Search Documents

By C. L. T. Edwards

IN the preparation of this paper, the author has drawn upon experience with the operation of a blast furnace on 100 per cent scrap burden, which he believes was the first operation of its kind in the country. It is the writer's further belief that much of the controversy attending discussions of this subject may be obviated by the presentation of a group of facts that should be known by blast-furnace men and open-hearth men alike. The following question has been raised: "Is iron made with scrap in the blast-furnace charge as good iron as that made without scrap-made with straight ore?" This question may be answered in part by the fact that the open-hearth men of the Bethlehem Steel Co. who used pig iron from a blast furnace that operated on 100 per cent steel scrap found no difficulty in the processing of such iron other than that to be expected from the known analysis. OPERATION WITH 100 PER CENT STEEL SCRAP During World War I, there was accumulated at the Bethlehem plant of the Bethlehem Steel Co. some 22,000 tons of alloy-steel turnings and borings. This scrap material was highly corroded and, like alloy-steel turnings of that period, were as a drug on the market. There was also a small tonnage of scale, rich in valuable metal. If this scrap could be worked up into pig iron, it would become readily available for use in the open hearth. In order that the pig iron should contain the maximum percentage of nickel, permission was obtained from the Management to try a 100 per cent scrap operation. Accordingly, a blast furnace was swung over on July 25, 1919; the percentage of steel scrap increased more or less irregularly until July 29, when l00 per cent steel turnings were charged. Except for occasional charges of nickel scale as an "extra," the operation continued uninterruptedly until Aug. 27, when the furnace was swung back to the regular ore-ore and scrap-operation. During this period, the furnace production ranged from a low of 568.60 tons to a maximum of 766.07 tons. At the swing-over from i00 per cent scrap to the regular burden, the charge hung up rather severely. While the latter condition has nothing to do with the object of the paper, a brief discussion of the experience will appear later because of the interest it may have for blast-furnace operators. In Table I, results of the first and last days of the ore charge are shown, July 25 and July 29. The last column shows a summary for the period of maximum scrap charge. The furnace employed had a hearth 16 ft. 0 in., bosh 22 ft. 0 in., stock line 15 ft. 6 in., bell 11 ft. 6 in., batter ¾ in., bosh angle 73° 27' and a Baker-Neuman top, with gas-engine blowers. Analyses Range of Material Charged Gravel: Si02, 64.40 to .7o.54 per cent; A1203,3-52 to 4.58; CaO, 7.27 to 9.49; M90, 5.09 to 6.14; FeO, 1.67 to 3.34, ignition loss, 9.50 to 13.83.

Jan 1, 1941

* The greatest and richest iron ore body in the world was discovered by U. S. Steel in Venezuela in April 1947, and is disclosed for the first time in this issue (p. 178), One solid mountain of ore, Cerro Bolivar, will furnish more tonnage than the famous Hull Rust pit at Superior has, or can produce. Total resources are on the order of 2 billion tons plus. Big Steel is now moving with great speed on construction to bring out this ore, and 10 million tons are scheduled for shipment into Baltimore and Birmingham by late 1952. This ore will arrive at, Pittsburgh at a price lower than present natural ores from Superior. The Venezuelan properties will be completely mechanized. •U. S. Steel and independent companies are embarking on a taconite beneficiation program of tremendous proportions, which must be speeded to completion in the 1950's (see p. 185). By 1960 over $l.2 billion dollars will be spent on Venezuela, taconite, and Labrador to solve the United States iron ore crisis. In addition, U. S. Steel will spend another $300 million plus for a new steel mill at Trenton, N. J., before 1955. •The Deister Concentrator Co. gave $500 to the 1950 Coal Division Scholarship Fund. •Howard N. Eavenson, in analyzing the bituminous coal situation (see p. 193), suggests that anti-trust laws be extended to labor unions, disinterested trustees to administer pension funds, begin pension funds now and stop the collection of all "check-offs" for union dues or funds. •Minerals and metals worth 13.9 million dollars were produced in the United States in 1949, Secretary of the Interior Oscar L. Chapman announced. Although this value was 11 pct less than in 1948, it was the second greatest in history. Nonmetallics was the only major group that in 1949 equaled the 1948 production high. Mineral fuels decreased 12 pct and metals 15 pct. • Prospects for making gas from coal are seen to be unattractive by the Pittsburgh Consolidated Coal Co. because the success of operation depends on price and supply of coal which presently are not attractive. The company has shut down its gasification plant at Library, Pa. * Economic prospects for the immediate future in the United States are good and business probably will continue at its present high levels throughout at least the early part of 1950, Secretary of Commerce Charles Sawyer said in his year-end report to the White House based on his personal survey of business conditions. •A 467-ft well 34 miles north of Rock Springs, Southwestern Wyoming, is said to be flowing a 5 pct solution of nearly pure trona (sodium carbonate) at the rate of 10,000 barrels a day. Trona, natural soda ash, is mined for the chemical trade at Searles Lake, Calif., and from about 1500 ft underground near Green River, Wyo., and has been in short supply. •The AEC is "very much interested" in a discovery of radioactive material that has been made in Baraga County bordering Lake Superior in the Upper Peninsula of Michigan, reported F. G. Pardee, Michigan State mining engineer. The material has been identified as uranium oxide in the form of pitchblende or uraninite. The discovery, made by a geologist of the Jones & Laughlin Ore Co., is the only instance in which the commission has certified samples of Michigan rock.

