain the volume of gas available is advisable. The use of present methods of estimation of gas reserves with modifications to account for the quantity absorbed by any water present in the producing formation is recommended, The Farnham anticline is used as an example and cornputationa are made of the probable volume of gas originally present in the structure. No attempt was made to compute reserves in the Niland area, California, for the reason that in such areas it is believed the volume is indeterminate. INTRODUCTION Carbon dioxide, in liquid and solid form, has found a wide variety of uses other than its primary application in carbonating beverages. It is now used in more than 40 different ways, ranging from cooling or freezing to use in gas or liquid form for mechanical purposes, chemical industry, explosive, fire extinction, and tire manufacturing. Undoubtedly the chief supply of carbon dioxide is obtained from industrial plants or artificial sources and until recently natural deposits of the gas have received little consideration. Few will question the utility and perhaps dependability of artificial sources, which possess the advantage over

Jan 1, 1937

By William E. Ford, Edward Salisbury Dana

1. Normal Class (31) Axinite Type 2. Asymmetric Class (32) Calcium Thiosulphate Type Mathematical Relations of the Triclinic System 216. Crystallographic Axes. - The triclinic system includes all the forms which are referred to three unequal axes. with all their intersections oblique. When orientated in the customary manner one axis has a vertical posi-

Jan 1, 1922

By W. L. Prehn, Adele Chambers, R. L. Slobod

The centrifuge has been found to be an extremely useful tool for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. The use of the centrifuge for determining the properties of small core plugs has been discussed in the literature,',' but practically no experimental evidence has been presented justifying the use of this method in preference to other methods (mainly disc method) now in use. Data have been accumulated and are now presented demonstrating the advantages of the centrifugal method, some of which are: (1) rapid establishment of equilibrium, (2) excellent precision yielding very reproducible results, (3) availability of high pressure differences between phases, (4) simple operational procedure, and (5) ability to establish connate water, residual oil, or to obtain complete capillary pressure curve in one day or less. A commercially available centrifuge capable of speeds up to 3,800 rpm, and a high speed attachment providing a maximum rate of rotation of 18,000 rpm were used in this work in conjunction with core holding tubes designed specifically for this application. In view of the outstanding advantages associated with the use of the centrifuge the conclusion has been drawn that this method should be used in place of the more tedious, slower, and less reliable disc method for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. INTRODUCTION The need for accurate values of connate water, residual oil, and capillary pressure curves in reservoir engineering has been recognized for many years, and the extent of the effort devoted toward solving these problems is reflected in the large number of papers3-" which have appeared in the literature during the past decade. Most of the methods discussed in the recent literature employ a porous disc as a semi-permeable membrane to separate two immiscible phases and make pos-ible the application of an explicit difference in pressure between two phases in the core. Thus, in the determination of the capillary pressure curve the wetting phase (water) is displaced by the non-wetting phase (air or oil). Several investigators1,2 have used centrifugal forces to develop pressure differences between phases. As a result of the first work' in this field the conclusion was reached that "the more rapid centrifugal method for measuring irreducible saturation may have equal value, (compared to use of discs) but more work is required to establish this point." This work was followed in 1945 by a more detailed study2 in which the concepts of this experimental work were more clearly enunciated. A method for calculating saturation for any given speed of rotation based on the observed volume of water displaced was developed and a wider application of the method was suggested. The absence of any subsequent pertinent literature on this subject is interpreted as indicating that no additional work has been completed to substantiate or deny the earlier claims and suggestions of promise contained in the original papers on this subject. One purpose of this report is to provide evidence designed to establish the practical value of centrifugal methods in determining core properties such as connate water and capillary pressure curves. It is also our purpose to suggest a broadening of the scope of this tool to include determinations of residual oil by gas or water drives. THEORY AND PRACTICE IN USE OF CENTRIFUGE Hassler and Brunner2 have clearly presented the basic concepts involved in the use of the centrifuge by relating the performance of a small core in a field of high acceleration to the

Jan 1, 1951

By M. C. Udy, P. C. Rosenthal

The use of minute boron additions to steel has been given considerable attention in recent years. Comparisons made between boron-free and boron-containing heats of otherwise identical analysis have indicated, beyond a doubt, the potent effect of boron for increasing hardenability. The actual hardenability increase has been expressed as a multiplying factor, or in terms of the percentage of other alloying elements boron might replace. The present study presents the results of a systematic survey of the use of boron as an addition to two types of alloyed steels and as a replacement for various percentages of molybdenum in these steels. Both cast and wrought steels of the two basic compositions were prepared. Molybdenum, because of its scarcity at the time the investigation was started, was selected as the element to be replaced by boron. Attention was also given to the effects of boron on other properties of the steels, particularly their notched-bar toughness, to investigate other advantages or limitations of this element as an alloy addition. Experimental Work Steels Investigated The two basic compositions used in this survey of boron as a replacement for molybdenum are given in Table I. The cast steels were higher than the wrought steels in silicon content to improve the casting quality. Table i.—Nominal Composition of the Two Base Alloy Steels composition. Per Cent. steel Mn Si Ni Cr Xi-Cr-Mo Wrought 0.28-0.70-0.15-o.45—o.45-0.32 0.90 0.25 0.55 0.55 Cast 0.28-0.70-0.35-0.45-o.45- 0.32 0.90 0.45 0.55 0.55 hln-&lo Wrought 0.28-I .go-o.0.15-0.32 1.70 0.15 Cast o. 28- I.40- 0.35- 0.31 1.70 0.45 a Sulphur was 0.040 per cent maximum and phosphorus 0.030 per cent maximum. Each of these base steels, both cast and wrought, was made with molybdenum contents of o, 0.10, 0.20, 0.30, or 0.40 per cent, the total comprising 20 steels. In addition, each of these 20 compositions was prepared with boron additions in amounts of o.oo15, 0.003, and 0.006 per cent as ferroboron; and in amounts of 0.002 and 0.005 per cent as two commercial intensifier alloys, designated alloys A and B. The boron-treated steels totaled 100, and the entire series 120. Test Procedure Each steel was melted as an individual heat in a 50-lb., magnesia-lined induction furnace. Ingot iron scrap or mixtures of ingot iron and steel. scrap were used for melting stock. Deoxidation was carried out in the furnace with 0.10 per cent aluminum. The aluminum addition was

