Search Documents

By P. Hazebroek, M. Prats, E. E. Allen

Well locations in water floods frequently do not coincide with the ideal well locations associated with the flood pattern which is used. A question of importance is. "How much oil is lost because of this?". This is the problem treated in this paper. It is assumed that each pattern in a five-spot flood has the proper number of production and injection wells but that the wells may be off-pattern. The distance by which a well is off-patern is given in terms of the pattern spacing, defined as the length of one side of a five-spot. The influence of off-pattern wells on the performance of a five-spot flood has been investigated mathematically for unit mobility ratio. All production and injection rates are assumed to remain equal. The loss in recovery resulting from pattern irregularitie: has been calculated at a cumulative water injection corresponding to a 98 per cent water-cut in a regular five-spot. Displacing a single production or injection well by about one-third the pattern distance reduces the total field recovery by 4.4/N per cent of the recovery obtainable with regular spacing, where N is the number of five-spots in the flood (assumed large). When off-pattern wells are separated by at least one regular five-spot and are displaced by less than one-third the pattern distance, the total loss in recovery in a large-scale flood is, at most, 1 per cent of the recovery obtainable from that field with a regular five-spot pattern. However, much higher losses may occur if the off-pattern wells are not separated by a regular five-spot, if the rates are imbalanced, or if the mobility of the injected water is higher than that of the crude. Although the loss in oil recovery due to pattern irregularity often may be low, the off-pattern case will always require injection of more water to reach the same final water-cut. The volume of water injected per unit volume of oil displaced has been calculated for each five-spot adjacent to a five-spot containing a single 08-pattern well. The cumulative water injection at the time of 98 per cent water-cut may be increased by as much as 37 per cent when a production well is displaced one-third the pattern distance toward an injection well. The existence of differences between actual subsurface locations and the idealized well patterns used in secondary recovery operations is well recognized. However, the methods commonly used for predicting waterflood behavior ignore such differences, even when subsurface locations are known. The reason for this is simple. The idealized well patterns are highly symmetrical and, as such, the production history of the pattern (and even of the field) can be determined from that of a few production wells—usually from only one. Consideration of the many irregular well spacings found in a specific field would entail a large amount of work, and then the results would be applicable only to that specific field. In an attempt to provide an answer to the more general problem, this paper considers a water flood having an idealized well pattern, except for one well which is not at its regular location. When several off-pattern wells are present, their contributions are assumed to be additive unless the off-pattern wells are close to each other. Only four positions of the off-center well (at x, y. of Fig. 1) are considered in this paper. These are shown

By W. J. West, W. W. Garvin, J. W. Sheldon

One of the most important problems of reservoir mechanics is the prediction of the behavior of a gas and oil producing reservoir for a variety of production programs. In the absence of a knowledge of the behavior of even idealized systems, it has been difficult, if not impossible, to determine which production program would yield maximum economic recovery. The problem was formulated mathematically many years ago, hilt a solution of the equations had never been obtained because of their extreme complexity. The solution of the problem became possible, however, with the advent of modern computing machines. This paper describes a digital method of solving the problem and discusses some of the results which have been obtained to date. The IBM Type 701 Electronic Data Processing Machines located at IBM's New York Scientific Computing Service were used successfully to perform the computations. The flow of gas and oil through a reservoir can be described mathematically by two second-order, nonlinear partial differential equations which must be solved simultaneously. All derivatives were replaced by finite differences to bring the equations into a form suitable for digital calculations. A number of finite ditference formulations were investigated and one form was found which resulted in stable, convergent solutions. This form was used to obtain .solutions for both radial and linear systems producing by solution gas drive. The results presented in this paper are: (a) saturation profile within the hypothetical reservoir vs. time, (b) pres.strre profile within the hypothetical reservoir vs. time. (c) gas-oil ratio vs. cumulative recovery, and (d) ultimate recovery. The saturation profile clearly shows the effect of critical gas saturation. The saturation near the well-bore drops quickly to the critical gas saturation and remains essentially at that value until the remainder of the reservoir also has dropped to the critical gas saturation. The pressure profile shows a smooth variation of pressure across the reservoir. The gas-oil ratio drops slightly during the early stage of production until the critical gas saturation is reached, rises rapidly from then on and eventually passes through a sharp maximum just before the economic limit of production is reached. For the radial example presented in this paper, the average oil .saturation of the reservoir at a time corresponding to the limit of economic production was 56.5 per cent and the ultimate recovery was 6.86 per cent. The difference between change in saturation and ultimate recovery is caused by .shrinkage of the oil phase. The solution time with the 701 Computer is sufficiently short to permit an economically feasible investigation of the effects of variation of the many parameters which describe an oil reservoir. In particular, the ultimate recovery for various systems can he determined as a function of rock and fluid properties, of well spacing. and of production rate. INTRODUCTION The effective planning for maximum economic depletion of oil reservoirs is one of the major problems confronting oil producers. The most important part of the planning is prediction of the response of the oil reservoir to a particular production program. The production program can be selected by imposing certain controls available to the operator. Some of these controls are: (a) well spacing, (b) production rate, (c) time

