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By K. Leutwyler

The key to realistic casing stress analysis in thermal recovery installations is accurate knowledge of the temperatures involved. Much information leading to prediction of heat losses from tubing string to wellbore has been published. This .same information permits calculation of casing temperature under certain conditions. This paper reviews the basis for most of the published work, the line source solution to the diflusivity equation and examines some of its application criteria in the light of unsteady-state conditions. An alternate finite differences method is presented for correlation, and experimental data pertaining to the heat transfer mechanism in the annulus is reported. In the light of the information presented in the paper, it appears that the assumption of a line source for the tubing-wellbore system is valid even for reasonably short periods of heat flow, .such as "steam soak" operations. The empirically modified equation presented earlier matches computer derived results of the finite differences approach lor periods as short as 50 hours. Previously predicted cas ing temperatures and the associated stress levels are thus verified based on these correlative computations and the reported experimental information. Fall out from the computer output resulting in some studies of the influence of insulating cement properties on casing temperature, and experimentally studied effects of nitrogen placed in the annulus at various pressures., are described. INTRODUCTION Generally speaking, predictions of average casing temperatures have been based on an idealized model involving a centralized tubing string at uniform constant temperature radiating energy towards the casing under steady-state conditions.'. ' Heat is transferred away from the casing to the formation by unsteady-state conduction across thermal barriers consisting of cement and the mud sheath. Heat balances written on the casing permit prediction of instantaneous casing temperatures. During early periods of injection, casing temperature varies appreciably as a function of time; however, for long injection times this variation decays as heat flow from the wellbore to the formation stabilizes, and it becomes virtually negligible as conditions surrounding the wellbore become quasi-steady-state (Fig. 1). Carslaw and Jaeger -escribe a solution to the diffusivity equation for a line source (Fig. 2). A constant supply of heat is introduced into the medium from the line placed into the origin of the x-y coordinate system and parallel to the z-axis. Heat spreads outward in the infinite cylindrical solid and the temperature increase on a line going through point (x, y) parallel to the z-axis at a distance r can be predicted by: The following criterion must be considered: the Carslaw and Jaeger equation is obtained on the basis of a large

Jan 1, 1967

By John Nunes, Frank R. Larson

Temperature-dependent functions of various ten-sile flour stress and fracture parameters were investigated on iron and low composition alloys of Fe-C, Fe-Cr, Fe-Mn, and Fe-Ni. Data were obtained over a range of test temperatures from 200" to -196"C at an initial strain rate of 0.01 min". It was found that the strain-hardening exponent, n, for the Fe-Ni alloys increased significantly at very low testing temperatures with increased alloy addition. Also, the stress and strain at fracture followed a predictable transitional type of behavior. The flour stress-temperature dependence was evaluated employing the relation: M where it is shown that composition can strongly influence the constant M. An empirical formula describing this effect is as follows: M = MI (equivalent at. pct Ni)-'" Some preliminay, tests were run on several commercial steels to test the generality of this relationship. One of the phenomenological explanations of the ductile-to-brittle transition encountered in bcc metals is based upon the difference in the temperature dependence of the flow and fracture stresses.' It states simply that the fracture stress is relatively insensitive to temperature and that the yield or flow stress rises rapidly with decreasing temperature so that, when the flow stress reaches the fracture stress, brittle fracture occurs without appreciable plastic deformation. This behavior is illustrated schematically in Fig. 1 where the ductile-to-brittle transition is shown to occur at two possible temperatures. The lowest temperature, TB, represents essentially completely brittle behavior while the higher temperature, TN, represents "notch" brittle behavior. Support for this theory is obtained when it is observed that fcc metals, which do not commonly have a ductile-to-brittle transition, also do not commonly exhibit any strong temperature de- pendence of the yield stress. This relationship of yield or flow stress behavior with the ductile-to-brittle transition has been generally observed for most metals representative of these two crystallo-graphic structures. One exception to this generalization appears in the case of tantalum where no apparent ductile-to-brittle transition has been observed. However, this may simply be an indication that this type of behavior is not directly related to the flow stress and that some other mechanism such as twinning must also be operative. A comparison of the typical temperature dependence of the yield stress of some representative metals is shown in Fig. 2. In the study of the temperature dependence of the strength of metallic materials, considerable ef-

Jan 1, 1963

By D. K. MACKAY

The production of oil and gas in Arkansas is confined to two distinct and widely separated regions of the state; namely: (1) South Arkansas in the Gulf coastal plain, where 49 fields-many containing two or more reservoirs or pools-yield oil, condensate and gas from beds in the Cretaceous and Jurassic, and (2) Northwest Arkansas, a part of the Arkansas Valley, where only dry gas is produced in 21 fields from sandstones of Pennsylvanian age. Exploration during the year 1945 centered largely in these two producing regions, but some of the geophysical surveys were made and wildcat drilling was done a considerable distance outside these regions.