Jan 1, 1948

By M. C. Udy, P. C. Rosenthal

The use of minute boron additions to steel has been given considerable attention in recent years. Comparisons made between boron-free and boron-containing heats of otherwise identical analysis have indicated, beyond a doubt, the potent effect of boron for increasing hardenability. The actual hardenability increase has been expressed as a multiplying factor, or in terms of the percentage of other alloying elements boron might replace. The present study presents the results of a systematic survey of the use of boron as an addition to two types of alloyed steels and as a replacement for various percentages of molybdenum in these steels. Both cast and wrought steels of the two basic compositions were prepared. Molybdenum, because of its scarcity at the time the investigation was started, was selected as the element to be replaced by boron. Attention was also given to the effects of boron on other properties of the steels, particularly their notched-bar toughness, to investigate other advantages or limitations of this element as an alloy addition. Experimental Work Steels Investigated The two basic compositions used in this survey of boron as a replacement for molybdenum are given in Table I. The cast steels were higher than the wrought steels in silicon content to improve the casting quality. Table i.—Nominal Composition of the Two Base Alloy Steels composition. Per Cent. steel Mn Si Ni Cr Xi-Cr-Mo Wrought 0.28-0.70-0.15-o.45—o.45-0.32 0.90 0.25 0.55 0.55 Cast 0.28-0.70-0.35-0.45-o.45- 0.32 0.90 0.45 0.55 0.55 hln-&lo Wrought 0.28-I .go-o.0.15-0.32 1.70 0.15 Cast o. 28- I.40- 0.35- 0.31 1.70 0.45 a Sulphur was 0.040 per cent maximum and phosphorus 0.030 per cent maximum. Each of these base steels, both cast and wrought, was made with molybdenum contents of o, 0.10, 0.20, 0.30, or 0.40 per cent, the total comprising 20 steels. In addition, each of these 20 compositions was prepared with boron additions in amounts of o.oo15, 0.003, and 0.006 per cent as ferroboron; and in amounts of 0.002 and 0.005 per cent as two commercial intensifier alloys, designated alloys A and B. The boron-treated steels totaled 100, and the entire series 120. Test Procedure Each steel was melted as an individual heat in a 50-lb., magnesia-lined induction furnace. Ingot iron scrap or mixtures of ingot iron and steel. scrap were used for melting stock. Deoxidation was carried out in the furnace with 0.10 per cent aluminum. The aluminum addition was

Jan 1, 1948

By R. L. Slobod, W. L. Prehn, Adele Chambers

The centrifuge has been found to be an extremely useful tool for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. The use of the centrifuge for determining the properties of small core plugs has been discussed in the literature,',' but practically no experimental evidence has been presented justifying the use of this method in preference to other methods (mainly disc method) now in use. Data have been accumulated and are now presented demonstrating the advantages of the centrifugal method, some of which are: (1) rapid establishment of equilibrium, (2) excellent precision yielding very reproducible results, (3) availability of high pressure differences between phases, (4) simple operational procedure, and (5) ability to establish connate water, residual oil, or to obtain complete capillary pressure curve in one day or less. A commercially available centrifuge capable of speeds up to 3,800 rpm, and a high speed attachment providing a maximum rate of rotation of 18,000 rpm were used in this work in conjunction with core holding tubes designed specifically for this application. In view of the outstanding advantages associated with the use of the centrifuge the conclusion has been drawn that this method should be used in place of the more tedious, slower, and less reliable disc method for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. INTRODUCTION The need for accurate values of connate water, residual oil, and capillary pressure curves in reservoir engineering has been recognized for many years, and the extent of the effort devoted toward solving these problems is reflected in the large number of papers3-" which have appeared in the literature during the past decade. Most of the methods discussed in the recent literature employ a porous disc as a semi-permeable membrane to separate two immiscible phases and make pos-ible the application of an explicit difference in pressure between two phases in the core. Thus, in the determination of the capillary pressure curve the wetting phase (water) is displaced by the non-wetting phase (air or oil). Several investigators1,2 have used centrifugal forces to develop pressure differences between phases. As a result of the first work' in this field the conclusion was reached that "the more rapid centrifugal method for measuring irreducible saturation may have equal value, (compared to use of discs) but more work is required to establish this point." This work was followed in 1945 by a more detailed study2 in which the concepts of this experimental work were more clearly enunciated. A method for calculating saturation for any given speed of rotation based on the observed volume of water displaced was developed and a wider application of the method was suggested. The absence of any subsequent pertinent literature on this subject is interpreted as indicating that no additional work has been completed to substantiate or deny the earlier claims and suggestions of promise contained in the original papers on this subject. One purpose of this report is to provide evidence designed to establish the practical value of centrifugal methods in determining core properties such as connate water and capillary pressure curves. It is also our purpose to suggest a broadening of the scope of this tool to include determinations of residual oil by gas or water drives. THEORY AND PRACTICE IN USE OF CENTRIFUGE Hassler and Brunner2 have clearly presented the basic concepts involved in the use of the centrifuge by relating the performance of a small core in a field of high acceleration to the