Jan 1, 1955

By A. S. Appleton, M. B. Bever, G. E. Dieter

A gold-silver alloy was deformed by explosive loading at shock pressures up to 510 kbars. The stored energy and hardness increased over the whole range of pressures; the largest rates of increase were observed between 120 and 150 kbars. In this range, markings rkavacteristic of defornation twins first appeared; higher pressures produced markings in all grains. These effects are compared with those of conventional deformation processes and are discussed in relation to probable structural changes. In recent years, increasing efforts have been devoted to the investigation of the effects produced in metals by the passage of high-intensity shock waves of explosive origin. By properly utilizing the energy released by the detonation of a high explosive, it is possible to generate pressure pulses of the order of 500 kbars and higher. (One kbar equals l0 9 dynes per sq cm or approximately 1000 atm.) The passage of a shock wave through a metal occurs at pressures which are very much greater than the yield strength. As the shock front passes a point in the metal, the pressure rises almost instantaneously, and continues to act at the point for a few microseconds. Thus, metals subjected to explosive shock loading experience a nearly instantaneous increase in pressure, and a subsequent release of pressure, which is almost as rapid. Under these conditions mechanical twinning and shear transformations occur readily. smith1 has investigated the metallurgical changes in copper and iron resulting from exposure to explosive shock waves. He found an appreciable increase in hardness in both metals. In copper, a hardness greater than that resulting from 95 pct reduction in thickness by rolling was obtained, yet in the explosive deformation, the thickness of the specimen decreased only a few percent. After explosive loading, the micro-structure of copper showed markings characteristic of mechanical twins. The amount of stored energy resulting from explosive loading is of interest. Measurements of the stored energy of cold work as a function of strain, temperature, strain rate, and composition have been made with gold-silyer alloys deforyed by rolling, orthogonal cutting,3 drilling,4 filing, wire drawing, and torsion. The investigation reported here was also carried out with a gold-silver alloy and its results can be compared with those for the deformation of this alloy by more conventional methods. EXPERIMENTAL PROCEDURES An alloy containing 82.6 wt pct Au and 17.4 pct Ag was purchased in several batches from Handy and Harman Co., New York, as annealed rod 1/4 in. dim. The rod was cold-rolled to a sheet approximately

Jan 1, 1962

By John E. Caffrey

The Federal Coal Mine Health and Safety Act of 1969, Title III, Interim Mandatory Safety Standards for Underground Coal Mines, is devoted to protection of workmen from hazards of electricity, roof, ribs, fire, and explosions. The Rules and Regulations, promulgated through the Federal Register, provide the criteria by which the law would be administered. Certain aspects of the law involve features that could be summarized under entrapment. These are sections 303 (y)(1), (y)(2) and 317 (f) (4). This paper is intended through the use of the figures to describe how these features of the law affect mine ventilation design, what are the problems, and possible solutions to them.

Jan 1, 1974

By M. G. Corson

The iron-silicon alloy series has always been one of the most puzzling among the binary alloys. Examining the well-known mechanical properties of the iron-rich alloys only we meet the following situation: The ultimate strength and yield point of alloys worked and annealed under the usual conditions represent nearly a straight line function of the silicon content up to 1.5 per cent. silicon (Fig. I). Starting at the ultimate strength of 35,000 lb. and at a yield point of 16,000 lb. for pure electrolytic iron, one reaches a maximurn strength of 93,000 lb. and a maximum yield point of 74,000 lb. at 4.5 per cent. silicon. This corresponds to an increase in ultimate strength by 13,000 lb, per each per cent. of silicon added and nearly the same rate applies to the yield point. The data mentioned are taken from the investigation by T. D. Yensen,1 and while they do not exactly corroborate the results obtained by earlier investigators, they seem to be the most correct. Plastic properties of the alloys are controlled by a much more complicated relationship. Up to 2..5 per cent. Si, the elongation stays close to 50 per cent. (in 2 in.) and the area reduction amounts to 85 per cent., a situation that forms the usual feature of all alloys representing strictly solid solutions. The plasticity of the latter is always nearly equal to that of their base metal. Beyond 2.5 per cent. silicon, the situation becomes much more complicated. Yensen observed an enormous drop in elongation and area reduction at about 2.65 per cent. silicon, where the first hardly reaches 10 per cent. and the second is still lower; he found, however, a considerable recovery in plasticity at about 2.8 per cent. Si and up to 1.5 per cent. Si it is represented by 20 per cent. for the elongation and 30 per cent. for area reduction. Yensen's graphs, as shown in Fig. 1, indicate also a considerable drop in strength and yield point at the same point of 2.65 per cent. Si,

By C. H. Mathewson

CONSIDERABLE progress has been made during the last few years in analyzing the action of plastic deformation in metallic crystals. This is due largely to the development of X-ray spectrographic methods for studying changes in the orientation of single crystals, or of conglomerates, as they occur during the process of plastic deformation, but partly to the widespread knowledge of suitable technique for preparing large (single or variously combined) crystals for direct crystallographic observation under stress or in various conditions of strain. These two methods of studying changes in the crystalline structure of metals may of course be used in conjunction with features of mutual support, but unfortunately the advantage of direct crystallographic observation is lost when we proceed to the study of severely cold-worked structures, owing to the occurrence of real or apparent crystalline discontinuities which become more and more complicated as the amount of plastic action increases. Furthermore, the X-ray methods do not appear to be adequate, at least in their present stage of development, to fix definitely the character of structural alteration in the parent crystal lattice by plastic deformation. The principal question at issue concerns the nature of the crystalline particles that remain after plastic deformation. These are generally known in our American metallurgical literature as crystalline fragments,1 and they seem, indeed, to diffract as individuals causing the Hull pattern of a, severely cold-worked metal to resemble the pattern of a fine powder,2 with certain features of preferred orientation among the particles determined by the manner and intensity of cold working.

