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By AIME AIME

THE CHAIRMAN of the fast growing Petroleum Division is not only a graduate of the University of California, but a third generation native son. After a few years spent in hard-rock geology, his professional efforts were transferred to the sedimentaries and to petroleum investigations, as a consulting geologist. For ten years these investigations covered the Rocky Mountain, Oklahoma, Texas, and eastern districts. After the war he returned to Casper, Wyo., as chief geologist for the Consolidated Royalty Oil and Western Exploration Companies. This employment afforded him the opportunity to study particularly the economic relationship between the lessor-lessee interests in development and production, a somewhat unusual type of petroleum specialization.

Jan 1, 1939

By M. Metzger, L. E. Hendrickson

Grain boundary attack in 16 pct HCl was found to be substantially the same at low penetrations in zone-refined aluminum (individual impurities 0.1 at. ppm), superior electrolytically refined aluminum (51 at. ppm), and aluminum with various impurities at much higher levels. It was concluded that impurity atom segregation affecting corrosion would have been detected and that the corrosion susceptibility did not originate in this segregation but in the structure of the boundary. It was pointed out that the significance of most previous studies in this system had been obscured by an unrecognized autocatalytic copper reaction. Although general corrosion rate was also impurity-insensitive , there was shallow pitting attributed to iron seg-regation and a hillocked surface texture associated with copper; these were interpreted as due to cathodic damage affecting- cathode distribution. THE grain boundary corrosion suffered by high-purity aluminum in hydrochloric acid has been the object of some interest (the earlier work is summarized in Ref. 1). The central metallurgical question here is whether the corrosion susceptibility of a boundary originates in its structure or in impurity atom segregation. An attempt to study this question revealed large catalytic effects associated with small quantities of the copper impurity in the aluminum, 220 ppm, or in the corrodent, and these magnified the preferential boundary attack and obscured the intrinsic susceptibility question.' After the catalytic effects had been examined,"' test conditions could be designed to avoid them and methods developed for studying the shallow boundary penetrations prevailing when they were absent.= It then became possible to determine whether intrinsic boundary corrosion in aluminum involves impurity segregation. The older work provided no firm information on grain boundary segregation of specific solutes influencing corrosion although several studies suggested iron segregates.4,5 perryman4 found in 10 pct HC1 that the slowly developing (microns per month) grain boundary grooves were deeper in material of higher iron content (range 10 to 550 ppm, with 5 to 80 pprn Cu) but he did not measure the depths of general corrosion, which were probably several times greater, and his reference surfaces may have varied more than did the groove depths. Metzger and Intrater's results for 20 pct HC~,' which yielded higher time-average rates (mm per month) and deeper penetrations, suggested that boundary segregation of iron (range 4 to 230 ppm, with 22 pprn Cu) decreased the penetration rate. However. in the stronger acid the autocatalytic l.E. HENDRICKSON, Student Member AIME ,and M. METZGER, Member AIME, are Research Assistant and Professor of Physical Metallurgy, respectively, Department of Mining, Metallurgy and Petroleum Engineering, University of Illinois, Urbana, Ill. Manuscript submitted March 11, 1968. IMD effect of the copper impurity is greater1,2 and it is now evident that their corrosion rates had been much magnified by this effect and did not provide a proper basis for the analysis of segregation. In exploratory studies of other solutes (made under the same conditions), 1000 ppm additions of Mg, Mn, or Si or 100 ppm Ca were without effect.1 Montariol6 noted that boundary attack in 22 pct HC1 persisted after zone refining although with fewer deep fissures (ranges 0.06 to 4 ppm Cu, 4 to 23 ppm Fe). Autocatalytic effects may have influenced these results also and those of Perryman.4 The present objective was, as a first step, to see whether quantitative tests designed to exclude autocatalytic influences would indicate the existence of low-level impurity effects on intrinsic boundary corrosion. Comparison of electrolytically refined with zone-refined aluminum of lower copper and iron contents revealed no differences in boundary corrosion, but certain impurity-sensitive differences in general corrosion morphology were noted and investigated further at higher impurity levels. I) EXPERIMENTAL PROCEDURE A) Material. A selection from commercially available material was made with the cooperation of several producers. An electrolytically refined lot (III-A, 1 ppm Cu, 2.4 ppm Fe) studied previously3 provided a starting point. Since material of substantially higher copper content could not be used if the autocatalytic corrosion reaction were to be avoided,2,3 a lot (III-B) of about the same purity was added as a check, two zone-refined lots (I-A and I-B) with copper and iron an order of magnitude lower were selected for comparison, and an intermediate lot (11) was included. Analytical data are given in Table I. For copper in I-B and iron in I-A and I-B, the actual concentration is thought to be near the limit given, i.e., about 0.1 ppm. For titanium, vanadium, and chromium in III-B, the actual amounts are thought to be, like those in III-A, substantially lower than in the zone-refined lots (these elements concentrate in the solid on freezing). Data are given later for some additional lots surveved. B) Specimen Preparation and Procedure. one by 3 cm blanks with a notched stem were cut from 1-mm cold-rolled sheet, annealed 24 hr in air at 650°C, and quenched in an air stream (42°C per sec initial cooling rate, 100 sec to cool to 100°C). The high annealing temperature maximized diffusivities and approach to equilibrium impurity distributions. A water quench, in principle more efficient in preserving the distribution established, was undesirable because the boundaries were almost plane and they tended to shear and migrate during the quench and thus to be separated from any existing impurity atmosphere. Test procedures, previously described,3 involved electropolish-ing, etching 2 min in 10 pct HF at 24.0°C, and expos-