Jan 1, 1951

By R. E. Jenkins

The Bell Canyon member of the Delaware Mountain group has yielded quite a large number of fields in which completion and production problems have been numerous and complex. Reserves are difficult to estimate due to the problem of evaluating the formation water saturation, and the feasibility of water flooding is questionable. Extensive laboratory investigations were undertaken to determine if normally measured rock and contained fluids properties could account for many of the peculiar characteristics of the formation. A statistical study or routine core-analysis data was made. Capillary-pressure data were obtained by several techniques. Fresh-water and brine permeabilities were measured and relative permeabilities of oil, water and gas were determined. Some qualitative wetta-bility tests were performed, and the petrography of a few thin sections was studied. The results of this work are presented, with typical or average data shown for each test. The permeability -to- water characteristic of the Delaware was found to be abnormally poor. Correlations of laboratory and field performance data indicate high water saturations in much of the formation. Pore geometry is highly uniform. INTRODUCTION The Delaware formation has undergone extensive exploration and development in the past few years. This has resulted in the discovery of quite a number of fields—producing oil for the most part. A large percentage of the productive wells have produced water along with the oil. Often there is no apparent pattern for the percentage of water cut experienced. In several instances vertical displacments of over 200 ft have been established between communicating wells in which the formation appears to be about the same, yet the structurally high wells yield a much higher water cut than the lower wells. Drill-stem tests have contributed little to well completion because they nearly always show small amounts of water (usually mud filtrate), regardless of what is produced later in the life of the well. Other formation evaluation methods have had no more than limited success in indicating ultimate productivity. Consequently, predicting the type of fluid productivity of Delaware wells has been very difficult. Hydraulic fracture treatments are almost universal, and unstimulated Delaware wells have not exhibited the productivity that normally would be expected of wells with the specific permeabilities encountered. Some operators have indicated that their Delaware wells need frequent re-stimulation. The uncertainty of reservoir water saturations reported for the Delaware has made difficult the task of evaluating oil in place in the reservoirs and estimating primary recovery. The unreliability of this data also will cause feasibility studies for water flooding or other secondary-recovery methods to be problematical. Several opinions have been voiced to explain why the Delaware performs as it does. Chronically poor well completions, dynamic water and tilted water tables, capillary inequi-libria, peculiar relative permeability characteristics and oil-wetness are among the suggested reasons. The dual purpose of this paper is (1) to describe the principal rock characteristics, and (2) to present an evaluation of those characteristics so that approaches can be made to explain the irrational behavior of wells completed in the Delaware. STUDY OF ROUTINE CORE-ANALYSIS DATA A statistical study of routine core-analysis data has been made to relate fundamental rock properties and characteristics of the formation to well productivity. For the most part, well production data were obtained from operators and augmented by production data from commercial information services. Only data which were available in detail and which were considered to be accurate were used. The core data used were obtained on samples from the perforated or open interval only and, thus, may not always represent the total productive interval in a well. All the core-analysis data included in this study are from the Bell Canyon member of the Delaware and were obtained by "plug-type" techniques, as opposed to whole-core or full-diameter techniques. Porosity values were obtained by the summation-of-fluids technique, permeability values are air permeabilities corrected for slippage to an equivalent liquid permeability, and the oil and water contents were determined by means of a high-temperature downdraft retort. All the procedures used are discussed at length in Ref. I. The core-analysis data were sorted