Jan 1, 1927

By C. G. Dunn, P. K. Koh

THE primary recrystallization texture in cold-rolled silicon iron, which is the matrix texture for developing the Goss texture or the cube-on-edge texture by secondary recrystallization at temperatures near 900°C,1-5,21 has not been adequately described. Thus from the present available information, it is not possible to explain satisfactorily both the grain-growth selectivity of the matrix and the often observed magnetic torque curve, which itself provides some information on the texture. Also lacking is information on the special annealing texture that develops in this material when the annealing temperature is 1200°C or higher and the rate of rise to temperature is extremely rapid. From the work of May and Turnbull5 and from unpublished work, it was known that isothermal annealing near 1200°C tends to reduce the extent of secondary recrystallization and that a much weaker cube-on-edge texture results if appreciable normal grain growth replaces secondary recrystallization. Koh and Dunn6,7 have obtained additional information on complex primary recrystallization textures from further studies made after normal grain growth. In these instances the initial textures were retained during normal grain growth. A similar result reasonably could be expected in the present study except for the presence of a grain growth ihibitor1-5,8,9.21 and its tendency to allow only a few grains to grow. However, any information on the orientations of grains in the special annealing texture, even if far from representative of the initial matrix texture, would provide useful information on the nature of the matrix texture. In the present texture study the method of Newkirk and Bruce,10 which is based on the methods of Geisler" and Schwartz, 12 is used to obtain a complete (110) pole figure of the primary recrystallization texture. The high-temperature annealing texture is determined simply from the orientations of a large number of selected grains. The kinetic nature of the process that produces the annealing texture is treated elsewhere13 and it is shown that a form of secondary recrystallization with a very high rate of nucleation occurs during rapid annealing at high temperatures. EXPERIMENTAL PROCEDURE Commercial 0.014-in. cold-rolled silicon iron strip (3.16 wt pct Si), prepared by two stages of cold rolling with an intermediate short anneal, was given a decarburizing 3-min anneal at 800°C. Me-tallographic studies indicated complete recrystallization. Short-time anneals at 900° C and at higher temperatures proved that secondary recrystallization had not begun at 800°C, in fact, the short additional anneals were still in the induction period of secondary recrystallization. A rapid rise to an annealing temperature of 1260°C (2300°F) was obtained in a BaC12and NaCl fused salt bath. The structures that resulted from anneals in the range 12- to 1000-sec duration were relatively finegrained, even though the growth was a form of exaggerated grain growth13 or secondary recrystallization with a high nucleation frequency.= Many of the grains were large enough for an X-ray study using a 5-mil X-ray beam. A transmission Laue Camera and an optical-mechanical stage for moving the grains into the X-ray beam were used. A total of 325 grains were X-rayed in this manner and the grain orientations determined. Complete (110) pole figures were obtained for the primary recrystallization texture using CoKa radiation at 30 kv in the back-reflection range, such as (220) for (110) poles, as described recently by Newkirk and Bruce.10 The low voltage serves to reduce the spurious white radiation to a minimum. A filter of 0.001-inch iron foil was located in front of the detector slit for transmission and in front of the beam slit for back reflection. A new and improved specimen holder extended the useful tilting angle range for transmission to 70 deg instead of 60 deg as previously reported.' A torque magnetometer was used to obtain the magnetic torque curves for a number of l-in. diam disk specimens. RESULTS The (110) pole figure of the material after recrystallization at 800°C is shown in Fig. 1. The positions of the pole concentrations are found to be

Jan 1, 1961

By J. W. Eckerd, P. S. Lewis, N. H. Coates

USBM designed, constructed, and operated an 18-in.-diam fluidized-bed combustor for highly caking coals to evaluate the method for possible application to power generation. In initial tests, combustion was carried on successfully, with carbon losses as low as 0.8%+ Coal ash was not satisfactory as a bed material, but mullite proved to be acceptable. Overall heat-transfer coeffients from the bed (-20 t 50 mesh mullite) to a water-cooled tube were about 75 Btuper hr-sq ft. Fluidized-bed combustion is being investigated by the U. S. Bureau of Mines (USBM) as a potentially cheaper method of firing power plant boilers. Lower combustion temperatures in fluidized beds—only 1400" to 1800°F-—should reduce fireside deposition and corrosion and nitrogen oxides production. Fluidized-bed combustion also offers possible advantages in the use of additives to control SO, emissions and amenability to processing of high-ash, high-moisture coals without special preparation. This paper describes development of a fluidized-bed combustor and the results of preliminary tests. Equipment and Procedure Fig. 1 shows the 8-ft-high combustor. A cone-shaped plate perforated by I/8-in.-diam holes supports the fuel bed and admits the fluidizing air; water passing through the 3/4-in. pipe extracts heat from the combustion bed. Fig. 2 is a flow diagram of the system. Coal is fed pneumatically to the base of the fuel bed. Combustion products are passed through two centrifugal separators to remove most of the entrained solids, then to a water

Jan 1, 1971

By H. C. Kenny

The annealing or softening temperature of cold-worked copper is appreciably increased by almost unbelievably small amounts of silver. As indicated by some data in this paper, the softening temperature of high-conductivity, tough-pitch copper may be increased from 200" to 350" C. by the addition of only 15 oz. per ton (0.052 per cent) of that element. Because it has this higher annealing temperature as compared with the silver-free metal, silver-bearing copper finds considerable use in industry. For example, when hard-rolled copper is used in operations that involve soldering or tinning, silver-bearing copper insures against loss of strength, whereas silver-free copper becomes "dead soft." Yet—though several investigators, beginning with Caesar and Gernerl in 1916, have shown that small amounts of silver do definitely raise the softening temperature of copper—data are lacking on the problem: What is the specific influence of different amounts of silver on this temperature? It was to help in filling this gap in the knowledge of what might be termed "alloy coppers" that the data given herein were obtained. The softening of cold-worked copper depends, of course, on a number of factors, of which the composition of the material is only one. Other highly important factors are the degree to which the material is cold-worked and the time it is held at the annealing temperature. The method of cold working and the grain size of the metal produced are also significant. All these variables were taken into account in the investigation reported here, and the influence of silver on the electrical conductivity and on the working was also considered. The coppers used in the softening tests were Lake coppers melted and cast by the Calumet and Hecla Consolidated Copper Co. The ires were fabricated by the Roebling Wire Co. and the sheets were rolled at the Battelle Memorial Institute. Partial analyses of some of the coppers are listed in Table 1, with their electrical conductivities.