Jan 1, 1969

Arthur Jarman, Sydney, New South Wales, Australia (communication to the Secretary*):—All designs for modern metallurgical and chemical laboratories should provide each student's desk with a hood or cupboard for the removal of fumes, but I doubt the advisability of placing air-baths and similar apparatus close to the hot plate. It seems to me that unless the draft be exceptionally strong the fumes from ordinary wet assay work will corrode the iron-work of the fittings, in which case the baths would have to be removed to a general desk in order to lighten the work of the laboratory attendant. Since the laboratory described by Mr. White has been in use for two years, I should like to ask if any inconvenience has resulted from this corrosion. If not, it is certainly an important improvement to have the air-baths and similar apparatus placed on the student's desk. The hoods described by Mr. White are supplied with a good draft by means of a fan, which gives them a great advantage

Jan 1, 1905

By F. W. Bloecher

S. Mortsell and J. Svenssofi (Royal Institute of Technology, Stockholm, Sweden)—Bloecher states that the apparatus described by him should be a suitable instrument in the mineral dressing laboratories for determining the specific surface of such granular products that are generally investigated. We want to express a somewhat different opinion, as we doubt that the gas adsorption method of surface measurement really is the most suitable method in mineral dressing laboratories. It is well known that the surface area, as measured by this method, does not coincide with the surface area calculated from the size, shape, and number of particles, i.e. the superficial surface of the particles. It can be seen easily from Mr. Bloecher's own determination on ilmenite-leucoxene concentrate that the surface area measured according to this method may be several hundred times larger than the superficial surface. It is supposed that the surface of cracks, fissures, and pores within the particles also is included in the measured surface. However, this is an assumption which scarcely can be proved and certainly has not been proved. We believe that the mineral engineer could better use a method giving the superficial surface of the particles, as in most cases this surface only is of importance to him. Such is certainly the case when calculating the resistance of the fluid flow through granu- lar materials and the capillary forces of such materials, problems which are of great importance in connection with dewatering, filtration, and pelletizing'" etc. The same may also be the case when studying flotation problems, partly since the quantities of the introduced reagents usually are so small that they can only cover the most accessible surface of the particles, and partly since the molecules of at least the collecting reagents are so large that they cannot enter the smallest cracks and pores. As to the surface, which is of consequence in the application of Rittinger's law of crushing, one is inclined to believe, from theoretical reasons and from the work by Gross and Zimmerley, that the total surface here is the most important one. However, it seems as if in that case the superficial surface was as important as the total surface. Other reasons making the gas adsorption method less suitable for use in the mineral dressing laboratories are that the granular materials there very often are too coarse to be measured by this method, that the experimental technique is rather difficult, and that it takes a long time to measure the specific surface of a sample. Besides, the validity of the method must still be considered questionable. It is thus well known that with different gases one usually gets different values of the specific surface of the same sample, which values, even with such an ideal material as metal foils, can differ as much as about 50 pct.'" Still more serious

Jan 1, 1952

By G. L. Hassler, E. Bruner

An apparatus and method is described whereby the relation between saturation and capillary pressure under decreasing saturation can be quickly determined for small core samples. The initially saturated core is cen-trifuged at increasing rates and the average saturation is measured at each rate with the aid of a stroboscope device. A theory and calculation procedure is given whereby the accelerations and saturation values can be converted into a true curve of capillary pressure versus saturation. The present work differs from previously described use of the centrifuge to obtain capillary-pressure curves of core samples3 in that the core is centrifuged alone, so that the whole range of saturations required by the properties of the sample and the radially varying centrifugal force occurs within the sample. The calculation procedure nevertheless secures correct results from simply obtained values of the average saturation. The apparatus described was developed in connection with studies of capillary pressure and wetting of oil-field rocks, and the paper provides the apparatus background for a previous publication' dealing more fully with the uses and implications of the data in petroleum engineering. The method is applicable, however, to general combinations of immiscible fluids and porous or comminuted solids, and may be useful in other fields. Introduction The importance of capillary phenomena in determining the behavior of liquids in porous media has long been recognized. The concept of capillary Pressure was early formulated, and in recent Years discussions of the application of the laws of capillarity to oil field problems have appeared.l-3 One reason why progress in the application of capillary phenomena to the solution of problems of reservoir mechanics has not been more rapid has been the lack of a, satisfactory technique for measuring the capillary pressures in reservoir rocks. It is the principal purpose of this paper to describe a method by which the relation between capillary pressure and saturation can be determined for small consolidated core samples which have been extracted and resaturated, Capillary Diaphragm Perhaps the most direct way to measure the capillary pressure in a rock is to make piezometric contact with the wetting liquid through a diaphragm of porous material with high displacement pressure saturated with the liquid in question.3-6 The liquid in the diaphragm assumes the pressure of the liquid in the core, which can then be measured with a manometer, while the atmospheric air is prevented by capillarity from entering the diaphragm and affecting the pressure measurements as long as the displacement pressure of the diaphragm is not exceeded. With an apparatus of the type illustrated schematically in Fig. I, the relation between capillary pressure and saturation can be measured for a small core sample by starting with the core saturated 100 per cent, applyillg successively greater suctions