By J. Lohrenz, C. R. Clark, B. G. Bray

Procedures to calculate the viscosities of in situ reservoir gases and liquids from their composition have been developed and evaluated. Given a composition expressed in methane through heptanes-plus, hydrogen sulfide, nitrogen and carbon dioxide together with the molecular weight and specific gravity of the heptanes-plus fraction, the procedures are capable of calculating the viscosity of the gas or liquid at the desired temperature and pressure. The procedure for reservoir liquids was developed using the residual viscosity concept and the theory of corresponding states, and was evaluated by comparing experimental and calculated results for 260 different reservoir oils ranging from black to highly volatile. The average absolute deviation was 16 per cent. This is the first known procedure for calculating the viscosity of reservoir liquids from their compositions as normally available, i.e., including the heptanes-plus fraction. The procedure for reservoir gases uses a sequence of previously published correlations. Evaluation of the procedure was accomplished by comparison of 300 calculated and experimental viscosities for high-pressure gar mixtures in the literature. The average absolute deviation was 4 per cent. The calculations are useful for (I) determining viscosities in compositional material balance computations and (2) predicting the viscosity decrease which occurs when gases, LPG, or carbon dioxide dissolve in reservoir oils. INTRODUCTION Methods to predict viscosities of reservoir fluids from the normally available field-measured variables have been presented. Beal,1 Standing,2 and Chew and Connally3 orrelated oil viscosities with temperature, pressure, oil gravity and gas-oil ratio. Carr, Kobayashi, and Burrows4 and Katz et al.5 have presented correlations for reservoir gas viscosities as a function of temperature, pressure and gas gravity. Lie all intensive physical properties, viscosity is completely described by the following function: Eq. 1 simply states that viscosity is a function of pressure, temperature and composition. These previous correlations1- hay be viewed as modifications of Eq. 1, wherein one assumes more simple functions may be used. The assumptions are practical, because the composition is frequently not known. Further, the assumptions are sufficiently valid so that these correlations are frequently used for reservoir engineering computations. In compositional material balance"' computations, the compositions of the reservoir gases and oils are known. The calculation of the viscosities of these fluids using this composition information is required for a true and complete compositional material balance. For reservoir gases, Carr, Kobayashi and Burrows4 have presented a suitable compositional correlation. For reservoir oils, no correlation is available, and data from reservoir fluid analyses have been used7-9 for compositional material balance calculations.* From a theoretical point of view, this is entirely invalid. The reservoir fluid analysis, whether flash, differential, or other process, does not duplicate the compositions which occur during the actual reservoir depletion process, therefore the viscosities measured during reservoir fluid analysis are not those which occur in the reservoir. From a practical point of view, the "error" of using viscosities from reservoir fluid analysis is of varying and unknown significance. One can say qualitatively that the error is greatest where compositional effects are greatest, i.e., for volatile oil and gas condensate reservoirs and pressure maintenance operations. The first requirement to obtain a quantitative estimate of the significance of the error is to develop a reliable compositional correlation for the viscmities of reservoir oils. No such correlation has been available. Consistent with this requirement, the objective of this study was to develop a procedure to predict the viscosity of reservoir fluids from their compositions. Normally, the compositions of reservoir fluids are available expressed as mole fractions of hydrogen sulfide, nitrogen, carbon dioxide and the hydrocarbons methane through the heptane-plus fraction, with the average molecular weight and specific gravity of the latter. The final correlation was to use the composition in this form. While the more challenging objective of the study was the development of a correlation for the viscosities of reservoir oils, the viscosities of reservoir gases were also studied. The end result of the study was a procedure to calculate the viscosities of reservoir gases and liquids suitable

Jan 1, 1965

By C. B. Alcock, R. A. Oriani

Some simple models of solutions are described; these include the regular solution, the subregular solution, and the quasichemical model. The assunzption underlying these models, the physical signzficance thereof, and the experimental manifestations are discussed. Examples are presented from the fields of liquid and solid metallic solutions, liquid slags, mattes, liquid and solid ionic solutions, and mixed carbides to show under what conditions and for which systems these solution models are fair descriptions. The deviations of real solutions from the models are of theoretical interest. Some such deviations, both for dilute and for concentrated solutions, arc pointed out and their Physical sigtzzficance discussed. DURING the past half century there has been a gradual accumulation of thermodynamic data for systems of interest to the metallurgist. There remain many gaps in the data, however, and the metallurgist must often face the problem of estimation of thermodynamic quantities where measured values do not exist. One might hope that the experimental progress would be matched by theoretical advances which would make such estimations possible with a high degree of confidence. However, theoretical progress has been disappointingly slow even for the simplest kinds of solutions, and since the multicomponent systems in which the metallurgist is interested are very complex, one cannot expect theory to be of much help to the metallurgist. In this situation, therefore, it seems worthwhile to examine some simple models of solutions from two points of view: firstly, to see if such crude models represent the thermodynamic facts in as many types of solutions as possible sufficiently well for the needs of the metallurgist, and secondly to see what the deviations from such models show to be important for consideration by theorists. BOND ENERGY MODELS OF SOLUTIONS The simple models that we will examine from these points of view may be termed statistical models, in that they are concerned with the thermodynamic consequences of some simple assumptions about the energy of an assembly of atoms, molecules, or ions, and do not inquire into the physical basis of the interaction. The underlying assumption of these models is that the energy of an assembly of molecules (by which we include also atoms or ions) is given by the sum over all interaction energies of molecules taken two at a time; we will discuss only those models in which the pairwise interactions are restricted to those between nearest neighbors. Thus, in a pure substance of bond energy EAA, the internal energy (with respect to some specific reference state) will be expressed as NAA EAA where NAA is the number of nearest-neighbor pairs. A solution of molecules A and B will be characterized by NAA EAA + NBB EBB + NAB EAB where the Eij represent the bond energies of the nearest-neighbor i-j pairs. If one assumes that the EAA and EBB are the same in the pure components as in the solution, and that the coordination numbers in the two pure substances and in the solution are the same, then the energy of the solution with respect to the pure components (i.e., the energy of solution) is a function of the following linear combination of the bond energies: EAB - 1/2(EAA +EBB) = w. The thermodynamically ideal solution is defined as one in which the activity of each component is equal to the mole fraction of that component at all concentrations and all temperatures. It follows that