Jan 1, 1934

By H. N. Mead

In a reservoir when gas comes out of solution and rises, additional pressure is created because of the change in position of this gar in the bounded volume. If this pressure effect is not taken into account as a pseudo-influx ill mate rial balance calculations on reservoirs in which there is evolving gas, an error is introduced that is directly proportional to the length of oil column and amount of gas evolved and inversely proportional to the reservoir pressure. In reservoirs with small oil column this pseudo-influx is of little importance. The larger the oil column the more important the effect becomes. The most important application, however, will be for reservoirs with declining pressure in which increasing water entry has been indicated by material balance calculations. It could be that this indication is the result of the cited pseudo-influx and not water entry at all. This paper attempts to explain this phenomenon in relation to material balance calculations and prevents an approximate method of determining tile pseudo-influx. INTRODUCTION Only recently has the pressure-volume relationship of gas rising in a liquid appeared in engineering literature, although its effect has been discussed for several years—especially among engineers engaged in drilling operations. The writer published a paper in 1957 in which this phenomenon was examined in relation to blowouts in drilling wells.' Also, in 1957 Stegemeier and Matthews' authored a paper in which the relationship was presented with respect to pressure build-up tests when shutting in producing wells. In this paper the effect will be called "pressure inversion" which is descriptive of the phenomenon. Fundamentally, the effect just mentioned is the result of changing the position of a quantity of energy contained within the gas itself (as a result of its compression) within the bounded volume in which the gas exists. If the gas were allowed to expand "beyond all bounds" there could be no pressure inversion effect. This is because all of the energy contained within the gas as a result of compression would have been re- PRESSURE INVERSION A phase that has not been discussed in the literature is the effect of pressure inversion upon material balance calculations in reservoirs in which the reservoir pressure drops with reservoir withdrawal and is below the bubble point. This action releases solution gas which, after the critical gas saturation has been reached, will tend to rise and collect at the top of the reservoir. The pseudo-influx caused by this effect could be great enough in reservoirs of large oil column and high permeability to render invalid any analyzer studies made on them — if pressure inversion has not been taken into account. Most suspect would be those reservoirs with large oil column in which increasing water entry has been predicted but the bottom wells have not yet produced water. Example 1 Simply stated, this phenomenon exists in oil reservoirs because of the difference in density and expansibility between gas and oil. For example, if a bubble of gas exists at the bottom of a 1,000-ft column of oil having a gradient of 0.30 psi/ft with the pressure at the top of the column zero, the bubble of gas will be compressed to a pressure of 300 psi. If temperature and the combined volume of the oil column and the gas bubble remain constant, as the gas bubble rises in the oil column it will have the same volume and consequently the same pressure at any point. Under these conditions when thc bubble reaches the top of the oil column, the pressure will be approximately 300 psi at the surface and approximately 600 psi at the bottom of the oil column. If it is assumed that the oil is incompressible the pressures will be exactly 300 and 600 psi, respectively.

By H. J. Ramey

As fluids move through a wellbore, there is transfer of heat between fluids and the earth due to the diflerence between fluid and geothermal temperatures. This type of heat transmission is involved in drilling and in all producing operations. In certain cases, quantitative knowledge of wellbore heat transmission is very important. This paper presents an approximate solution to the wellbore heat-transmission problem involved in injection of hot or cold fluids. The solution permits estimation of the temperature of fluids, tubing and casing as a function of depth and time. The result is expressed in simple algebraic form suitable for slide-rule calculation. The solution assumes that heat transfer in the wellbore is steady-state, while heat transfer to the earth will be unsteady radial conduction. Allowance is made for heat resistances in the wellbore. The method used may be applied to derivation of other heat problems such as flow through multiple strings in a wellbore. Comparisons of computed and field results are presented to establish the usefulness of the solution. INTRODUCTION During the past few years, considerable interest has been generated in hot-fluid-injection oil-recovery methods. These methods depend upon application of heat to a reservoir by means of a heat-transfer medium heated at the surface. Clearly, heat losses between the surface and the injection interval could be extremely important to this process. Not quite so obvious is the fact that every injection and production operation is accompanied by transmission of heal between wellbore fluids and the earth. Previously, the interpretation of temperature logs',' has been the main purpose of wellbore heat studies. The only papers dealing specifically with long-time injection operations are those of Moss and White3 and Lesem, et al.' The purpose of the present study is to investigate wellbore heat transmission to provide engineering methods useful in both production and injection operations, and basic techniques useful in all wellbore heat-transmission problems. The approach is similar to that of Moss and White:' DEVELOPMENT The transient heat-transmission problem under consideration is as follows. Let us consider the injection of a fluid down the tubing in a well which is cased to the top of the injection interval. Assuming fluid is injected at known rates and surface temperatures, determine the temperature of the injected fluid as a function of depth anti time. Consideration of the heat transferred from the injected fluid to the formation leads to the following equations. For liquid, Eqs. 1, 1A and 2 are developed in the Appendix. These equations were developed under the assumption that physical and thermal properties of the earth and wellbore fluids do not vary with temperature, that heat will transfer radially in the earth and that heat transmission in the wellbore is rapid compared to heat flow in the formation and. thus, can be represented by steady-state solutions. Special cases of this development have been presented by Nowakl and Moss and White.3 Both references are recommended for excellent background material. Nowak' presents very useful information concerning the effect of a shut-in period on subsequent temperatures. Since one purpose of this paper is to present methods which may be used to derive approximate solutions for heat-transmission problems associated to those specifically considered here, a brief discussion of associated heat problems is also presented in the Appendix. Analysis of the derivation presented in the Appendix will indicate that many terms can be re-defined to modify the solution for application to other problems. Before Eqs. 1, 1A and 2 can be used, it is necessary to consider the significance of the over-all heat-transfer coefficient U and the time function f(t). Thorough discussions of the concept of the over-all heat-transfer coefficient may be found in many references on heat transmission. See McAdams5 or Jakob," for example. Briefly, the over-all coefficient U considers the net- resistance to heat flow offered by fluid inside the tubing, the tubing wall, fluids or solids in the annulus, and the casing wall. The effect of radiant heat transfer from the tubing to the casing and resistance to heat flow caused by scale or wax on the tubing or casing may also be included in the over-all coefficient. According to McAdams, on page 136 of Ref. 5>