Jan 2, 1950

By James A. Lewis

It is the purpose of this paper to show the importance of sand characteristics, when combined with other physical data, in evaluating production obtained by secondary recovery operations, and to indicate the benefits to be gained from the application of these principles to primary production. Introduction During the past 10 years there has been a growing interest within the industry regarding the movement of fluids through oil reservoirs. A number of research projects have been directed toward the development of the physical laws governing this movement. In the period 1933 to the present, correlations between laboratory analysis of cores, reservoir fluids and well performance have been established and have been applied to successful secondary water-flooding recovery operations; and to the completion, production, reconditioning and evaluation of wells in new fields. The application of these data to water-flooding, either natural or artificial, is comparatively new, but the principlcs involved were set forth in 1880 by John F. Carll,1 who said: The flooding of an oil district is generally viewed as a great calamity, yet it may be questioned whether a larger amount of oil cannot be drawn from the rocks in that way than by any other, for it is certain that all the oil can-not be drawn from the reservoir without admission of something to take its place. If one company owned all of the wells drawing upon a pool, and had accurate records of the depth and characteristics of the oil producing stratum in each well, it is quite possible that some system might be devised by which water could be let down through certain shafts, and thus the rocks be completely voided of oil and left full of water. As it is, however, no systematized plan of action can be adopted. The careless handling of one well. by which water is let down to the oil rock, may spoil several others belonging to different parties. A clashing of interests at once arises and is likely to result in disaster to the whole district. In judging of the probable effects of the intro-duction of water into any particular oil district several things are to be considered. (1st) The time of flooding—whether early in the progress of development, while yet a large percentage of oil remains unexhausted or at a later period after the supply has suffered from long continued depletion. (2nd) The structure of the rock—whether regular and homogeneous throughout, or composed of fine sand inter. bedding connected and irregular layers of gravel, sometimes lying near the top and at others near the bottom. (3rd) The shape of the area being flooded. (4th) The position of the point at which water is admitted. in relation to the location of the surrounding wells still pumping oil. (5th) The height (which governs the pressure) of the column of water obtaining admittance. (6th) The duration of the water supply. Although we may take exception to part of Carll's reasoning, particularly " and thus the rocks be completely voided of oil and left full of water," we must give him credit for pointing out the increased effectiveness of water encroachment in displacing oil from a sand and for his recording six of the present seven considerations necessary for evaluation of production of oil by water