Jan 1, 1962

By J. R. Low, D. F. Stein

Single crystals of iron have been grown from three different lots of Ferrovac "E" of somewhat different chemical composition by the strain anneal technique. Using a technique to seed the crystal similar to Dunn's for silicon-iron, it has been possible to orient the crystals grown in both direction and plane of growth. Crystals having the plane of the strip oriented (100) , (110), (111), (112), (123), and (491) have been grown. The growth directions used have been [100], [110], 45 deg from a [110}, and various others of no specific crystal orientation. The usual dimensions of the crystals were 8 by 1 by 0.08 in. Attempts to grow crystals were about 90 pct successful. METHODS of growing single crystals of high purity iron have been reported in the literature.1-4 However, each of these methods was not completely reliable when used on materials having slightly different chemical composition and in some instances a small number of successes were obtained using identical materials. Except for the method used by S. Dohi and T. Yamoshita,1 it has not been possible to reorient single crystals of high purity iron to give any desired orientation. The method to be described has made it possible to grow single crystals from three different lots of material having different compositions, and to orient the crystals with respect to growth direction and surface. STARTING MATERIAL The material used during this investigation was a vacuum melted high purity iron marketed by the Vacuum Metals Corporation designated Ferrovac "E." Three lots of Ferrovac "E" having the following composition were used with equal success: The compositions listed are those of the as-received material; and they may have been modified before the growth of single crystals. Analysis of heat B just before growth and after growth revealed that the heat treatment prior to growth did not change the carbon content, but the oxygen content was changed from 0.0092 pct to 0.0034 pct and the nitrogen content from 0.0003 pct to 0.0001 pct. After growth of the single crystals, the carbon had dropped to 0.001 pct. None of the heat treatments would be expected to change any of the other impurities very markedly. Heat C would be expected to have a metallic impurity content similar to heats A and B. PROCEDURE Ferrovac "E" iron which had been obtained in bar form having a diameter of about 1 in. was rolled into strip for growing single crystals. By passing the 1-in. bar through a cold rolling mill several times, it was reduced to a strip 0.15 in. thick. The strips obtained were then cut into suitable lengths for heat treating (about 9 in. long), annealed at 925°C for 2 hr in dry hydrogen and water quenched. It was then necessary to bake the strip at 200°C for 24 hr in air in order to prevent cracking during further rolling operations. While it was possible to cold roll the 1-in. bar directly to the desired 0.080-in. strip, the intermediate anneal was used because the strip so obtained produced better single crystals. The strip obtained by rolling the 1 -in. bar directly to 0.080-in. strip produced single crystals having a large number of occluded grains. Experiments showed that the optimum reduction in area by rolling prior to the growth of single crystals was about 50 pct. Attempts to grow single crystals from material that had been reduced less than 40 pct were unsuccessful presumably because the matrix did not possess the critical amount of texture necessary for growth. The strip obtained after the rolling operations had very irregular edges which were ground to give a strip with uniform dimensions. The strip was then annealed at 825°C for 3 hr in hydrogen and furnace cooled. Fig. 1 illustrates the grain size obtained. A temperature of 940°C was used for the annealing temperature on one group of strips

Jan 1, 1962

By P. Majani, F. P. Kokesh, M. Grosmangin

Determination of the quality of cementation of casing in oil wells in the past has involved inflow and circulation tests to insure that the producing zones were adequately sealed off from the adjacent zones. Existing logging methods, such as temperature and radioactivity surveys, may detect the presence of cement behind the casing. However, the qualities of the cement (i.e., its hardness and particularly its bond to the casing) are not indicated. The new logging method described in this paper operates on the principle that the attenuation of a sonic pulse transmitted by a casing is greatly increased when that casing is bonded to an outer annulus of hard material (such as set cement) which has an appreciably smaller sonic-wave velocity than that of the casing. The down-hole tool contains a source of recurrent sound pulses which are detected by a receiver spaced a few feet from the source The amplitude of the detected casing-borne pulse is measured, and the resulting signal is transmitted to the surface where it is recorded vs depth. Since amplitude is a function of attenuation, the log is readily interpreted. Laboratory studies have shown straightforward relationship between attenuation and such variables as source-detector spacing and per cent of circumference bonded. It is shown that cement not set or not bonded to the casing has compara- tively little attenuating effect. Field examples show not only the cement top, but also the variation in cementation quality below the top. Further, the increase of bonding with time and after squeeze cementation is depicted. The detection of poor cement jobs is confirmed by production tests and by formation-test results. It is anticipated that the method will have wide application in evaluating cementation quality prior to formation testing in completions and recompletions. The analysis it affords may aid in further improving cementation techniques. INTRODUCTION The main purpose of oilwell cementing is to isolate a production zone from other undesirable zones. To investigate whether this purpose has been accomplished, several logging methods have been used such as temperature logs, radioactive tracer logs, etc. While these logs all respond to the presence of cement behind the casing, they do not indicate the degree of bonding of the cement to the casing. Early in the application of sonic logging, it was noticed that considerable attenuation of sound signals takes place in cemented pipe and is often made evident on the standard Sonic log by cycle skipping.' The development of a circuit capable of continuously recording the amplitude of the casing-borne sound signal has made possible an extensive series of laboratory and field tests, which gave the following results. The amplitude of a sound signal after it has traveled in a firmly cemented pipe is only a small fraction of that recorded by the same device in free pipe. This provides a wide spectrum of energy levels; for given local conditions, empirical values of the amplitude can be correlated with the quality of cementation. Interpretations made in this manner generally have been confirmed by production tests, circulation tests and squeeze cementation. The purposes of this paper are to give a general description of the new logging method and to present some laboratory and field results. CYCLE SKIPPING Early attempts to study the quality of the cement behind the casing were performed with a standard Sonic log, which measures the transit time At, and were based on the well known phenomenon of cycle skipping.' Cycle skipping normally is interpreted as being a manifestation of weak signals at the receivers. The log of Fig. 1 was run with the recording instrumentation adjusted to enhance cycle skipping. A mirror-image presentation was used for better visual interpretation. The transit time of sound in steel is about 58 microseconds/ft (corresponding to a velocity of 17,000 ft/ sec), and the portions of the log where this value is recorded are interpreted as zones with no cement bond. Where cycle skipping produces a higher value of At, weak signals (or a high rate of attenuation) are indicated, and a good cement bond may be present. The occurrence of cycle skipping, however, depends too much on instrument adjustment to give a uni-