Jan 1, 1945

By R. W. Snyder, H. J. Ramey

This paper presents the results of applying the Buckley-Leverett' displacement theory to petroleum reservoirs consisting of a finite number of layers. The layers are assumed to communicate only in the wellbores, and the reservoir may be represented as a linear system. Most previous investigations of this nature were limited by assumptions and by inconsistent calculation techniques. This study improves on previous work by applying the Buckley-Lev-erett displacement theory to a noncommunicating layered system where permeability, porosity, initial saturation, residual saturation and relative permeability vary from layer to layer in a logical and consistent manner. Gravity and capillary-pressure effects are neglected. A modification of the Higgins-Leighton calculation method was used in this study. Waterflood predictions were made with all properties varying, and then with only permeability varying using several inability ratios. These results were compared with the Stiles and Dykstra-Parsons predictions. It is shown that the latter methods generally give poor values for the breakthrough recovery and pessimistic predictions for the performance after breakthrough. Similar results were obtained for a gas-displacement case. lNTRODUCTION Field experience with immiscible displacement usually shows constant producing conditions until breakthrough of the displacing fluid. Then oil production continues at increasing displacing-to-displaced fluid ratios until the economic limit is reached. Three different ideal mechanisms are known that will produce this behavior: (1) relative permeability effects as described by Buckley-Leverett frontal advance theory,' (2) vertical stratification as considered by Stiles,2 Dykstra and Parsons5 and others and (3) different path lengths involved in areal (two-dimensional) flow between wells as described by Dyes et al.4 Without question, a combination of these factors modified by formation heterogeneity and other known and unknown factors actually does control the behavior of real systems. This paper presents results of an investigation of certain factors that should affect performance but which have received little attention to date. In 1944, Law5 demonstrated that porosity and perme- ability are often found to have normal and logarithmic-normal distributions, respectively. throughout cored intervals in natural formations. This led to the concept of the noncommunicating, multilayered reservoir model for immiscible displacement. This model assumes that the reservoir is composed of a number of layers that communicate only at the wellbores. Each layer is individually homogeneous, but may be different from every other layer. Stiles' presented one of the earliest applications of this model to waterflood performance. In addition, Stiles assumed that the initial saturations and relative permeabilities were the same for each layer, porosity was the same. displacement was piston-like, fluids were incompressible and injection into each layer was proportional to that layer's permeability capacity (permeability-thickness product). The last assumption would be true if the mobility ratio for the displacement were unity.21 Dykstra and Parsons" used the same model as Stiles, but rigorously included mobility ratios other than unity for piston-like displacement. Dykstra and Parsons used their general result to produce charts for log-normal permeability distributions between layers. Similarly, Muskat6 Pub1ished analytical solutions for linear and exponential permeability distributions. In 1959, Roberts' described a scheme for calculating water-drive performance for the noncommunicating, layered reservoir model which considered two-phase flow in the displaced region. Roberts used the same model and assumed that the injection rate into a layer was proportional to that layer's permeability capacity, but that flood front locations could be evaluated from the Dykstra-Parsons results. These assumptions are inconsistent, and a material balance cannot be maintained except for a mobility ratio of unity. At the same time, Kufus and Lynch8 coupled Buckley-Leverett displacement theory with the layered model to provide an improvement of the Dykstra-Parsons method that was consistent. In 1960, Higgins and Leighton9 resented a numerical method for calculating waterflood performance also considering two-phase flow in the displaced region. The result was used to investigate variation in absolute permeability and oil viscosity. An excellent, detailed history of using the noncomrnunicating, layered reservoir model was presented by Nielsen.'" The preceding techniques (and many related ones) were similar in that differences in initial saturations, residual saturations and relative permeabilities from layer to layer were neglected. It is well known that the irreducible water saturation is an important function of absolute permeability. Calhoun11 showed that the irreducible water saturation

By Henry P. Ehrlinger, James C. Bradbury

Tripoli is a naturally occurring, very finely divided form of silica found chiefly in some midwestern and southeastern states and used commercially as fillers and abrasives. Definitions Tripoli is a microcrystalline, finely particulate, more or less friable form of silica that appears to be the product of leaching of siliceous limestone or calcareous chert. The term was originally applied to a deposit near Seneca, Mo., that resembled material of that name found near Tripoli in North Africa (Hovey, 1894). The two deposits were subsequently found to have different physical characteristics -the North African tripoli, now called tripolite, is a diatomite, composed of the siliceous skeletons of microscopic marine plants called diatoms, and the Missouri tripoli contains no diatom remains; the term tripoli, however, continued to be used for the Missouri material and is now applied in a general way to most silica deposits similar to it in characteristics and geologic origin. In commercial trade tripoli is commonly understood to designate material from the Missouri-Oklahoma field; silica from southern Illinois, the other major producing area, is referred to commercially as amorphous silica. Each term, however, may be used commercially for material, regardless of place of origin, that has the characteristics or uses commonly ascribed to the material from one or the other major producing area. For example, in the commodity price listings, Engineering and Mining Journal routinely lists under Tripoli, prices "f.0.b. Elco, III." and "f.0.b. Seneca, Mo., and Rogers, Ark.," and under Silica, amorphous, prices "f .o.b. Ill.," and "f .o.b. Dierks, Ark." Amorphous silica, the commercial designation given to southern Illinois tripoli, is, like the term tripoli, a misnomer. Mineralogically, the southern Illinois deposits are composed of microcrystalline quartz, and no amorphous material has been detected during X-ray and scanning electron microscope investigations (Leamnson, Thomas, and Ehrlinger, 1969; Thomas et al., 1970). Soft silica is another term that has been applied to Illinois and Tennessee tripoli, presumably to distinguish it from the more compact Missouri material. It has also been used in the ceramic trade to distinguish tripoli from "hard" silica, or silica flour, produced by pulverizing silica sand (Heinz, 1937). Rottenstone, produced commercially in Pennsylvania, is similar to tripoli in that a major constituent is finely particulate silica, and its uses are much the same as those of tripoli- as abrasives and fillers. The origin of rottenstone also is similar to that of tripoli-decomposition of a siliceous sedimentary rock. The parent rock is defined as a siliceous limestone (Gary, McAfee, and Wolf, 1972; Thrush, 1968) or as shale (personal communication). Heinz (1937) quotes a brief statement describ-