By W. C. Winegard, W. J. Bratina

Internal friction characteristics and temperature dependence of the torsion modulus for iodide zirconium containing 2.4 pct Hf were investigated, using a low frequency pendulum technique. The internal friction curve consists of a background which increases as the temperature increases, a maximum at 860°C apparently a background due to the al-lotropic transformation, a maximum due to grain boundary relaxation with an associated heat of activation of 58,000 cal per mol, and an anomaly below 350°C which may be associated with a precipitation perphenomenon, Oxygen in below small amounts reduces the grain boundary maximum substantially. The variation of the torsion modulus at 20°C was found to be 3450 Kg per mm2 for the zirconium used in the present work. IT is well known that small amounts of certain solutes materially affect the ductility of zirconium. Lely and Hamburger,&apos; as early as 1914, found that high purity zirconium exhibited a remarkable ductility, while Fast&apos; has shown that oxygen and nitrogen can cause substantia1 embrittlement. Treco" has recently demonstrated that the ductility decreases sharply with the oxygen content, and that 2 atomic pct O2 embrittles zirconium to such an extent that cold working is impossible. The marked decrease in ductility is difficult to understand in view of the fact that Domagala and McPherson4 report the solid solubility of oxygen in zirconium to be 29 atomic pct at 500 °C. Another metal which behaves much the same as zirconium in this respect is titanium. Pratt et al." investigated the internal friction characteristics of titanium and the effect of oxygen on the internal friction values. It is evident that internal friction measurements are of value for studying grain boundary segregation, as shown by Pratt et al. for oxygen in titanium, by Pearson for oxygen in copper, and by Maringer and Schwope for oxygen in molybdenum. With this in view, the internal friction characteristics of zirconium and the qualitative effect of oxygen on the grain boundary relaxation phenomenon were investigated. Materials and Experimental Procedure The zirconium used in the present work was supplied by the Foote Mineral Co. in the form of wire 0.05 in. diam. The analysis supplied by the manufacturer indicates the amount of hafnium as 2.4 pct, less than 0.01 pct O less than 0.01 pct N,, less than 0.02 pct H,, and less than 0.001 pct C. Additional spectro-graphic analysis indicates the other main impurities as follows: 0.01 pct Fe, 0.05 pct Si, 0.008 pct Cu, <0.005 pct W, <0.001 pct Al, <0.05 pct Mg, <0.001 pct Ni, <0.02 pct Ca, and <0.01 pct Ti. Microscopic examination of the material in the as received condition revealed very fine grains with numerous twins. Specimens were annealed either in situ in the internal friction apparatus or in evacuated silica tubes in an auxiliary furnace. When the specimens were annealed in the auxiliary furnace, they were wrapped in identical zirconium wire to prevent contamination by the container. Metallographic sections were taken in all cases. Some were taken from the specimens used for internal friction measurements after completion of the experiments, while others were taken from control specimens at intermediate stages of the experiments. lnternal friction values were obtained by measuring the free decay of a low frequency torsion pendulum (1 cycle per sec), the suspension of which was

Jan 1, 1957

By M. E. de Morton

Recovery and early recrystallization of heavily deformed, 99.98 pct Cr was investigated by studying metallographic structure. X-ray line sharpening, electrical resistivity, plastic properties, internal friction, and shear modulus. Appreciable recovery of resistivity, internal friction, and shear modulus together with some hardening and relief of internal strains occurred before the visible growth of a textured substructure above 350°C (recrystallization in situ). The complex behavior of shear modulus, internal friction, and its strain amplitude dependence during annealing are discussed qualitatively in terms of the relative mobility of dislocations. BY plastically deforming fully recrystallized 99.98 pct Cr above the brittle to ductile transition temperature, at -350°C. as in wire drawing, chromium can be made very ductile at room temperature. However, this ductility is lost on annealing at high temperatures when recrystallization takes place.&apos; The present investigation was made to determine the general pattern of the changes in a number of physical and mechanical properties during recovery and recrystallization of heavily deformed chromium as part of an effort to elucidate the reasons for lack of ductility in the fully recrystallized condition. PREPARATION OF MATERIAL Wire specimens 0.027 in. in diam were prepared from arc-melted, electrolytic chromium by extruding, hot swaging and finally wire drawing at 300" to 350°C, i.e. above the brittle-to-ductile transition temperature. The total reduction in area of the wire was 98 pct and the last 3 pct of reduction was made at 100" to 150°C before cooling to room temperature. The impurity content of the material is shown in Table I. Internal friction and modulus measurements were made on a single specimen after annealing in situ at successively higher temperatures. For all other measurements, a fresh specimen was used for each temperature and annealing of these specimens was done in evacuated (0.001 mm Hg) and sealed silica tubes for 1 hr at the various temperatures up to 700°C. EXPERIMENTAL METHODS AND RESULTS The occurrence of a. transition in some physical properties of chromium at - 40°C2 imposed limitations on the temperature region where some of the measurements could be made. The reason for this transition in chromium is at present unknown but is probably associated with an antiferromagnetic state observed below - 40°C.* Heavy deformation produces an anomalous decrease in resistivity when measured at temperatures below -40°C4 though a normal increase is observed above this temperature. On the other hand internal friction in heavily deformed chromium5 over the temperature range 40" to 50°C is invariant with temperature. Above and below this range internal friction is strongly temperature dependent, increasing with increasing temperature. A temperature in this range was therefore convenient for both resistivity and internal friction measurements and for consistency the measurements of the mechanical properties were also made at about this temperature. No structural change has, however, been observed in careful X-ray measurements6 between -195" and 50°C, i.e. departure from cubic symmetry was not greater than 3:10,000; X-ray line sharpening measurements were therefore more conveniently made at room temperature.