Jan 1, 1946

By F. H. Buchella, J. F. Buchanan

The San Manuel copper deposit is located about 45 miles northeast of Tucson. The concentrator, smelter, administration building, and other plant facilities are located about seven miles southeast of the ,nine area at the new town of Sari Manuel as shown on Figure 1 (Sketch).

Jan 1, 1961

By J. Geertsma, F. de Klerk

During the hydraulic fracturing treatment of an oil or gas well the liquid pressure in the borehole is increased until tensile stress in the surrounding rock exceeds tensile strength. Once a tensile fracture is initiated, it is penetrated by liquid from the borehole and fracture propagation under continuous hydraulic action takes place. The fracturing liquid carries a propping agent to ensure a highly permeable flow channel after pressure release. Field results range from failure to obtain increased production to outstanding success. In all cases, however, it unfortunately remains uncertain whether the values chosen for the operational parameters, such as injection rate, pumping time and fluid viscosity, were in fact the ideal ones. Though experience provides a lead, a more satisfactory way to predict results would seem to be to subject the fracture propagation process to a theoretical analysis that (1) makes the maximum use of the relevant physical information and (2) so simplifies the resulting calculations that the field engineer gets practical data that he can handle comfortably. We are attempting here to do this in connection with the prediction of fracture width and areal extent before pressure release. What remains of the fracture afterwards depends on the distribution of the propping agent between the fracture walls, and that is a separate story. Idealization of the Problem To keep the problem tractable, a number of simplify- ing assumptions have had to be made: 1. The formation is homogeneous and isotropic as regards those of its properties that influence the fracture-propagation process. 2. The deformations of the formation during fracture propagation can be derived from linear elastic stress-strain relations. 3. The fracturing fluid behaves like a purely viscous liquid; i.e., any peculiar flow behavior due to the addition of gelling agents or other additives is neglected. Moreover, the effect of the propping agent distribution on the distribution of fluid viscosity in the fracture is not taken into account. 4. Fluid flow in the fracture is everywhere laminar. 5. Simple geometric fracture-extension patterns are assumed — either radially symmetrical propagation from a point source (Fig. 1A) or rectilinear propagation originating from a line source (Fig. 1B). In the first case the periphery of the fracture is circular, in the second case it is rectangular. 6. A rectilinear propagation mode can be accomplished only by injection over a large perforated interval, thus forming a line source. Such a rectilinear fracture must therefore be located in the vertical plane. A circular propagation mode might be expected from injection through a narrow band of perforations. This forms a point source. Because gravity effects are excluded from our considerations, the fracture propagation plane may in this case assume any angle with respect to the wellbore as far as the

Jan 1, 1970

By D. A. Elgillani, M. C. Fuerstenau, J. D. Miller

Adsorption of lead and ferric iron on quartz and alumina is presented as a function of pH. Only the hydrolyzed species of these metal ions, FeOH++ and PbOH+, adsorb significantly on each of these minerals. Zeta potentials of quartz were measured as a function of pH in the presence of various additions of aluminum, lead, and magnesium salts. Sign reversal occurs at the pH values where significant concentrations of hydroxy complexes are formed. Models of adsorption are presented in the absence and presence of collector. The mechanism of adsorption of metal and collector species in the activation of nonmetallic minerals is still the center of considerable discussion in spite of the extensive study given this system. Until recently, the view was widely held that hydrated metal ions were responsible for this phenomenon. This fact is surprising, since it had been shown that the pH range in which flotation is effected corresponds to that in which metal ion hydrolysis occurs.' Additional support of this concept was pro vided by the work of Wolstenholme and Schulman in another system.' Later work has shown that hydroxy complexes of metal ions are the active species. These studies have also indicated that basic aqueous complexes of metal-collector may be necessary for flotation.3-7 Depending on the molecular weight of the collector, formation of these complexes may occur before or after precipitation of the metal-collector salt has occurred. Ion pair formation can occur when low molecular weight collectors are involved because relatively high concentrations of metal hydroxy complex and collector can be present in solution before precipitation occurs. This is not the case when high molecular weight collectors are used. A model of aqueous complex adsorption has been presented6,7 in which it has been assumed that adsorption occurs by the formation of water from adsorbed hydroxyl and hydrogen of the hydroxyl contained in the complex. Other authors8 have suggested that hy-droxy complexes are involved in these systems but that collector adsorption occurs by replacement of the hydroxyl of the adsorbed metal hydroxy complex with a fatty acid anion. All of these investigations have involved mineral surfaces that were negatively charged so that it is not possible to state with certainty whether hydrated metal ions or hydroxy complexes are the active species in this system. Use of a positively charged mineral should be helpful, however, since the hydrated metal ion will be repelled from this surface. On the other hand, if the hydroxy complex adsorbs by splitting out water, surface charge should have no effect because of the free energy decrease that the system will experience when water is formed. In this regard, sapphire is well-suited for study, since its surface is positively charged until approximately pH 9. Electrokinetic studies of quartz in the presence of various metal ions should also be useful in establishing the mechanisms of adsorption in these systems. That is, if the hydroxy complexes adsorb by water formation, drastic changes in the zeta potential should occur in the pH range in which hydrolysis occurs. In this view, adsorption of ions of widely different hydrolysis characteristics on both sapphire and quartz was measured. In addition, zeta potentials of quartz were measured as a function of pH in the presence of various metal ions and compared with flotation responses obtained under similar conditions. Experimental Materials and Techniques Reagent-grade aluminum, ferric and magnesium chlorides, and lead nitrate were used in this investigation. Adjustments in pH were made with reagent-grade HCl or KOH. Conductivity water, made by passing distilled water through an ion exchange column, was used in all of the experiments.