Jan 1, 1975

By K. P. Gupta, P. C. Panigrahy

The stabilization of the R, a-Mn, and 0-Mn phases have been studied in the Mn-Ti-Fe and Mn-Ti-Co systems. Iron and cobalt both appear to stabilize the (Mn-Ti) R phase to almost the sarne extent. The R-phase region was found to extend from the lowest e/a to slightly beyond the maximunz e/a limit known for this phase. But, while iron appears to stabilize the a-Mn phase, cobalt tends to stabilize the p-Mn phase. In the two systems manganese appears to get replaced by iron and cobalt in each of the mentioned phases. The instability of the a-Mn phase in the Mn-Ti-Co system and the /3 -Mn phase in the Mn-Ti-Fe system cannot be explained on the basis of adverse size effects because atomic diameters for both iron and cobalt (C.N. 12 at. diam) are ziery similnr and not much different from manganese which they replace. Qualitatively, the reason for the stability of the a-Mn and the p-Mn phases can be traced to the more favorable e/a ratio prevailing in the respective systems and to a competing tendency between the two phases. In transition metal alloy systems the o, p,P, R, a- Mn,' and p-Mn2 phases have been claimed as electron compounds. A large volume of work has been done to establish the criterion for the formation of the o phase but until very recently practically no systematic work was done on the a-Mn and the /3-Mn phases. A recent investigation on the P-Mn phase3 indicates the e/a criterion for p-Mn phase stabilization. Since the R phase was first known to appear only in certain ternary systems1 no detailed work was then possible for this phase. The R phase has been recently discovered as a binary intermetallic compound in the Mn-Ti~ and Mn-si~-' binary systems. The existence of binary R phases opens up the possibilities of studying the effect of alloying elements on the stabilization of the R phase. Of the two binary systems possessing an R phase, the Mn-Ti system appears to be more interesting because at a suitable high temperature it is possible to find the three electron compounds, the a-Mn, p-Mn, and R phases, side by side and it is possible to study the effect of a third transition element on these three electron compounds. For the present investigation iron and cobalt, so called B elements for the formation of electron compounds, have been used as the third element to study the stabilization of the a-Mn, P-Mn, and R phases. EXPERIMENTAL PROCEDURE The alloys were prepared by using 99.9 pct pure electrolytic Fe and Mn, 99.5 pct Co, and crystal bar titanium, supplied by Semi Elements Inc., New York and Gallard Schelsinger Mfg. Co., New York. Weighed amounts of the components were melted in recrystal-lized alumina crucibles in an inert atmosphere (argon) high-frequency induction melting unit. Titanium was made into fine chips for easy dissolution and a special charging procedure was adopted to avoid contacts of titanium chips with the alumina crucibles. Up to 20 at. pct Ti, the maximum titanium content in the investigated alloys, there was no visible sign of reaction of titanium with the alumina crucibles. With a careful control of melting time and temperature the losses were minimized and were always found to be below 0.1 pct. Because of such small and almost constant weight losses, the alloys were not finally analyzed. The alloys were wrapped in molybdenum foil and annealed in evacuated and sealed silica capsules at 1000" * 2°C for 72 hr and subsequently quenched in cold tap water. Annealed samples were examined metallographically and by X-ray diffraction. For all high manganese alloys oxalic acid solutions of various concentrations and 1.0 pct HN03 solution were found suitable as etching reagents. Best contrast between the a-Mn and the R phases could be obtained by using freshly prepared 60 pct glycerine + 20 pct HN03 + 20 pct HF solution. For high iron and cobalt containing alloys, especially for alloys containing the a-Fe, y-Fe, and P-Co phases, 15 cc HNOJ + 60 cc HC1 + 15 cc acetic acid + 15 cc water solution was found to be the best etching reagent. All X-ray diffraction work was carried out (using specimens prepared from annealed powders) with a 114.6 mm diam Debye-Scherrer camera using unfiltered FeK radiation at 25 kv and 10 ma. All calculations for X-ray diffraction work were carried out using an IBM 7044 digital computer RESULTS AND DISCUSSION The two ternary systems, MnTiFe and MnTiCo, were investigated near the manganese rich end, Figs. 1 and 2, and show some common features. In both alloy systems large extensions of narrow R phase regions occur at almost constant titanium contents. At titanium contents higher than that of the single phase R-phase alloys, the same unidentified X phase was found in both ternary systems. The extensions of the X phase close to the Mn-Ti binary indicate that this phase could be the TiMns phase. Too few X phase diffraction lines were present in the diffraction patterns to make positive identification of the X phase. In contrast to this similarity the two systems show opposite behavior in the extensions of the a-Mn and 8-Mn phase regions; while iron tends to stabilize the a-Mn phase, cobalt