By Frank A. Howard

WHAT are the reasons for the present public interest in the synthetic fuel industry, an interest which has culminated in the recommendation of the Secretary of the Interior that we start at once on a nine billion dollar program of construction? Three separate factors seem to have combined to create this pressure. First are recurrent seasonal and spot shortages of gasoline, fuel oil, and natural gas. Second is the international outlook, which forces us to face the possibility of war, with all that means in the way of increased call on our domestic resources and interference with our foreign commerce. The shortages we have experienced are superficially the result of lack of transportation, but basically they reflect a rapidly rising demand which has outstripped the expansion of productive facilities of all kinds. Not only oil and gas, but steel, coal, automobiles, and meat are temporarily in short supply for much the same reasons. The military problem has both long-range and short-range aspects, but the immediate necessity is to create reserve capacity in the United States to supply perhaps 2,000,000 barrels daily additional liquid fuel in time of war.

Jan 1, 1948

By J. J. Gilman

The data presented indicate that the critical shear stress and strain-hardening Thedatapresentedrate of a zinc monocrystal depend on the orientation of its slip direction with respect to its external boundaries. The tendency of a crystal to form deformation bands also depends on its shape. THE plastic behavior of pairs of zinc monocrystals in which both members of the respective pairs had the same orientation with respect to the longitudinal axis, but each had different orientations with respect to their rectangular external shapes, were compared in this investigation. The purpose of the investigation was to see what influence the shape or surface of a zinc crystal has on its mechanical properties. In a previous investigation of triangular zinc monocrystals,1 anomalous axial twisting was observed which seemed to be related to the triangular shape of the crystals. Wolff,' in 400°C tensile tests of rectangular rock-salt crystals bounded by cubic cleavage planes, found that, of the four equivalent slip systems, the two with the "shorter" slip directions yielded and produced slip lines at lower stresses than the other two. This observation and the work of Dommerich³ as formulated by Smekal4 as a "new slip condition" for rock-salt: "among two or more slip systems permitted by the shear stress law, with reference to the formation of visible slip lines by large individual glides, that slip system is preferred which has the shortest effective slip direction." More recently, Wu and Smoluchowski5 reported essentially the same effect for ribbon-like (20x2x0.2 mm) aluminum crystals at room temperature. Experimental Chemically pure zinc (99.999 pct Zn), purchased from the New Jersey Zinc Co., was the raw material. Glass envelopes, containing graphite molds and zinc, were evacuated while hot enough to outgas the graphite but not melt the zinc. At a vacuum of about 0.2 micron the envelopes were sealed off and then lowered through a furnace at 1 in. per hr so as to melt and resolidify the zinc and produce mono-crystals. One-half of one of the molds is shown in Fig. la. Each mold consisted of four pieces from a cylindrical graphite rod that was split longitudinally and transversely at its midpoints. Rectangular milled grooves 0.050 in. deep and % in. wide formed the mold cavity when the split halves were assembled with twisted wires. Fig. lb shows the specimen shape obtained when the top and bottom mold-halves were rotated 90" with respect to each other. Good fits prevented leakage and excess zinc was necessary to provide enough liquid head to fill the mold completely. In removing soft crystals from the molds it was impossible to avoid small amounts of bending. However, manipulations were carried out whenever possible with the crystals protected by grooved brass blocks. All specimens were annealed prior to testing. From the top and bottom sections of each crystal, X-ray specimens and tensile specimens 7 to 8 cm long were sawed. The tensile specimens were annealed inside evacuated tubes for 1 hr at 375°C. Next the crystals were cleaned and polished by 2-min dips in a solution of 22 pct chromic acid, 74 pct water, 2.5 pct sulphuric acid, and 1.5 pct glacial acetic acid.' Cleaning was followed by a 10-sec dip in a 10 pct caustic solution, then washed in water and alcohol, and dried. This treatment results in a bright surface covered by an invisible oxide film. The testing grips were a slotted type with set screws and were supported in a V-block during the mounting operations in order to avoid bending the crystals. A schematic diagram of the recording tensile-testing machine is shown in Fig. 2. The machine has been described elsewhere.' The head speed was 0.3 mm per sec for all tests. The crystal orientations were determined by the Greninger X-ray back-reflection method with an estimated accuracy of 1. Description of Crystal Geometry A schematic picture of a rectangular zinc mono-crystal is shown in Fig. 3. ABD designates the front edge of a basal plane (0001) of the crystal, the only active slip plane for zinc at room temperature. Of the three possible (2110) slip directions, the active one is indicated by an arrow. Cartesian coordinates are taken parallel to the specimen edges. The normal, n, to the basal plane (n is parallel to the hexagonal axis) has the direction cosines a, ß and ?. X0 = 90 — y is the angle between the longitudinal axis and