Jan 1, 1971

By K. P. Fournier

This report describes work on the problem of predicting oil recovery from a reservoir into which water is injected at a temperature higher than the reservoir temperature, taking into account effects of vis cosity-ratio reduction, heat loss and thermal expansion. It includes the derivation of the equations involved, the finite difference equations used to solve the partial differential equation which models the system, and the results obtained using the IBM 1620 and 7090-1401 computers. Figures and tables show present results of this study of recovery as a function of reservoir thickness and injection rate. For a possible reservoir hot water flood in which 1,000 BWPD at 250F are injected, an additional 5 per cent recovery of oil in place in a swept 1,000-ft-radius reservoir is predicted after injection of one pore volume of water. INTRODUCTION The problem of predicting oil recovery from the injection of hot water has been discussed by several researchers. l-6,19 In no case has the problem of predicting heat losses been rigorously incorporated into the recovery and displacement calculation problem. Willman et al. describe an approximate method of such treatment. 1 The calculation of heat losses in a reservoir and the corresponding temperature distribution while injecting a hot fluid has been attempted by several authors.7'8 In this report a method is presented to numerically predict the oil displacement by hot water in a radial system, taking into account the heat losses to adjacent strata, changes in viscosity ratio with temperature and the thermal-expansion effect for both oil and water. DERIVATION OF BASIC EQUATIONS We start with the familiar Buckley-Leverettg equation for a radial system:* This is sometimes referred to as the Lagrangian form of the displacement equation. If the injection water is at some temperature Ti which is above reservoir temperature TR, then lw, the flowing fraction which is water, is a function of both water saturation and fluid temperature at any given time and position in the reservoir. The temperature dependence of lw results from the temperature dependence of the viscosity ratio µo/µm of which lw is a function. Thus:

Jan 1, 1966

By H. L. Miaw, A. M. Gaudin, D. W. Fuerstenau

A quantitative method for evaluating density of slime coatings has been developed and applied to formation of iron oxide slime coatings on quartz and on corundum. Slime coating density is related to flotation recovery and to properties of the electrical double layer at mineral surfaces. IN spite of considerable study, the nature of slime coatings in flotation is still not completely understood. However, phenomena that control floc-culation and dispersion of colloidal systems are now interpreted in terms of electrical double layers.",' Colloids will flocculate even though the particles carry the same charge, but when two dispersed colloids of opposite charge are mixed. flocculation ensues even more rapidly. Analogous phenomena seem responsible for slime coating on minerals in flotation systems. To shed new light on the issue it was considered desirable to devise a tool that would measure slime coatings. The usual method has been to examine photographs of presumably representative surfaces, after. an intervening washing in running water. But such an examination is non-quantitative, and the changes in chemical environment represented by the washing may have removed the slime coatings that existed during flotation. To provide the possibility for a correlation with electrical double layer phenomena, the experiments were made with quartz, corundum, and iron oxide, for which elec-trokinetic data are available.'-" Since the properties of the electrical double layers of these oxides depend on the pH of the solution, pH will be the most important variable. Furthermore, because the zero point of charge for silica, iron oxide, and alumina occurs at pH 3.7, 8, and 9.5, respectively, the relative charge on the slime and mineral can be changed over wide ranges. Because of its practical importance in quartz flotation, iron oxide powder was chosen as the slime. Also, its uniform composition, contrasting color, and ease of analysis make experimentation simple. In this investigation, correlation was sought between the effect on flotation recovery of slime addition and slime coating density. Materials and Methods Details are available in a thesis by Miaw." The quartz was selected from pure Brazilian crystalline quartz, crushed, sized (65/150 mesh) acid-cleaned, washed, and stored in conductivity water. The corundum (synthetic alumina of high purity prepared by Linde Co., Chicago) was crushed, sized (65/100 mesh) deslimed, boiled in nitric acid, washed, and stored in conductivity water. The iron oxide slime, reagent-grade ferric oxide (—400 mesh) from Allied Chemical & Dye Corp., was heated to 160°C, cooled, and stored in a vacuum desiccator. In the electron microscope the slime particles appeared to be about 0.3µ in size, but their large specific surface (87,900 cm per g, by gas-adsorption method, using krypton) suggests that the actual particles are smaller than 0.3r. Had they been perfect nonporous spheres, they would have had a diameter of 0.13µ.