Jan 1, 1970

By AIME AIME

TWO papers, "Calcium, Strontium, and Barium Metals," by Charles Hardy and Paul M. Tyler, and "The Mining of Gems and Ornamental Stones by American Indians," by Sydney H. Ball, were presented before the Rare Minerals and Metals group at its session Tuesday afternoon in the Auditorium. Donald M. Liddell, chairman, presided. Mr. Tyler summarized the first paper, outlining the uses, history, occurrence, manufacture, production and trade, markets and prices of the three metals. In discussion, in response to the chairman's query on "what are they doing in Russia with calcium, strontium, and barium," Guy C. Riddell replied that nothing is being done on a production basis. The great rare metals plant in Moscow is active, however, on other elements. "They are making radium chloride, uranium oxide, vanadium, cadmium, tungsten, molybdenum, selenium, antimony compounds; and mercury, nickel and arsenic are under production at interior plants. The rare metals plant is busily conducting research on beryllium, rhenium, lithium, bismuth, strontium and zirconium. These are the main rare metal activities. Much hard-alloy work. for cutting and facing, is under way:

Jan 1, 1933

By N. R. Morrow, C. C. Harris

The experimental points which describe capillary pressure curves are determined at apparent equilibria which are observed after bydrodynamic flow has ceased. For most systems, the time required to obtain equalization of pressure throughout the discontinuous part of a phase is prohibitive. To permit experimental points to be described as equilibria, a model of capillary behavior is proposed where mass transfer is restricted to bulk fluid flow. Model capillary pressure curves follow if the path described by such points is independent of the rate at which the saturation was changed to attain a capillary pressure point. Aemodified suction potential technique is used to study cyclic relationships between capillary pressure and moisture content for a porous mass. The time taken to complete an experiment was greatly reduced by using small samples. INTRODUCTION Capillary retention of liquid by porous materials has been investigated in the fields of hydrology,l soil science,2 oil reservoir engineering,3 chemical engineering," soil mechanics,5 textiles: paper making: and building materials In studies of the immiscible displacement of one fluid by another within a porous bed, drainage columnsl and suction potential techniques2 have been used to obtain relationships between pressure deficiency and saturation (Fig. 1). Except where there is no hysteresis of contact angle and the solid is of simple geometry, such as a tube of uniform cross section, there is hysteresis in the relationship between capillary pressure and saturation.2 The relationship which has received most attention is displacement of fluid from an initially saturated bed (Fig. 1, Curve R2), the final condition being an irreducible minimum fluid saturation Swr. Imbibition (Fig. 1, Curve A), further desaturation (Fig. 1, Curve R), and intermediate scanning curves have been studied to a lesser but increasing extent.2 ,3,9-12 This paper first considers the nature of the experimental points tracing the capillary pressure curves with respect to the modes and rates of mass transfer which are operative during the course of measurement. There are clear indications that the experimental points which describe these curves are obtained at apparent equilibria which are observed when viscous fluid flow has ceased; and any further changes in the fluid distribution are the result of much slower mass transfer processes, such as diffusion. Unless stated otherwise, this discussion applies to a stable packing of equal, smooth, hydrophilic spheres supported by a suction plate5 with water as the wetting phase and air as the nonwetting phase. The discussion can also be applied, in many

Jan 1, 1966

By William Hurst

This is a presentation of the diffusivity theory for the calculation of the water drive on an oil reservoir in which the history of reservoir pressure with time are the essential parameters for the determination of the rate and cumulative water encroachment into a field. The main body of the paper is essentially the application of the principles underlined here to actual field data. It consists of the work plots of the radial-flow case, and includes a discussion of an illustrated problem for which the water-drive calculations are treated in conjunction with the volumetric-balance equation. The appendix is a mathematical treatment of the linear, radial, and spherical cases of water influx into a reservoir. Introduction The evaluation of oil reserves and the prediction of pressure behavior with different rates of production are related to the volumetric balance of the fluids entering and leaving the space occupied by the oil and gas originally present in the formation; that is to say, important information can be gleaned from a volumetric study of the oil, gas, and water produced from a formation as it affects the extent of change in volume of oil zone, the gas cap, and the amount of water influx from the adjoining water sands. It is not the purpose of this paper to enter into a discussion of the equation of volumetric balance, in which such pertinent information as subsurface sampling and the measurement of reservoir pressures play a predominant part, as this has been discussed in detail by others.1,2 However, there is an inherent difficulty that has limited the general application of this equation to a study of oil reservoirs; that is, the insufficient knowledge of the analytics for expressing the water drive on a field as a function of reservoir pressure. This to a large degree has been overcome and it is the purpose of this paper to present this theory in such form as to be applicable for reservoir calculations. Water Drive If the amount of oil originally in place and the gas space are known, it is a relatively simple matter to determine, by the volumetric equation, the cumulative water influx into a reservoir from the adjoining water sands. Often, however, the oil reserve as well as water influx must be 'determined, and in order to be able to make this calculation it is essential to assign a mathematical relationship for the varying water term that is compatible with conditions known to exist in the formation and gives an accuracy acceptable for engineering calculations. Various equations have been employed empirically by different investigators in making reservoir studies of water drive. One form used by Schilthuis2 expresses the rate of water influx into a reservoir at any time as proportional to the pressure