Jan 1, 1954

By R. H. McLean

Jet impingement produces two mechanisms to clean the bottom of a borehole during jet-bit drilling operations. One is an impact-pressure wave in the immediate area of jet impingement. The other is crossflow, which spreads across the bottom away from the pressure wave. Measurements of the vertical distribution of the cross-flow at several positions beneath a 4 3/4-in. tricone jet bit in a laboratory model show that the maximum velocity in the crossflow is directly proportional to the square root of the product of the rate of flow and the velocity of the jets through the nozzles (QV). Other measurements in the laboratory model show that gradients in the impact-pressure wave are directly proportional to the jet QV if the diameters of the nozzles are held constant. Consistency of the basic relationships through changes in the Reynolds numbers of the jets from 31,000 to 93,000 suggests that the laboratory results should be representative of typical flow in field operations having higher Reynolds numbers. Estimates of the impact-pressure waves under conditions other than those in the jet-bit model may be made by comparison with a less complex model—impingement of a jet against an unrestricted flat surface normal to the jet. Equations derived from current jet technology describe the wave in this simple system for a wide range of conditions. INTRODUCTION The efficiency of rotary drilling operations is strongly linked to the efficiency with which cuttings are removed. Cuttings remaining on the bottom of the borehole will impede further penetration by the bit until they are removed. Wasteful regrinding is prevented if the fluid circulated past the bit removes cuttings as rapidly as they are made. Most investigations of bottom-hole cleaning under bits have been concerned with the rate-of-penetration effects of bit type, nozzle configuration, fluid properties, pressure gradients and utilization of hydraulic horsepower. These investigations have shown that drilling muds, weighted to keep the pressure in the borehole greater than in adjacent formations and carrying material which forms a filter cake, apparently plaster cuttings against the bottom, making them difficult to remove. In addition to a demonstration of the factors causing poor cleaning, the most significant result of these previous investigations has been the increased use of jet bits accompanied by better hydraulic programs and better selection of drilling fluids. Undoubtedly, these practices have improved bottom-hole cleaning, but rates of penetration when drilling with muds are still often lower than would be expected with perfect cleaning." Although there is general agreement with the concept that increasing hydraulic energy at a jet bit often increases the rate of penetration by improving cleaning, research workers have differed as to the best criterion for evalyating hydraulics. Some lean toward maximizing the product of the rate of flow and the velocity through the nozzles (QV) others prefer to maximize the hydraulic horsepower at the bit;'"-' "till another says that neither criterion is universally suitable."' This controversy shows that conclusive field evidence has not established the superiority of either of these criteria. Analysis of the fluid flow which cleans the bottom should contribute to resolving the controversy. Impinging jets clean the bottom by creating two mechanisms capable of dislodging cuttings. One is the impact from the momentum of the jet and the other is the flaw parallel to the bottom away from the area of impingement. The impact force appears in the form of a pressure wave on the bottom and, in this paper, is called the impact-pressure wave. The flow parallel to the bottom is called crossflow. Fig. 1 illustrates these two mechanisms. This paper describes crossflow and the impact-pressure wave beneath jet bits and relates them to controllable parameters. Through these relations, criteria for use in designing hydraulics to achieve maximum use of the mechanisms of cleaning are derived. PROPERTIES OF CROSSFLOW CONCEPTS DEVELOPED IN PREVIOUS INVESTIGATIONS Concepts of scavenging the bottom by crossflow have been well discussed by Bobo, et al." They examine the means by which crossflow may create forces on cuttings and conclude that the cleaning action of crossflow can be increased by increasing the velocity of the flow stream close to the bottom. Using boundary layer theory, they indicate that a reduction in the viscosity of the drilling

Jan 1, 1965

By Henry Lewelling

An experimental investigation of the relative effectiveness of standard bullets and "shaped charges" in perforating dense, hard formations is reported. A method is described which simulates the conditions under which a shot is normally fired. Results are evaluated on the basis of depth of penetration, extent 01 Fracturing. extent and nature of formation damage, and other physical characteristics. INTRODUCTION A study was made of the relative merits of bullets and "shaped charges'' as applied to well completions in hard, dense formations such as those encountered in the Permian Basin. The planning of the laboratory program stipulated that core samples should be prepared and mounted in such a way that perforation shots of either kind"" could be fired into them, keeping the factors pertinent to good shooting practice similar to what they would be in a well. The shooting was done in a buried tank. with the sample and shooting equipment covered with water. The depth of water was calculated to he sufficient to simulate the inertial effects of well fluids for the duration of an explosion (a few micro-seconds). Flow measurements were attempted on the specimens after perforation. Due to the lack of uniformity of the limestone, shale breaks. etc., these measurements proved to be of little value to the study. The mounting materials were removed. so that the character of the penetration. fracturing, etc., could be observed. METHOD Laboratory samples were selected from the hard. dolomitic sand cores from Block 31 Field. Core pieces having a 3 3/4 in. diameter and a useful length of 10 to 12 in. were used. Selection was aimed at those pieces having a minimum of shale streaks and other irregularities. The ends were cut off square Manuscript received in the Petroleum Branch office June 28, 1951. Paper presented at the Petroleum Branch Fall Meeting in Oklahoma City, Okla., Oct. 3-5, 1951. with the diamond saw. Prior to lbeing mounted. the cores were soaked in water to prevent them from absorbing water out of the wet concrete, thus weakening it. A set of steel capsules was fabricated for holding the core Samples. Seven-in. casing was cut in two-ft lengths. of which one end was closed by "orange-peeling" and welding, and the other was threaded to accept a standard bull plug. The bull plugs were fitted with copper tube connections .so that pressure could be applied when the capsules were made up. The cores were mounted in the capsules by means of wire centralizers whose function was to hold the Core in proper position while concrete was poured and set. A special aggregate was prepared wing a graded sand and gravel mixture