Jan 1, 1959

By JOHN LANE DYNAN

HE Tonopah Extension property consisted originally of three claims, with an area of 38 acres. In 1902 a shaft, now known as No. 1, was started near the eastern end of the property, close to the Tonopah Mining Co.'s boundary line, in the. andesite cap rock' which covers the ore-bearing formations in the western end of the Tonopah district. A short distance below the 60-ft. level, the orebodies pinched out, although the veins continued. This shaft has not been used since 1916. Before 1910, the production was small, coming mostly from small shoots of high-grade shipping ore. In that : year, the, company started its 30-stamp mill and cyanide plant; the mill was later enlarged to 50 stamps, with a corresponding increase in the cyanide-plant capacity, which brought the capacity of the mill up to 350 .tons per day. The total production of the mine to Oct. 1, 1920, is 871,177 tons of ore, from which was recovered 15,267,216 oz. of silver and 156,241 oz. of gold.' This makes an average recovery per ton of 17.5 oz. silver and 0.179 oz. gold. The average price received for silver since' the beginning of operations is 65.87 c. per oz., and the average value recovered from the ore-'is $15.25. The area of the property has been gradually increased by purchases and consolidations of adjoining ground until it is now 647 acres. A new shaft, known as No. 2, was started in 1912, 1600 ft. west .of No. 1, and in the following year a crosscut on the 750-ft. level of this shaft resulted in the discovery of the. Murray Vein system, from which the greatest prosperity of the mine has come. This vein, with its related veins,

Jan 1, 1921

By R. F. Rolsten

VAN Arkel 1 prepared ductile tantalum by the thermal decompoiition of tantalum pentachloride on a resistively heated wire (2000° C) in an evacuated bulb maintained at 100°C. Burgers and Basart2'3 observed the formation of a mixture of tantalum carbide and free metal when a carbon deposition base was used. campbel14 suggested the thermal decomposition of the iodide if a lower decomposition tem- perature was desired. To date, the details for preparing high-purity iodide tantalum have not been disclosed. EXPERIMENTAL The tantalum to be purified was symmetrically placed around the clear quartz deposition surface centrally located within a 64 mm cylindrical Vycor bulb. The deposition vessel usually employed5 was modified6 by incorporating a reentrant fin,mer in place of the customary metal filament in the head

Jan 1, 1960

By Gorr W. W., Wyche E. H, R. Smith

The combination of high strength and corrosion resistance of cold-worked 18 Cr, 8 Ni steel has been advantageously utilized for some time, particularly in aircraft and rail car structures. There are, however, certain limitations on the use of such materials because the high strengths can be obtained only by cold-working, limiting the available products to sheets, strip, wire and tubes. The authors sought to overcome these limitations by resorting to precipitation-hardening, which has been used so successfully in nonferrous metallurgy but only to a limited extent in iron-base alloys. Accomplishment of this objective not only overcame the limitations, but also effected certain improvements in mechanical and other properties. This paper is an account of the development by Carnegie-Illinois Steel Corporation of a precipitation-hardening 18-8 stainless steel (called Stainless W‡ and tentatively identified as type 322). A description is given of its composition and metallurgical characteristics, heat-treatment, physical and mechanical properties and corrosion resistance. Development of the New Steel For a considerable length of time the authors were unable to determine the mechanism of the precipitation-hardening process that had been noted by Ffield18,19 in 18-8 Ti or 18-8 Cb after cold-working and reheating to moderately elevated temperatures. All known variables were exhaustively studied, but with little success. However, results began to indicate that chemical composition was the most important variable, particularly the ratio of austenite-forming to ferrite-forming elements. The investigators then focused their attention upon the composition, and, in particular, upon the element titanium and its mode of alloying in the presence of other elements. A heat was obtained that could not be brought to the softness level of annealed 18-8. The response to cold-straining and aging* was very marked by previous standards, and, more important, cold-straining was found to be entirely unnecessary to produce the precipitation-hardening effect. The chemical composition of this heat was: C, 0.06 per cent; Mn, 0.54; P, 0.016; S, 0.016; Si, 0.58; Ni, 7.28; Cr, 17.60; Ti, 0.90; Al, 0.17. For some time the development work, particularly on composition, was carried