Jan 1, 1942

By Roscoe E. Bell

BETWEEN 1945 and 1948 the author made studies of the western phosphate industry and its potentialities. These included an appraisal of the opportunities for western development of the industry, studies of production costs, of market potentials, of transportation economics, and of industry location. This paper will be directed toward pointing up the factors which have an important bearing on the establishment of fertilizer plants in the western area. Industry Location Factors: There are, of course, an infinite number of possible organizational setups which might require consideration. However, the phosphate industry is simple enough so that studies of the most probable alternatives can be made conveniently. The salient factors which require special consideration in such a study are: (I) the location of the raw materials, (2) the location, size, and character of the present and potential markets, (3) the location of energy sources and materials required for fertilizer processing, (4) the location and capacity of present manufacturing facilities, (5) the cost of assembling the materials and energy needed in manufacturing, and (6) the cost of distributing the manufactured product. Raw Material Supplies: Rock phosphate is the raw material for the manufacturing of phosphate fertilizer. In the United States the important known deposits of this material are located in three general areas (fig. 1). The western deposits, comprising about 60 pct of the nation's supply, are in the four-state area—Idaho, Wyoming, Utah, and Montana. The Florida deposits comprise roughly 38 pct of the national supply. The Tennessee deposits, comprising about 2 pct of the national supply, have been the most important source until recent years. The western deposits, which are virtually undeveloped, have not been used to any extent to meet the nation's need for phosphate rock and phosphate fertilizer. Fertilizer Markets: The large national markets for fertilizer are in the midwestern and eastern United States (fig. 2). The principal far-western markets are along the Pacific Coast, especially in California. Until recent years the western markets have been extremely limited, whereas the markets in the eastern United States have long been established and manufacturing facilities have been provided to meet these needs (fig. 3). In recent years the western markets have expanded very rapidly, continuing to grow throughout the war years and postwar period at a similar rate. The question always arises as to whether this is a temporary war-swollen market which will shrink back to its original size as soon as the present agricultural price levels drop. In order to answer this question consideration must be given to the character of the market (fig. 4). I have considered seventeen western and midwestern states in the western market area where transportation costs from the western deposits are equal to or lower than those from Florida. They include all states west of a line drawn through Chicago, Kansas City and the western boundary of New Mexico. In the mewar period this was a small market totaling only 37,000 tons of P,O, annually. The 1946 total for this same area was approximately 200,000 tons. Considerably more fertilizer would have been used in 1946 had adequate supplies been available. Estimates of future markets are difficult to make, but we do have some indices that are useful. The

Jan 1, 1951

By B. C. Wonsiewicz, G. Y. Chin

THE presence of deformation bands in cold-worked metals is known to influence the development of deformation textures1 but has not been considered in any theoretical treatments. At the present time the most rigorous theory of deformation textures appears to be based on Taylor's concept of homogeneous deformation of a crystal within a polycrystalline aggregate.' For each crystal the Taylor theory allows the operation of several equivalent combinations of five or more slip systems. Hence deformation bands can arise from the operation of a separate combination of slips in each of several portions within a crystal. On the other hand, a second type of band may occur as a consequence of slip on systems other than those selected on the basis on homogeneous deformation. This type appears to be associated with crystals of symmetrical orientations, such as the [loo] and [lll.] axial orientations in drawn wires of fcc single crystals studied by Ahlborn.3 In this note we propose a simple mechanism of deformation banding of the second type, and compare the theoretical results for wire drawing of [loo] and [Ill] with Ahlborn's observations. In outlini the model requires that the work to accomplish a given overall shape change by banding be less than or equal to the work to accomplish the same change by homogeneous deformation. While the work by homogeneous deformation, WH = ?T ;dri, can be calculated exactly by the equivalent methods of Taylor2 or of Bishop and Hill,4 the work by banding, WB, is less certain. The latter consists of 1) Wi, work by slip within a band, 2) Wb, work associated with formation of a boundary between bands, and 3) Wc, work to correct the difference in shape change arising from banding and homogeneous deformation. The Wi term can be evaluated explicitly for a band with an assumed set of slip systems, but a satisfactory analysis of Wb and Wc has not been obtained. Since WB = Wi + Wb + Wc WH, for banding to occur, however, a necessary condition is Wi = WH . Hence it seems reasonable to choose a band with the lowest value of Wi among competing bands consistent with Wi = WH, and then minimize Wb and Wc by arranging the physical configuration of the selected band. Wc is minimized by combining neighboring bands such that their net strain matches the macroscopic strain as closely as possible, and Wb is minimized by enforcing strain compatibility across the boundary between two neighboring bands, similar to the case of a grain boundary.5 It is realized that this procedure is not completely satisfactory, but it does seem to explain Ahlborn's observations reasonably well. The procedure is now outlined for the two corner orientations. a) [l00]. Fig. 1 shows a (100) stereographic projection. The results of the Taylor analysis for axi-symmetric flow by homogeneous deformation6 show that, while [loo] itself is unstable, the rotation of the tensile axis will nevertheless be confined to within about 15 deg from [loo]. Alternatively, less work may be expended by banding with slip on a pair of systems with primary-conjugate relationship, e.g., (ll1)[10l.I + (li1.)[110]. The latter represents minimum Wi for all possible bands.* Since there are four symmetrically