Jan 1, 1943

By William Hurst

This is a presentation of the diffusivity theory for the calculation of the water drive on an oil reservoir in which the history of reservoir pressure with time are the essential parameters for the determination of the rate and cumulative water encroachment into a field. The main body of the paper is essentially the application of the principles underlined here to actual field data. It consists of the work plots of the radial-flow case, and includes a discussion of an illustrated problem for which the water-drive calculations are treated in conjunction with the volumetric-balance equation. The appendix is a mathematical treatment of the linear, radial, and spherical cases of water influx into a reservoir. Introduction The evaluation of oil reserves and the prediction of pressure behavior with different rates of production are related to the volumetric balance of the fluids entering and leaving the space occupied by the oil and gas originally present in the formation; that is to say, important information can be gleaned from a volumetric study of the oil, gas, and water produced from a formation as it affects the extent of change in volume of oil zone, the gas cap, and the amount of water influx from the adjoining water sands. It is not the purpose of this paper to enter into a discussion of the equation of volumetric balance, in which such pertinent information as subsurface sampling and the measurement of reservoir pressures play a predominant part, as this has been discussed in detail by others.1,2 However, there is an inherent difficulty that has limited the general application of this equation to a study of oil reservoirs; that is, the insufficient knowledge of the analytics for expressing the water drive on a field as a function of reservoir pressure. This to a large degree has been overcome and it is the purpose of this paper to present this theory in such form as to be applicable for reservoir calculations. Water Drive If the amount of oil originally in place and the gas space are known, it is a relatively simple matter to determine, by the volumetric equation, the cumulative water influx into a reservoir from the adjoining water sands. Often, however, the oil reserve as well as water influx must be 'determined, and in order to be able to make this calculation it is essential to assign a mathematical relationship for the varying water term that is compatible with conditions known to exist in the formation and gives an accuracy acceptable for engineering calculations. Various equations have been employed empirically by different investigators in making reservoir studies of water drive. One form used by Schilthuis2 expresses the rate of water influx into a reservoir at any time as proportional to the pressure

Jan 1, 1943

The following record of the important responsibilities already shouldered by Dr. Ricketts will give some indication of the trust and confidence reposed in him by his colleagues. The Institute is to be congratulated that a man who is already so much engaged should be willing to assume the further responsibility of guiding the Institute's Ship of state during the ensuing year. Louis Davidson Ricketts, who is brother of Professor Palmer or Chamberlaine Ricketts, President of Rensselaer Polytechnic Institute, was born at Elkton, Md., Dec. 19. 1859, was graduated from Princeton University in 1881 with the degree, Bachelor of Science, chosen a Fellow in Chemistry and W. S. Ward Fellow in Economic Geology, and after two years' study given the degree Doctor of Science. Following the completion of Iris work at Princeton, Dr. Ricketts went to Colorado and started to work as a mine surveyor. For the 15 years following, his time was chiefly occupied in reconnaissance work, geological work and mine examination. From 1887 to 1890 Dr. Ricketts was Geologist for Wyoming, and at, the end of that period transferred his operations to the Southwest. where he has since been steadily engaged in large mining projects. He was identified with the acquisition of the property now owned by the Moctezuma Copper Co., a , subsidiary of Phelps, Dodge & Co., at Nacozari, Sonora, Mex. From 1899 to 1901 he was General Manager of the property and during his administration the concentrator and reduction works were completed and the mines put on a dividend-paying basis

Jan 3, 1916

MARCH 15-Industry is rapidly snapping back from another coal crisis, other business news is in general favorable and the outlook through the Spring is by most observers considered quite promising. Most industries report comfortable backlogs of unfilled orders, department store sales in recent weeks have equalled in dollars those of the corresponding period last year, retail sales of automobiles show again over the same period a year ago, and new orders for machine tools are at the highest figures since August 1946. Orders for railway freight cars have shown a very encouraging pickup, with a total of 9385 cars in January and the N. Y. Central alone ordering 4500 in February. Construction continues very active. In January new housing starts totaled 80,000 against 50,000 a year ago and the daily average contract awards, according to the Dodge reports, were 57 pct larger. In the first 22 days of February the increase in awards was 27 pct. Lumber orders since Jan. 1 have run 22 pct above last year. All of these favorable factors bolster the opinion that the upturn in industrial output and employment which began last summer has not yet spent itself and that the setback caused by the strikes will be made up when people get back to work. Only in a few lines are there indications that primary production may be outrunning the consumption of finished goods, although inventory build-up would seem to be rather modest as the National Association of Purchasing Agents reported in February that 78 pct of its members were buying for 60 days or less. Industrial prices as a whole show no significant trend despite the continued alarm over both the immediate and the long-term possibility of inflation caused primarily by the government's increasing expenditure and its inability to balance the budget. A recent advance of 1.9 pct in primary market prices is viewed by some people as the surface symptom of renewed inflation, but even so it is more than two years since the alltime high was reached by the daily index of sensitive commodities in November 1947. Over two years have passed since prices received by farmers hit their peak and about a year and a half since all wholesale prices and the consumer price index touched their highest points in August 1948. The decline in the wholesale price index has been almost continuous, interrupted only twice by slight advances in the monthly figures from February to March 1949, and, later in the year, from August to September. Of course, this continued decline in the last half of 1949 largely reflects a downward movement in farm and food prices. Wholesale prices for commodities other than farm and food leveled out after June and now stand only slightly under the June level. Farm products are down by 22 pct from January and by 18.6 pct from August 1948. Food prices are down only slightly less. Consequently, the farm price support program is in serious trouble and has imposed a heavy financial burden on the Treasury. In those commodities other than farm products only building materials, chemicals and textiles have come down as much as the average, while housefurnishings and metals and their products have fallen hardly at all. Glancing away from the domestic front, the results of the British general election indicated a highly inconvenient situation, that public opinion there is so exactly deadlocked as to divest the victors of much ability to make forceful decisions or create significant policy. It is generally considered that another election in the near future would give substantially the same result. The British people are equally divided and the politicians are not likely to precipitate another appeal to the country until there is manifest reason to believe that external and internal circumstances have changed sufficiently to permit one party or the other to obtain a decisive verdict. Because of the lack of a clear mandate steel nationalization will likely lag in Britain. In the meantime there is considerable discussion going on as to whether the European steel industries as a whole are at a disadvantage in world competition with the American industry. An article in the "Statistical Bulletin" for January of the British Iron and Steel Federation takes issue on this point with the authors of the Geneva report, observing that they wrote before devaluation, and this particular conclusion "has been overtaken by events." The "Bulletin" also contends that the statement was in any case incorrect so far as Britain was concerned, and that it was based on scanty and insufficient evidence. To support the rebuttal a detailed and extensive comparison is made of the home prices of certain steel products in Britain and in other countries of the world. The accompanying table gives a selection of the prices published. It sets out the changed position since devaluation and since the recent increases in American steel prices. These are home market prices; no doubt in competitive export business some of the price levels could be brought closer together at need.