Jan 1, 1947

By Gorr W. W., R. Smith, Wyche E. H

The combination of high strength and corrosion resistance of cold-worked 18 Cr, 8 Ni steel has been advantageously utilized for some time, particularly in aircraft and rail car structures. There are, however, certain limitations on the use of such materials because the high strengths can be obtained only by cold-working, limiting the available products to sheets, strip, wire and tubes. The authors sought to overcome these limitations by resorting to precipitation-hardening, which has been used so successfully in nonferrous metallurgy but only to a limited extent in iron-base alloys. Accomplishment of this objective not only overcame the limitations, but also effected certain improvements in mechanical and other properties. This paper is an account of the development by Carnegie-Illinois Steel Corporation of a precipitation-hardening 18-8 stainless steel (called Stainless W‡ and tentatively identified as type 322). A description is given of its composition and metallurgical characteristics, heat-treatment, physical and mechanical properties and corrosion resistance. Development of the New Steel For a considerable length of time the authors were unable to determine the mechanism of the precipitation-hardening process that had been noted by Ffield18,19 in 18-8 Ti or 18-8 Cb after cold-working and reheating to moderately elevated temperatures. All known variables were exhaustively studied, but with little success. However, results began to indicate that chemical composition was the most important variable, particularly the ratio of austenite-forming to ferrite-forming elements. The investigators then focused their attention upon the composition, and, in particular, upon the element titanium and its mode of alloying in the presence of other elements. A heat was obtained that could not be brought to the softness level of annealed 18-8. The response to cold-straining and aging* was very marked by previous standards, and, more important, cold-straining was found to be entirely unnecessary to produce the precipitation-hardening effect. The chemical composition of this heat was: C, 0.06 per cent; Mn, 0.54; P, 0.016; S, 0.016; Si, 0.58; Ni, 7.28; Cr, 17.60; Ti, 0.90; Al, 0.17. For some time the development work, particularly on composition, was carried

Jan 1, 1947

By J. H. Brophy, M. H. Kamdar, J. Wulff

A constitutional diagram for the Ta-W-Re alloy system is presented. Rhenium dissolves in the complete range of solid solutions between tungsten and tantalum up to 48 wt pct in tantalum 'to about 30 wt pct in tungsten. Intermediate x and u phases only are found. X-ray diffraction and fluorescence, metallography and melting-point measurements were employed. THE constitution diagram of ternary alloys of tungsten, tantalum, and rhenium for temperatures above 1000°C is reported in this paper. Alloys in this system rich in tantalum and tungsten are of interest for high-temperature applications, and those rich in rhenium for electronic applications. No ternary phase diagram appears to be available in the literature. The three-component binary diagrams have been previously established1-3 and the present ternary data are consistent with these. EXPERIMENTAL TECHNIQUES Commercially pure tantalum (99.7 pct), rhenium (99.99 pet), and tungsten (99.9 or 99.95 pct) powders were purchased from Fansteel Metallurgical Corp., Chase Brass and Copper Co., and Fansteel or Westinghouse Electric Corp., respectively. These powders were pressed without binder and arc-melted under helium. The preparatory and analytical techniques employed were identical to those used for the Ta-Re system investigation carried out in this laboratory.324 These included X-ray diffraction and metallographic phase identification, X-ray fluorescent and wet chemical analyses, solidus determinations and heat treatments in a resistance-heated tantalum-filament vacuum furnace. For microstructural examinations standard mechanical polishing techniques were used through diamond laps. Polished speciments of all compositions were etched by swabbing with 4 parts HI?, 4 parts HNO3, and 1 part H20. Since the microstruc-tures of alloys containing one or two phases closely resembled their counterparts in the respective binary systems, typical examples are omitted in this presentation. In all the alloys examined, it was possible to observe the number of phases present. Particularly when there were small amounts of one phase involved, it was possible to identify it only by a combined conclusion based on X-ray diffraction, position of an alloy in a composition series, and the phase rule. A total of 100 different alloy compositions was arc-melted and studied in the as-cast condition metallographically and by X-ray diffraction. Specimens of each of these compositions were heat-treated at 2680, 2530, and 2020°C for 1, 2, and 4 hr, respectively. Those which were treated at 2020 were given a preliminary homogenization treatment at 2500°C for 1 hr. Specimens of 25 alloys were heat-treated at 1200o C for 168 hr. Solidus temperature measurements were made by the detection of incipient melting in eighteen alloy compositions. The metallographic and X-ray diffraction results are summarized in Table I. Graphically, this information appears in the isothermal plots of Figs. 2 and 3. Within the accuracy of the experimental methods, two such plots are sufficient to locate these data, since the results for 1200°C were similar to 2020 and those at 2530 resembled 2680