Jan 1, 1962

By H. R. Hose

The total crude fluorspar reserves in Western Europe, including the USSR and the Soviet sphere, Thetotalare estimated to exceed 17 million metric tons. The total fluorspar production in 1951 in Western Europe, excluding the USSR and Soviet sphere, amounted to 371,109 metric tons. The chief fluorspar-producing countries in Europe, excluding Russia and the Soviet sphere, are France, Western Germany, Italy, Spain, and the United Kingdom. TOTAL crude fluorspar reserves in western Europe, containing more than 35 pct CaF2, are estimated at 12 million metric tons, while reserves in the USSR and Soviet sphere may exceed 5 million metric tons. The bulk of these reserves are concentrated in the USSR, Spain, United Kingdom, Western Germany, and Italy. Since published estimates of the tonnages of individual mines and explored deposits are not available for most countries in Europe, the estimates given in Table I for individual countries are necessarily approximate, as they have been compiled from various sources and modified and combined according to the author&apos;s judgment. The majority of fluorspar deposits in Europe belong to the late Paleozoic metallogenetic epochs and have been found within or along the borders of the Hercynian massifs. Deposits in the Central and Esterel massifs of France, those of Western and Eastern Germany, Sardinia, the Catalonian coastal range and the Sierra de los Santos in Spain, and those of Devonshire and Cornwall belong to the Hercynian metallogenetic epochs. The deposits in southern Norway and Sweden belong to the middle Paleozoic or later, those of northern England to the late Paleozoic or later, those of northern Spain and Greece to the late Mesozoic, and those of northern and probably central Italy and Switzerland to the early Tertiary. Fluorspar occurs typically in veins, lenses, and stringers, but also in bedded replacement deposits and pockets, and may be colorless to white, yellow, green, pink, brown, blue, or purple to almost black. Except for the colorless variety, the only kind which can be used for the optical industry, the color of the fluorspar does not affect its ultimate use. Crystalline cubic or octahedral fluorite of CaF2 composition, with 48.9 pct fluorine and 51.1 pct calcium, has a specific gravity of 3.18. The ore in place, however, usually averages 3.0 metric tons per cubic meter owing to the quantity of other minerals asso- ciated with the fluorspar in the veins and the physical state of the fluorspar, which may vary from sugary to massive crystalline or microscopic inter-growths with barite or quartz. Barite of 4.5 sp gr, quartz of 2.66 sp gr, and chert and calcite are commonly associated with fluorspar. Other minerals usually present in lesser amounts are celestite, wad, silver, lead, zinc, copper, iron, and uranium minerals. In some cavity fillings the rhythmic deposition of the fluorspar, barite, and quartz into successive crusts may make it possible to handpick the crude ore on belts or to separate the fluorspar from other minerals while the actual mining is carried on. Where metallurgical grade lump spar is required for foundries, separation of quartz and barite may be made also by jigs and heavy media, and in some mines the lead and zinc sulphides may be separated and recovered by vibrating tables. However, except in the case of unusually high grade deposits, acid grade fluorspar is obtained by flotation. By this process fluorspar deposits grading down to 35 pct CaF2 in the crude ore can be worked at a profit when fluorspar, lead, zinc, and silver prices are high, as the sulphides of these ores can be separated from the fluorspar by flotation and concentrated.

Jan 1, 1956

By D. R. Irving

Prior to this time, ample supplies of high grade mineral fillers, such as clay, have been available close to consuming centers. Now depletion of these accessible deposits, coupled with other factors such as increasing demand due to population expansion and standard of living rise, has made development of upgrading techniques attractive to producers. Various investigations being carried out by the U.S. Bureau of Mines are described. Factors making the development of improved methods for upgrading clays attractive to producers include: depletion of accessible deposits of high-grade clays, rising transportation and labor costs, more exacting specifications, and increased demand resulting from an expanding population and a constantly rising standard of living. Industry recognizes the need for upgrading presently unusable materials and has cooperated with the U.S. Bureau of Mines by providing samples from submarginal deposits and by evaluating the products that USBM upgrades. Following are some examples of recent clay beneficiation work by the Bureau. FIRE CLAY BENEFICIATION At the Rolla Metallurgical Center, Rolla, Mo., the Bureau is conducting research to develop technically and economically feasible mineral-dressing methods to remove quartz, pyrite, and other impurities from submarginal fire clays. The research has been spurred by the growing shortage of high-grade bur-ley, flint, and plastic clays in the Missouri fire-clay district resulting from increased consumption and the low rate of discovery of new deposits of adequate quality. There apparently is ample tonnage of submarginal flint and plastic clays to maintain the industry for many years if such material can be upgraded to commercial quality. Samples have been submitted to USBM by several major producers of refractories, including A. P. Green Fire Brick Co.; Harbison-Walker Refractories Co.; Mexico Refractories Div., Kaiser Aluminum and Chemical Corp.; and Wellsville Fire Brick Co. Research on some samples has been completed and still is in progress on others. The Bureau has found that specimens containing quartz or pyrite in grains coarser than the accompanying clay generally can be upgraded either with a gravity table or hydraulic cyclone. The improvement in quality is notable not only in chemical analysis but in an increase in pyrometric cone equivalent (PCE) of one or more cones. As an example, consider the results attained on a sandy flint—a fine-grained mixture of kaolin and halloysite with quartz and minor quantities of iron and manganese oxides. Chemical analysis was: 35.4 pct alumina (A12O3) and 47.8 pct silica (SiO2). The sample contained 9.2 pct free silica as quartz. The PCE was 33. The sample was crushed to -10-mesh, blunged with water, and then stage-ground to -48-mesh. The ground sample was tabled to yield a clay fraction containing 37.6 pct A12O3, and 45.3 pct SiO2 of which 2.4 pct was free silica. The PCE was 34. Recovery of alumina by this process was 73.6 pct. Concentration of the same clay in the hydraulic cyclone was even more effective in respect to quartz removal. The clay fraction analyzed 38.6 pct A12O3, 45.0 pct SiO2 of which 0.5 pct was free silica as quartz, and had a PCE of 34. Recovery of alumina was 71.9 pct. The hydraulic cyclone was also effective in reducing the pyrite content of a plastic clay which likewise was a mixture of kaolin and halloysite, plus some pyrite, quartz, and carbonaceous material. It analyzed 30.6 pct Al2O3, 52.3 pct SiO2, 2.3 pct Fe2O3, and 0.76 pct S. The sample was blunged and screened through 10-mesh to remove some coarse pyrite, then ground to -65-mesh and cycloned to remove most of the remainder. The final product recovered 81.8 pct of the alumina at a grade of 32.3 pct A12O3, 50.9 pct SiO2, 1.4 pct Fe2O3, and 0.1 pct S. The PCE was 32-1/2, compared with a PCE of 31-1/2 for the crude clay. The fine beneficiated clays, of course, must be pelletized and dried or fired to meet commercial acceptance. This operation has already been solved by industry. Little progress has been made on two remaining problems. One is that of fine-grained impurities, not separable by table or cyclone. Flotation is being investigated to solve this. Although fine pyrite is readily rejected, a satisfactory quartz-clay separation has not been attained. The second problem, a stubborn one, is that of alkali. Samples containing as much as 5 pct potas-