Jan 4, 1950

By William Hurst

Muskat's depletion performance equation is here derived considering the expansion behavior of the reservoir hydrocarbon system and a simple fractional-flow equation. This nietkod of derivation leads logically to the two extensions that follow. The first of these is concerned with gravity segregation in a depletion-drive reservoir. The second is concerned with including an empirically determined tern? for water influx in the performance equation. The more general equation for gravity segregation when there is a primary gas cap and empirically-determined water influx is stated for completeness. These equations have been found useful in reservoir performance calculations in Eastern Venezuela. A discussion on the methods of solving these equations follows, and considers firstly the effect of taking finite intervals in the numerical integration, and sec-ondly, methods of incorporating the time functions involved in segregation in with the expansion behavior. The paper concludes with a brief general discussion on further extensions to the depletion performance equation. INTRODUCTION The two fundamental sources of energy by which oil is produced from a reservoir result from pressure depletion inside the boundaries of the reservoir and fluid encroachment across the boundaries of the reservoir. The wells in either case form low pressure outlets through which oil and gas may be produced by the expansive force of the reservoir fluids and associated encroaching fluids. When the reservoir pressure is higher than the bubble-point pressure of the oil, so that there is no free gas in the reservoir, these expansive forces are the only ones available for the production of oil. However, when the reservoir pressure is less than the bubble-point pressure of the oil, free gas is vaporized as the pressure falls. With both oil and free-gas phases present, the additional forces of gravity and capillarity may operate on the gas-oil system, as they have previously operated on the oil-interstitial water system. Gravity tends to segregate the free gas from the oil due to their density difference. Capillarity opposes and eventually balances gravity as the more extreme free gas and oil saturations are reached, preventing the independent move- ment of free gas until it is above a certain saturation, and the independent movement of oil when it is below a certain saturation. The type of depletion performance equation chosen for predicting the future performance of a reservoir depends on the amount of past history available. When the reservoir is somewhere past the halfway mark in depletion, some form of decline curve is often used. With less past history, material balance equations which incorporate empirical factors based on the past performance are often used. When, however, the amount of past history is small, the Muskat depletion performance equation will usually be used. The distinguishing feature of this type of equation is that empirical factors based on the over-all or macroscopic reservoir behavior are almost or entirely absent. Each parameter affecting the reservoir performance is ascribed an independent set of values based on measurements made on laboratory samples; that is, incorporating microscopic empirical factors. In establishing Muskat-type depletion performance equations, it is necessary to consider the reservoir as consisting of a number of associated blocks, in each of which the saturations and pressures may be considered uniform, and in each of which all substances have uniform pressure-volume characteristics. Thus, a primary gas cap can usually be considered as one block and an aquifer as another. Gravity segregation may be negligible for practical purposes when the rock and oil properties are adverse and/or the dip or thickness of the reservoir is too small. In this case the whole oil leg may be considered as one block, except in very large reservoirs. In very large reservoirs the fluid and rock properties may vary enough, particularly in the dip direction, for it to be necessary to divide the oil leg into a number of blocks, in each of which the relevant quantities may be considered uniform. When gravity segregation of the oil and free gas is not negligible, it is necessary to consider the space occupied by the initial oil leg as divided into two blocks, a secondary gas cap and an effective oil leg, in each of which saturations may be considered to be uniform. The total volume of these two blocks is thus constant, but the secondary gas cap grows continuously at the expense of the oil leg. Muskat1 derived depletion performance equations for the basic case of an oil reservoir with closed boundaries and without segregation, and for the case of an oil

By W. B. Humes

The use of high vacuum on a large industrial scale in the ferrosilicon process for the production of magnesium marks the coming of age of an important new metallurgical technique. The economical production of reactive metals, such as magnesium, which combine with all the well-known furnace atmospheres, has until recently been successfully carried out only by electrolytic methods. It is now apparent that, through the use of high vacuum, the distillation or sublimation of many metals can be done industrially at much lower temperatures, and hence in much simpler equipment, than heretofore has been thought possible. At the beginning of the present emergency, when the ferrosilicon process of producing magnesium was brought to the fore, little was generally known about vacuum engineering, practices, and techniques. In a comparatively short time, the available equipment has been adapted, new equipment designed and built, and a fund of know-how evolved to make possible the production of thousands of pounds of magnesium per day at pressures less than 1/ r0,000 of an atmosphere. Pilot-plant operations have been consistently maintained at pressures even as low 2s one micron (0.001 mm.). These low pressures, which previously were regarded as prohibitively costly or impossible to attain, have been demonstrated as economically feasible on an industrial scale. Necessity for Vacuum The main function of vacuum in the ferrosilicon process, and hence in most vacuum smelting processes, is to lower the temperature at which the metal may be distilled or sublimed from the reduction mixture. A secondary function is to protect the distilled metal from attack by the furnace atmosphere and to permit the formation of a dense condensate. In the ferrosilicon process, magnesium is formed by the reaction between dolomite and ferrosilicon: 2(Mg0-Ca0) -\- HFeSU / t=> aMg + MFe + (CaO)2-SiO2 The metal is distilled from the pelleted charge at a free air pressure of about 0.100 mm. of mercury (100 microns). This low pressure is not needed for the reaction, but rather serves to protect the metal vapor from the oxygen or nitrogen of the atmosphere and permits the formation of a condensate free of pyrophoric material. The reaction proceeds at air pressures as high as several millimeters of mercury, and evidence has been offered to show that the actual equilibrium pressure of magnesium at operating temperatures of 2I50°F. is somewhat higher. Experimentation indicates that the yield begins to decrease at pressures above 500 microns. While no real operating data are yet available on the relationship between