Jan 1, 1970

By James A. Lewis

It is the purpose of this paper to show the importance of sand characteristics, when combined with other physical data, in evaluating production obtained by secondary recovery operations, and to indicate the benefits to be gained from the application of these principles to primary production. Introduction During the past 10 years there has been a growing interest within the industry regarding the movement of fluids through oil reservoirs. A number of research projects have been directed toward the development of the physical laws governing this movement. In the period 1933 to the present, correlations between laboratory analysis of cores, reservoir fluids and well performance have been established and have been applied to successful secondary water-flooding recovery operations; and to the completion, production, reconditioning and evaluation of wells in new fields. The application of these data to water-flooding, either natural or artificial, is comparatively new, but the principlcs involved were set forth in 1880 by John F. Carll,1 who said: The flooding of an oil district is generally viewed as a great calamity, yet it may be questioned whether a larger amount of oil cannot be drawn from the rocks in that way than by any other, for it is certain that all the oil can-not be drawn from the reservoir without admission of something to take its place. If one company owned all of the wells drawing upon a pool, and had accurate records of the depth and characteristics of the oil producing stratum in each well, it is quite possible that some system might be devised by which water could be let down through certain shafts, and thus the rocks be completely voided of oil and left full of water. As it is, however, no systematized plan of action can be adopted. The careless handling of one well. by which water is let down to the oil rock, may spoil several others belonging to different parties. A clashing of interests at once arises and is likely to result in disaster to the whole district. In judging of the probable effects of the intro-duction of water into any particular oil district several things are to be considered. (1st) The time of flooding—whether early in the progress of development, while yet a large percentage of oil remains unexhausted or at a later period after the supply has suffered from long continued depletion. (2nd) The structure of the rock—whether regular and homogeneous throughout, or composed of fine sand inter. bedding connected and irregular layers of gravel, sometimes lying near the top and at others near the bottom. (3rd) The shape of the area being flooded. (4th) The position of the point at which water is admitted. in relation to the location of the surrounding wells still pumping oil. (5th) The height (which governs the pressure) of the column of water obtaining admittance. (6th) The duration of the water supply. Although we may take exception to part of Carll's reasoning, particularly " and thus the rocks be completely voided of oil and left full of water," we must give him credit for pointing out the increased effectiveness of water encroachment in displacing oil from a sand and for his recording six of the present seven considerations necessary for evaluation of production of oil by water

Jan 1, 1942

By I. W. Alcorn

THE cost of drilling in the past few years of proration and ever decreasing allowables has received increasing thought and study. It seems to parallel the strides made with respect to pumping problems in 1932 and 1933. Low profit margins stimulate the search for economies. Any discussion of slim-hole drilling involves a multitude of abstract values, and the problem can be attacked only by a study of records and rational thinking. In a measure, traditional methods must be studied with a questioning attitude. The words "slim hole" may be somewhat misleading, as the term is entirely relative. For that reason I wish to define it as used in this discussion. On the Gulf Coast, I would define a normal hole as one in which 10 3/4-in. surface casing has been set and below which a 9 7/8-in. hole is dug. With this as a datum, holes of larger diameter below surface would be called "large holes," with 12 1/4 in. as the "extra large" class and holes of smaller diameter classed in the slim-hole range, 6 1/4 in. representing about the minimum size. The optimum size has not been definitely determined, but the preference is for a program that would call for setting 8 5/8-in. surface casing and digging a 7 3/4-in. hole. Different sections of the country might very properly deviate from this practice because of differences in depth, formations, regulations, or other factors. This paper will be confined to a discussion of the drilling of exploratory wells, as the drilling of this class of wells is quite a different problem from that of drilling a proven field, although many of the same considerations apply in both cases, as will be apparent. Although for many years shallow slim-hole and core-test holes of small diameter had been dug, it was not, I believe, until the fall of 1937 that serious consideration was given to its application in drilling wells 7000 ft., 8000 ft. and 9000 ft. deep on the Gulf Coast. This does not mean that nearly all such wells drilled on the Gulf Coast now are of the slim-hole variety, but only that efforts have been aimed in that direction with very encouraging results and there has been a very definite trend to reduce the size of holes, a trend that probably will continue. As to exploration policy, there appear to be two distinct and opposite views. The one usually followed in the past was more or less designed to "shoot the works" on one well. Generally on the Gulf Coast, the depth at which production might be obtained is limited by the drilling equipment and economics. With this thought in mind, wildcat wells are often planned with the idea of carrying the depth to 10,000 ft., or even 15,000 ft. All of the possible hazards are anticipated and the general drilling and casing programs are so predicated. Such wells contemplate the drilling of large-diameter holes; the setting of at least one protective string of casing and an extensive coring policy, all of which finally adds up to an expensive well. As opposed to this general policy is the slim hole. This, on the Gulf Coast, recognizes that new discoveries represent gam-