Jan 1, 1961

By C. H. Mathewson

THIS paper was prepared upon request as a contribution to a symposium covering the manufacture, properties, and uses of the important non-ferrous metals. In approaching a subject as broad as this, there is a natural desire to build up a comprehensive and finished production which shall constitute a dependable source of information on all questions properly belonging to this branch of metal technology. There are, however, a number of circumstances, apart from the mere routine of labor and thought involved, which operate rather effectively against the possibility of completing such an ambitious program at the present time. First of all, as far as any public record of results is concerned, the commercial rolling, drawing, and forming of zinc with relation to changes of structure and properties-and this we consider to constitute the elements of metal technology-might as well be an unpractised art. We have never seen a published photomicrograph showing the structural characteristics of either hard or soft sheet or strip, although the structure of castings has been frequently described, and other coarse-grained structures resulting from hard-hammering and annealing have been reproduced. Thus, an author in this field must proceed to his task without much assistance from the literature, and the outcome can represent only a personal estimate of principles, facts, or findings, and not a summary

Jan 9, 1919

By J. W. Matousek, C. S. Samis

me thermodynamic properties of the components in the Cu-Ni-S ternary system have been studied by measuring the H2S/H2 ratios in a gas phase equilibrated with the molten matte at 1200°C. The measured sulficr potentials have been extended by extrapolation and combtned with previously published data to permit the thermodynamic analysis of the ternary system by integration techniques. A simplifying assumption of ideality in the Ni3Sz-CuS pseudobinary has been made. SINCE copper and nickel metals were first extracted from their sulfide ores the interaction between the two metals and sulfur has been of industrial and theoretical interest. The processes developed to extract copper and nickel have been reported periodically in the literature. The theoretical studies on the Cu-Ni-S ternary have been restricted to problems directly associated with production. It is only within recent years that the binary systems related to this ternary have been analyzed thermodynamically and mathematical devices developed to permit a corresponding treatment of the ternary system. In 1910 an investigation of the role of nickel in Cu-Ni-Fe-S mattes was reported,&apos; It was concluded from this work that nickel is not an element replacing iron in mattes, but rather that Cu-Ni alloys behave as a single metal during the matte converting operation. The laws which govern the converting of Cu-Ni alloys were found to be the same laws as those that govern the conventional converting of copper alone. Although considerable information has been reported on the theoretical aspects of copper smelting, little data is available on the smelting of Cu-Ni ores except for phase diagrams and process descriptions. The available information on the Cu-Fe-S ternary and related systems prior to 1953 has been summarized by Ruddle.2 Since Ruddle&apos;s publication, Rosenqvist and coworkers have completed phase equilibria investigations of the Fe-S, Co-S, and Ni-S binaries,3 the Fe-S-O ternary,4 and the Cu-Fe-S-O quaternary.4 An extensive investigation of the Cu-Fe-S ternary system at smelting temperatures has been made by Krivsky and Schuhmann.5 At these temperatures, the Cu-Fe-S system is very similar to the Cu-Ni-S ternary with respect to the location of the single-phase and two-phase liquid matte regions. In the former, however, the area of immiscibility is more extensive and the region of liquid matte-liquid metal-solid metal equilibria is much more extensive. Krivsky and Schumann observed that the Cu2S-FeS pseudobinary system is, for practical purposes, an ideal mixture. This investigation has served as a valuable guide in analyzing the Cu-Ni-S ternary. EXPERIMENTAL The experimental procedure employed in this investigation was the conventional technique of equilibration of the sulfide matte with gaseous mixtures of hydrogen and hydrogen sulfide at 1200°C. The thermodynamic properties of sulfur (S2) in the gas phase are determined by means of Eq. [I] and the activity of sulfur in the matte by Eq. [2].

Jan 1, 1963

By G. A. Mancini, V. Bharucha, J. W. Spretnak, G. W. Powell

The characteristics of the motion of the a interface during the "down" transformation was studied in zone-refined iron and dilute binary alloys containing nickel and molybdenum by means of the thermionic emission microscope and high speed photography. The frontal movements were found in all cases to be definitely discontinuous with time and an appreciable number of incremental jumps were found to proceed in the reverse direction (a to b). Molybdenum was found to be particularly effective in increasing the frequency of the increments of transformation from the stable to the metastable phase. A knowledge of the mechanism by which alloying elements affect the hardenability of a steel is desirable from both the practical and scientific viewpoints. It is well established that microstructures consisting of tempered martensite and lower bainite exhibit the best performance in terms of toughness and resistance to crack propagation. The presence of some upper transformation products, namely ferrite and pearlite, is in general undesirable. Various researches have indicated that the ferrite matrix grain structure is a very important difference between the upper and lower transformation products, namely equi-axed vs acicular. Any comprehensive theory of the decomposition of austenite should explain the dependency of the morphology of the matrix on undercooling. The contribution of various alloying elements to hardenability has been determined experimentally and catalogued in considerable detail. A rationalization of the basic mechanism or mechanisms by which individual elements affect the kinetics of the decomposition of austenite to products other than the phase "martensite" has not been evolved as yet. Interest in this problem was stimulated by the effects of minute quantities of boron in hardenable steels. This paper deals with one aspect of this problem, namely the characteristics of the ?-a transformation in high-purity iron and in two carbon-free iron binary alloys. A detailed historical account of the scientific developments in the study of the decomposition of austenite would be a prodigious undertaking and will not be attempted here. There are several excellent reviews in the literature on the formation of pearlite, martensitic reactions, and kinetics of solid-state reactions. The thinking on reaction mechanisms has been influenced to a large degree by the "classical" Tammann nucleation and growth model, in which an embryo springs into being by a fluctuation, and grows to a critical size through atom by atom deposition. Such a process is expected, accordingly, to be diffusion controlled. Considerable research attempting to relate the contribution of alloying elements to hardenability on the basis of their effect on the diffusivity of carbon in iron has not been productive from a mechanistic viewpoint. The formation of pearlite and ferrite has been treated in terms of nucleation and growth processes in which presumably the lattice transformation also occurs by a diffusion process. The other prominently considered mechanism is the "martensitic" or cooperative shearing mechanism. It seems generally, but not entirely, agreed that the phase "martensite" forms by this mechanism, and that it is involved to some extent in