Jan 1, 1944

By J. R. Kyte, V. O. Naumann, C. C. Mattax

Imbibition and waterflooding tests at reservoir conditions show that conventional tests at room conditions sometimes lead to recovery estimates that are too low. Core samples which are of intermediate wettability at normal test conditions may be strongly water-wet at reservoir conditions. This was found to be true for samples from two of three reservoirs investigated. For the other reservoir, less difference was observed between the wettability of samples at normal test conditions and at reservoir conditions. Samples which became more water-wet at reservoir temperature and pressure also water flooded more efficiently at reservoir conditions. These results show that core analysis tests on intermediate wettability samples should be performed at reservoir conditions to obtain representative data. INTRODUCTION Throughout the oil industry, core analysis tests normally are performed using refined oils and at room temperature and pressure. This procedure has always been subject to question because the possibility is generally recognized that the reservoir environment may influence displacement behavior. Burkhardt, et al,' have performed waterflood tests at reservoir conditions on East Texas cores. They found little difference between results obtained at reservoir conditions and results of conventional flooding tests at room conditions. As they pointed out, however, this situation might not be general since they obtained data on only one rock and crude-oil system. This paper presents data which demonstrate that it is sometimes necessary to perform core analysis tests in a simulated reservoir environment to properly represent the reservoir wettability and displacement characteristics. The work is specifically concerned with reservoirs which were thought to be of intermediate wettability on the basis of conventional test results at room conditions, i.e., core samples imbibed only small amounts of either oil or water and exhibited no decided preferential wettability characteristics. Tests were performed on cores from three such reservoirs to determine their behavior in the reservoir environment. lmbibition and waterflood tests were used to demonstrate the effect of reservoir environment on reservoir rock wettability and displacement characteristics. Results of tests performed at reservoir conditions were compared with results from conventional tests. Imbibition tests were performed on samples from all three reservoirs. Waterflood tests were performed on samples from only one reservoir. Fluid properties for the three reservoirs studied are shown in Table 1. Tests at reservoir conditions were performed using bottom-hole crude oil at reservoir temperature and pressure. The aqueous phase used in these tests was a synthetic brine approximating the reservoir brine composition. Conventional tests were performed at room conditions with refined oils and synthetic reservoir brine. The oil-to-water viscosity ratios were adjusted to the reservoir values. The cores used in all the tests were taken from the reservoirs using either brine alone or a bentonite-car-boxymethylcellulose mud without additives as coring fluids. Previous tests show that these fluids have no significant effect on the wettability of reservoir rock samples.1 The cores were preserved in brine at the wellsite to prevent wettability changes during shipment and storage. Wellsite imbibition tests have been performed on fresh samples from several reservoirs (including Reservoir A) and compared with later laboratory imbibition tests on samples preserved in brine. The comparison showed that the wettability of the preserved cores was the same as that of fresh, surfaced cores at the wellsite.2 IMBIBITION TESTS Conventional imbibition tests were performed on preserved cores using the apparatus and procedures described by Bobek, et al.2 A sketch of the apparatus for imbibition tests at reservoir conditions is shown in Fig. 1. The preserved samples were first centrifuged to expel excess water and then placed in a stainless-steel container which served

By Ross Blake

THE St. Joseph Lead Co. became interested in the Tri-State district in 1921 through acquisition of prospecting and development rights on approximately 20,000 acres of land extending northeastward from the Picher mining field, mostly in Kansas. Prospecting with churn drills was begun the same year and the first commercial ore body was found on the Jarrett tract at the then northern limit of the main Picher field. Operations at this mine began in 1923. Kansas Explorations, Inc., was organized in 1923 by the St. Joseph Lead Co. as a wholly-owned subsidiary to carry on its operations in the Tri-State District from an office at Joplin, Mo. As prospecting of the original acreage proved largely negative, attention was subsequently turned to other sections of the district. Numerous additional leases were acquired and prospected. The Company was successful in developing into operating properties the Jarrett, Isherwood, Robinson, Sullivan and Lotson tracts and, in more recent years, the Ritz, Snapp, Buckingham, Gibson and Jasper mines.

Jan 1, 1947

By Arthur Notman

DESPITE the tremendous drop in the volume of domestic production of metals, their prices, and profits, the world as a whole has managed to produce and consume nearly as much as in 1937. Measured by production, 1937 was the record year for copper, lead, and zinc. The Copper Institute figures for 1938 (estimating December as equal to November) show that although apparent domestic consumption declined 309,422 tons, foreign consumption increased 133.035 tons. The total for 1938 was 1,971,790 tons compared with 2,148,177 tons for 1937. The domestic decline was 38.5 per cent, the foreign increase 9.9 per cent, and the total decline 8.2 per cent.

Jan 1, 1939

Jan 1, 1934