Jan 1, 1962

By Charles Jones

IN the winter of 1902, while occupying the position of mining and examining engineer for the Mountain Copper Co., Ltd., of Keswick, Cal., I had occasion to discuss with the General Manager, among other things, the question of the enormous waste of sulphur in smelting cupriferous, pyrite ore, and to cast about for means to utilize this waste or to render the fumes innocuous to vegetation. The decreasing rate of production of California farms, the consequent need of fertilizers, and the opportunity thus offered to utilize large quantities of sulphuric acid in the manufacture of superphosphates naturally brought the subject to the practical and commercial side of phosphates. I was informed that the company had made efforts to find phosphates in the West, without success. I advised as a start placing inquiries for phosphate deposits on the Pacific coast in the current mining ,journals. This was done, with the result that in January, 1903, from an advertisement in the Mining and Scientific Press we got track of a deposit in Rich county, Utah, through T.J . Wilson, of the Southern Pacific railroad in San Francisco. As soon as snow in the mountains would permit, in May, 1903, I undertook an examination of the property, with the result of recognizing the importance of the find, in spite of its lack of facilities for transportation at a commercial figure. On June 15, 1903, I concluded my report by saying, "This may be one of the world's deposits of phosphates." On Nov. 17, 1903, I concluded my report for the season in the following words : " I have now no hesitation in saying that I believe the Carboniferous formation so largely developed in the Wasatch mountains of Utah and the mountains of the Great Basin will prove to be one of the greatest storehouses of phosphoric acid in the world."

Jan 10, 1913

By C. C. Harris Discussion by B. K. Loveday

B. K. Loveday (National Institute for Metallurgy, Johannesburg, Republic of South Africa) - The paper and subsequent technical note' describing a method of determining the parameters of the three-parameter size-distribution equation developed in the paper were read with much interest. This equation was also used at National Institute for Metallurgy (NIM) to describe size distributions in grinding tests, because it was necessary to have a single equation to describe the size distribution at any time during a test. A graphical method also was used to determine the three parameters, and the use of this method as an alternative to Professor Harris's latest method is discussed here. The three-parameter model can be expressed as follows: Eq. 1 can be rearranged and transformed to Yield a linear reiationship between Y and X (transformed) log

Jan 1, 1970

By J. D. Rice, S. C. Pitzer, C. E. Thomas

Interpretation of pressure build-up data obtained in the conventional manner has often been difficult because of the deviation from theoretical behavior. Major causes of this deviation have been attributed to damage and afterflow, and to fluid redistribution in the wellbore which, in extreme cases, can result in a pressure hump in the early portion of the build-up curve. Theoretical investigations show that bottom-hole pressure is definitely influenced by phase redistribution in the tubing column during surface shut-in tests, and that the magnitude of the effect is sensitive to the producing gas-oil ratio and stabilized rate of flow in the well. For field experiments a wire-line tubing packer, which can be run in the tubing against a stabilized flow rate, was developed for bottom-hole shut-in tests. By use of this bottom-hole .shut-in method, pressure humps previously observed in surface shut-in tests were completely eliminated and the effects of afterflow minimized. Analog and digital computer studies have been made to obtain theoretical curves for comparison with field curves, and remarkable agreement between the results of bottom-hole shut-in tests and theoretical curves has been obtained. INTRODUCTION Pressure build-up data from shut-in wells have been used by the petroleum industry to determine the permeability of the formation, to estimate wellbore damage, to evaluate the static reservoir pressure and to speculate reservoir volume. Calculation of these factors is based on methods of analysis developed for theoretical systems whose build-up curves have a charac- teristic shape when the wells are shut-in at the sand faCe.1,2,3,5,8,10 However, field curves obtained by conventional surface shut-in methods do not always exhibit this characteristic. Such factors as stratification, rock heterogeneities and irregular reservoir geometry can cause the character of a build-up curve to deviate from that predicted by theory for a simple system. In addition, all field build-up data are affected by the methods utilized in obtaining the measurements. Conventional surface shut-in techniques allow two effects to occur which contribute directly to the manner in which pressure builds up at the sand face. The first, afterflow, has been recognized for some time and methods are available for estimating the magnitude of its effect and for correcting its influence.' The second, phase segregation in the tubing column after shut-in, has been reported only recently and appears to exert a considerable influence on the character of field build-up curves.!' In extreme cases, phase segregation can produce "pressure humps" in the early portion of the build-up curve. Such curves have been considered anomalous and have defied analysis. It is the purpose of this paper to discuss the effect of phase segregation in the tubing string during build-up and to present a bottom-hole shut-in technique for obtaining field build-up data which minimizes the influence of afterflow and eliminates phase segregation effects. It will be shown that reliable reservoir information can be calculated from build-up measurements obtained using this method, even though conventional surface shut-in tests on the same wells yield anomalous data. DISCUSSION OF PHASE REDISTRIBUTION EFFECTS Some of the effects of phase redistribution on pressure build-up curves have been described previously by Matthews and Stegemeier" who have presented evidence that phase segregation is responsible for the pres-