Jan 1, 1962

By R. C. McFarlane, T. D. Mueller, J. E. Walstrom

In evaluating uncertainty, experiments are usually performed repeatedly and then conclusions are drawn from the distribution of results. With the advent of high-speed electronic computers, it is possible to perform experiments using mathematical models constructed to simulate complex experiments or operations. Statistical methods are then applied to the results of the simulated experiments. This procedure forms the busis of this paper. Demonstrated is the need for properly accounting for uncertainty in petroleum engineering problems. How uncertainty affects solutions is evaluated in three example illustrations. The method used to evaluate uncertainty in petroleum engineering studies is the Monte Carlo simulation procedure.&apos;-" INTRODUCTION The solution to most technical problems may be derived from interrelationships among several quantities called variables or parameters. There may be only a few variables or several hundred. Interrelationships among parameters may be explicit or implicit, well established or only approximate. Some variables that fully or partially depend on the magnitude of others are called dependent variables. Input variables for most practical problems are not precisely known; there is usually an uncertainty in their value. The degree of uncertainty may vary from one variable to another. Variables that are known accurately are called determinates.&apos; For instance, the gravity of crude obtained from a particular pool may be known precisely, and therefore is a determinate. The degree of precision with which a quantity can be determined increases as data describing the pool are accumulated during the development of the field and the producing life of the pool. The uncertainty of a parameter may result from difficulty in directly and accurately measuring the quantity. This is particularly true of the physical reservoir parameters which, at best, can only be sampled at various points, and which are subject to errors caused by presence of the borehole and borehole fluid or by changes that occur during the transfer of rock and its fluids to laboratory temperature and pressure conditions. Uncertainty may also result in attempting to predict future parameter values. This type of uncertainty is particularly evident in investment analyses involving future costs, prices, sales volumes and product demand. Uncertainty in the solution to investment problems is often called risk, and its study is called risk analysis.&apos; Uncertainty also enters into biological and sociological analyses in which indeterminate factors are often important due to limited control of the experimental material. It is customary, in evaluating uncertainty, to perform repeated experiments and to draw conclusions from the distribution of the results of these experiments. With the advent of the high-speed electronic computer, it is possible to construct mathematical models which simulate complex experiments or operations and to perform the experiments repeatedly, utilizing the models. Statistical methods are then applied to the results of the simulated experiments This method forms the basis of the investigation reported here. PROBABILITY DISTRIBUTIONS FOR VARIABLES The uncertainty in the value of a variable may be indicated by a probabilistic description accomplished by expressing the quantity by a probability distribution. Many recognized probability distributions can be used to describe physical quantities. Recent studies used various types of distributions to describe core analysis data.&apos;,&apos; However, for the examples in this paper, the uniform and triangular distributions are believed to reasonably approximate the data used (Fig. 1). The uniform distribution confines the variable between an upper and a lower limit. The variable may lie anywhere between the two limits. This distribution is used when no one range of values for a variable is more probable than any other, but information or intuitive reasoning indicates the variable will lie somewhere between the chosen limits. The triangular distribution is used for a variable when more data are available to indicate a central tendency of distribution. This allows postulating a "most likely" value to the distribution and upper and lower limits. In this case, as for the uniform distribution, the variable is not expected to assume a value less than the lower limit or greater than the upper limit. However, with improved quality of data it can be postulated that the variable will tend to assume a value close to the most likely value, and that there will be a decreasing probability for values away from the most likely value. The area under either of these probability distributions is equal to unity since it is assumed that there is a 100 percent probability that the variable will lie somewhere under the curve. An ordinate erected at any particular value of the variable divides the area under the curve into two parts: the area to the left of the ordinate represents the probability that the value of the variable will be equal to or less than the value of the variable at the position of the ordinate, and vice versa. The probability is zero that the variable will have any specific deterministic value. If two ordinates are drawn for any two values of the variable, the probability that the variables will have a value lying between these ordinates is equal to the area under the curve lying between the ordinates.

By Gunnar Thaning, Goran Mathisson

The iron ores mined by LKAB in the north of Sweden have excellent beneficiation properties. This gives LKAB a favorable position as regards the production of low silica pellets for direct reduction. LKAB has concentrated on developing and marketing grades of pellets for the Midrex-Purofer-HyL process group, i. e., such direct reduction processes carried out in a shaft furnace or a static bed using reformed natural gas as a reducing agent. The paper deals with properties and quality demands of iron ore pellets for such processes. Matters such as the effect of the residual magnetite in the fired pellets on the degree of metallization, the amount and composition of the slag phase in the pellets, the mechanism of the disintegration during reduction, the state of swelling of the pellets during the conditions prevailing in these processes, the importance of the porosity, the improvement of the reducibility and lowering of the sticking tendency of the pellets by small additions of suitable additives, and the influence of the pellet size are discussed. A special test procedure for direct reduction pellets has been elaborated by LKAB. Thus, three metallurgical properties are routinely determined separately, namely reducibility, reduction strength, and sticking. The test methods are described. Finally the present and future LKAB pellets for direct reduction are presented with respect to chemical analyses and metallurgical properties.

Jan 1, 1980