Jan 1, 1952

By G. L. Chierici

Starting from Muskat's theory of water and gas coning, maximum permissible oil production rates without water and/or free-gas production have been determined, in a broad range of reservoir and well parameters, using the potentiometric model technique. The main assumptions made are as follows: (1) the reservoir rock is homogeneeous (either isotropic or anisotropic); (2) the volume of the aquifer underlying the oil zone is very small, so that it does not contribute to reservoir energy; and (3) the gas cap expands at a very low rate, so that it can be assumed to be in quasi-static conditions. The results obtained are presented in the form of diagrams which can be used for solving two types of problems: (1) given the reservoir and fluids characteristics, as well as the position and length of the perforated interval, determine the maximum oil production rate without water and/or free-gas production; and (2) given the reservoir and fluids characteristics only, determine the position and length of the perforated interval which optimize the maximum permissible oil production rate, without water and/or free-gas production. INTRODUCTION In oil reservoirs where the oil-bearing formation is underlain by an aquifer which does not participate in the production mechanism, water-coning is a limiting factor to the flow rates of producing wells. Production rates are usually kept to a value that will prevent the water from entering the wells. The entry of water into a well lowers its productivity by increasing the weigbt of the fluid column; moreover, the separation of water from the effluent, at the surface, may constitute a very difficult problem in cases of heavy viscous oils. A similar situation is encountered in oil reservoirs with a gas cap overlying the oil-saturated zone; here a downward gas cone is induced by the flow of oil towards the producing wells. Production rates must be low enough to prevent the gas from being produced; producing gas from the gas cap would be a waste of energy. Of course, water-coning and gas-coning phenomena can occur at the same time in the same reservoir if the oil-producing formation is both overlain by a gas zone and underlain by a water zone. Due to its relevant practical importance, the mechanism of coning was studied by many people.2,3,5-8 Defining the conditions for getting the maximum water-free and/or gas-free oil production rate is a difficult problem, often encountered under one of the following aspects: 1. Predict the maximum flow rate that can be assigned to a completed well without the simultaneous production of water and/or free-gas. 2. Define the optimum length and position of the interval to be perforated in a well, in order to obtain the maximum water and gas-free production rate. A systematic study of these problems was made by means of the electrical analog technique. The results of this study are presented here, under the form of a set of curves providing solutions for the above stated problems. These curves are valid only for homogeneous forrnations, either isotropic or anisotropic. Should the formation be non-homogeneous (by horizontal or vertical variation of permeability, shale diaphragms, fractures, etc.), a specific potentiometric study would be required for each specific case. Especially when shale diaphragms of some radial extension are present, the critical rates observed are much larger than would be expected from the diagrams. STATEMENT OF THE PROBLEM In the present study the aquifer is supposed to be of such limited volume that it does not contribute to the energy of the reservoir. Moreover, the gas cap is supposed to expand at such a low rate that the potential gradient in the gas cap is negligible. Under static conditions water-oil and gas-oil interfaces (T1 and T2) are both horizontal. When the reservoir production starts, below each well these interfaces take a cone-like shape (Fig. 1) having as an axis the axis of the well. This shape results from the equilibrium between potential gradients in the oil zone and gravitational forces due to density differences between oil and water and between oil and gas. Assuming the oil-bearing formation to be homogeneous and the oil to be incompressible, the analysis of the problem (see Appendix) shows that the oil-water and gas-oil interfaces are stable only if the oil production rate of the well is not higher than the following values.

Jan 1, 1965

By R. S. Hooper

IN attempting to describe recent mining developments at the Bunker Hill mine, it may be well to recall first the old days of hand mining when holes were laboriously drilled by hand to a maximum depth of three feet, and were shot one or two at a time, in order that the miner could take advantage of every slip, crack or bedding plane, and so save as much drilling as possible. Broken muck, of course, was loaded by hand shoveling into wheelbarrows or small cars, and heading advances or stope ton¬nages were governed by the number of men that could find room to work in any given place. The first big improvement over these old methods was the introduction of the reciprocating type of air-powered rock drill. This innovation, crude as it was, enabled the miners to set up a machine and drill a complete round of holes in one shift; but broken muck was still loaded by hand, and the size and rate of advance in headings were limited by time required to remove the broken rock. The next improvement of consequence was the appearance of the hammer-type rock drill, which greatly increased drilling speed over the reciprocating type, and made possible the completion of a full cycle in one shift, by the use of crossbars in headings, and permitted drilling and mucking to be carried on at the same time. Rock drills continued to improve as time passed, and finally the smaller and more efficient mucking machines appeared on the scene, and it became possible to muck out a round of broken rock and have a clean setup for one or more drill columns and machines. A complete cycle of mucking, drilling, and blasting was completed in one shift with an average advance of five feet. These conditions prevailed for several years, but as the mine grew deeper, the distances to transport the workers grew longer, and this fact together with the shortening of the working day, soon presented the problem of attempting to complete a cycle of operations in a shift of only six hours at the working faces. Anticipating this condition, the operating heads at the Bunker Hill had started an intensive study of more and better mechanization, and over a period of comparatively few years have adopted and placed in service methods and machines that make it possible for a three-man crew to consistently advance headings seven by nine feet in cross section, at the rate of eight feet, and more, per shift, doing all the mucking, switching, drilling and loading. These improvements consist of the following major items: I. The development of a light, flexible, easily transported jumbo equipped with pneumatic columns (Fig I), that has decreased the "setting up" and "tearing down" time an average of 1 1/2 hr per shift, or 25 pct of the available working time. These jumbos were developed at the Bunker Hill mine by members of the staff and consist of two pneumatic columns attached to a suitable carriage. They fold

Jan 1, 1947

Jan 1, 1911