By D. W. Fuerstenau

In 1940 Schuhmann1 showed that the size distribution of a comminuted material can be expressed by the following empirical relationship: y = 100 (|f [i] where y is the cumulative percentage of material finer than size x, k is a size modulus, and a is a distribution modulus which is constant for a given material and machine. During the past few years, considerable emphasis has been given to the investigation of the extent of size reduction resulting from the expenditure of mechanical energy in crushing and grinding. Recently Schuhmann' presented a derivation of the energy-size reduction relationship by postulating that comminution in a device such as a ball mill can be considered to be the summation of many single comminution events, each of which yields a size distribution of particles following the Schuhmann size distribution equation. By grinding

Jan 1, 1961

By R. M. Waterstrat

X-ray diffraction and metallographic examination of binary Mn-rich alloys with Ti revealed the presence of intermediate phases in this system. A binary R phase has been identified and also a phase having an a-Mn type structure. The X-ray pattern of the phase TiMn3 is presented and a tentative phase diagram for the Mn-rich portion of this binary system has been constndcted. MANGANESE-rich alloys with titanium have been subjected to thermal analysis at temperatures down to 1100°C by Hellawell and Hume-Rothery.1 Their results indicate the existence of an intermediate phase TiMn3 in this binary system. This phase appears to coexist with the Laves phase TiMn2, and with terminal solid solutions based on the allotropes of manganese, at least down to 1100°C. The above investigators did not attempt to determine the crystal structure of this phase, however. Since, by analogy to the binary systems Mn-V and Mn-Cr3 one might expect to find a phase in this region of the diagram, it seemed desirable to obtain X-ray diffraction patterns of alloys in the concentration range in question, in order to ascertain whether the sigma phase or related structures occur. EXPERIMENTAL PROCEDURES Alloys were prepared by arc-melting electrolytic manganese and iodide titanium in a water-cooled copper crucible under a helium atmosphere. Excess manganese was added to each melt in order to allow for losses incurred during melting. The alloys were then wrapped in molybdenum foil and sealed in evacuated quartz tubes for annealing at various temperatures, as shown in Table I, followed by quenching in cold water. Although the inside of the tubes showed evidence for some loss of manganese from the specimen during annealing, there was no evidence of any reaction between the specimen and either the molybdenum foil or the quartz tube at these temperatures. It was later found that the manganese loss was considerably reduced by annealing these alloys in sealed quartz tubes containing one atmosphere of purified argon. As an added precaution the surface of each specimen was ground off before crushing the alloys to -270 mesh powder, using a hardened steel mortar and pestle. X-ray powder patterns were obtained using either FeKa or CrKa radiation in an asymmetrical focusing camera, which gave excellent dispersion of the closely spaced lines. Pictures were also obtained using a Debye camera of 5-cm radius which provided data in the angular region not covered by the focusing camera. The alloy specimens were polished and examined metallographically, using an etchant consisting of 60 pct glycerine, 20 pct nitric acid, and 20 pct hydrofluoric acid. The 10-g buttons were in each case broken in half and found to be well-melted and free of any gross segregation. One half of certain alloy buttons was submitted to chemical analysis in the "as-cast" condition. No appreciable change in composition seemed to occur during annealing . RESULTS The X-ray pattern of alloy Ti1.17Mn0.83 was found to agree well with that of the ternary R phase which was first found in the Mo-Cr-Co system,' and re-

Jan 1, 1962

By W. H. Boyer, J. W. Gabelman

The concept of metal zoning has long been recognized (Spurr, 1907, 1923; Emmons, 1924, 1926; Lindgren, 1933; Rateman, 1950), although it has been considered indistinct for most epithermal districts. The geometric relation of barren zones of hydrother-mally altered rock to ore deposits was emphasized in the work of Lovering (1941, 1949, 1950), Sales and Meyer (1948, 1949, 19501, Burbank (1941, 1950), Schwartz (1939, 1950), and Kerr (1947). Lovering (op. cit.) and Sales and Meyer (op. cit.) emphasized the consistent presence of barren alteration envelopes enclosing individual ore bodies, particularly of the vein type. Schwartz (1950) noted a difference between the distribution of alteration zones described by Lovering and by Sales and Meyer, as compared with those associated with the porphyry copper deposits of the Southwest. The disseminated deposits of the Southwest usually occur within large bodies of altered rock whereas most veins do not. In the following discussion the mineralization process is conceived of consisting of two distinct phases: pre-ore nonmetallic alteration and metallization. In the present investigation the position, size, and shape of all known hydro thermally altered areas and the position, size, and metal type of all known ore deposits were plotted on base maps of southwestern and west-central Colorado (Figure 1). The maps indicate a generally consistent geometric relation between altered and metallized areas. The addition of alteration to the pattern of metal deposits establishes a temperature zoning pattern of much greater clarity than that formed by the epithermal metal deposits alone, and allows a more precise definition of mineral belts. The center of strongest mineralization is indicated to be the area of greatest barren alteration, and metal deposits are grouped about it both under structural control and crudely in response to temperature zoning. The combination of an area of strong alteration and associated marginal clusters of metal deposits is defined as a mineral district. The strong similarity in individual deposits, in groups of different types of deposits, and in the alteration-metallization relation in districts throughout the region implies that a single metallogenic province is represented in southwestern and west-central Colorado. The occurrence of deposits in Tertiary voi-canics indicates a late Tertiary metallogenic epoci., although an early Tertiary epoch is known locally as at Ouray. Patterns formed by mineral districts can be

Jan 1, 1961

By M. Felsenthal

Engineers are frequently faced with the problem of having to predict oil recovery from a solution gas drive reservoir in the early life of a field. This is often the time when actual laboratory or field-derived gas-oil permeability (kg/k0) data are not yet available. Although excellent collections of k0/k0 data for various types of rocks may be found in the literature,1,2,3 a need exists for a more detailed correlation of k0/k0 data with core properties such as porosity, permeability, clay content or pore-size distribution. It is the purpose of this article to present this type of correlation for sandstone material. The correlation is based on laboratory tests performed on over 300 core samples from 19 reservoirs in the United States and Canada. EXPERIMENTAL Cores were analyzed by routine procedures, using samples of conventional size (7/8-in. diameter, 7/8-in long) cut parallel to the bedding planes. Air permeability was measured at 1.67 atm mean pressure in a Hassler-type apparatus. Porosity was determined with the aid of a Ruska bulk volume meter and a Boyle's Law rock volume meter, An evaporation method' was used to evaluate irreducible water saturations. Core samples were saturated with 25,000 ppm NaCl brine. The brine was reduced to the irreducible saturation, and the remainder of the pore space was filled with kerosene. This was followed by multiphase flow tests using the so-called "dispersed feed" technique.5 n this technique, gas and oil (kerosene and kerosene-saturated air) were dispersed with the aid of a porous Alun-durn feed head, the face of which contained a waffle-shaped system of Lucite-lined grooves. Oil entered the back side of the feed head and emerged at the raised areas of the front face. Gas was introduced directly into the system of grooves at the front face. The gas-oil mixture then entered the test core which was kept in capillary contact with the feed head. Permeabilities were determined from rate and pressure measurements and saturations from weights. All determinations were performed at equilibrium or steady-state conditions. Pore-size distributions were determined on selected samples by a mercury injection technique.6 GENERAL CORRELATIVE TRENDS When examining data from a given reservoir, it was noted that k0/k0 vs saturation curves became generally less steep as specific air permeability increased, a development that has a favorable effect on oil displacement efficiency by solution gas drive. This trend has also been reported by others in the literature.' An effect of porosity on k0/k0 data was also noted. This effect was not generally discernible in a study of relative permeability data for a given reservoir but became apparent when data for sandstone reservoirs of similar lithology but differing average porosity were compared. For instance, in a comparison of argillaceous and/or calcareous sandstones from 11 reservoirs ranging in average porosities from 14 to 28 per cent, a definite trend was noted, indicating that for a given permeability k0/k0 curves became less favorable (i.e., steeper) as porosity increased. A similar trend was observed for a group of comparatively clean sandstones from five reservoirs ranging in average porosities from 15 to 21 per cent. For a given permeability and porosity, comparatively clean sandstones gave more favorable k0/k0 curves than argillaceous and/or calcareous sandstone or chert reservoirs. The laboratory studies also showed that least favorable k0/k0 curves were exhibited by shaly sandstone, conglomerate, and sandstone containing carbon inclusions. Table 1 lists the various source reservoirs classified by lithology types. To facilitate a correlation of k0/k0 data with core characteristcis, it was found expedient to work with