Jan 1, 1941

By Fred H. Poettmann, J. K. Welchon, A. F. Bertuzzi

A series of gas-lift tests was made which verified conclusions reached from previous studies and which showed that gas-lift performance could be calculated if reasonably accurate data on the producing characteristics of the well are available.' The test installation is described. Its essential features consisted of a rate-of-flow controller to regulate the input gas and an auxiliary string of small diameter tubing to conduct the input gas to the point of injection in the eductor tubing. In general, it was shown that for continuous gas-lift operation, injection should be as deep as possible consistent with available gas pressure and rate of production desired. Calculated curves are presented which completely characterize the gas-lift performance of the well tested. INTRODUCTION A correlation based on field data from a large number of flowing and gas-lift wells, covering a wide range of oper- ating conditions, was developed which permitted the logical design and prediction of the performance of continuous gaslift installations.' The procedure made it possible to calculate the depth, pressure, rate at which to inject gas, horsepower requirements, and the effect of production rate and tubing size on these quantities. As a result of these calculations certain significant facts were brought to light or re-emphasized. The presence of efficient ranges of operation and an optimum injection depth for a given rate of production were shown to exist as well as the fact that the lower the tubing pressure the less the horsepower requirements to lift the reservoir fluids. The fact that the gas lift performance can be predicted by calculation does not mean that any given installation will perform over the entire range predicted. Many of the conventional continuous gas-lift installations will not permit operation over the entire range predicted by calculation (particularly in the efficient range of operation) because of the performance characteristics of the installation. Consequently, field tests were initiated for the purpose of investigating and arriving at a simple continuous gas-lift installation which would operate under all conditions predicted by calculation. The first series of tests involved the use of mechanically operated valves. These valves were slip-joint type valves which are opened and closed by lowering or raising the tubing at the surface by means of a hydraulic jack. These valves were chosen because it was hoped that they could be opened or closed at will and did not depend on the gas pressure in the annulus or the pressure of the fluid in the tubing for their operation. Unfortunately, the valves did not operate satisfactorily and it was imossible to open or close each valve at will. Some limited data were obtained, however, which verified the predicted benefits resulting from the use of lower tubing pressures. In the next series of tests the valves were removed and the gas was injected from the annulus through a 14/64-in. orifice equipped with a reverse check valve. A packer was set below the valve to seal off the space between the 2-in. tubing and 5-in. casing. The injection point was located at 3,810 ft. This arrangement provided satisfactory mechanical operation. However, it was impossible to obtain low rates of liquid production at low tubing pressures as predicted by calculation. A minimum gas injection rate existed below which steady flow was impossible. Liquid pro-

Jan 1, 1953

By A. W. Demmler

RECENTLY, Chaudron,&apos; Montariol,2 and their co-workers published the results of their studies on zone-refined aluminum. They found their material to be capable of recrystallization at —50°C, but gave no data as to the percentage reduction or time required. Their material was found to be practically non-work hardening at room temperature, but after 96 pct cold work at a low temperature and storage in liquid nitrogen it was found to recrystallize to coarse grains in less than 3 hr at 20°C. Recently, a study was made of the room temperature recrystallization characteristics of zone-melted aluminum. An ingot 14 in. in length, with a 3hx3 in. cross section, was made in an extremely high purity graphite boat under an atmosphere of dried commercial argon. It was made by first passing the molten zone along the ingot of 99.99+ pct A1 15 times. At this point, the most impure 3 in. (the end toward which the eutectic forming impurities migrated) were replaced with more of the original starting material, and 15 more traverses were made. Each traverse of the zone along the ingot required approximately 3 hr. Three ingots were prepared in this identical fashion and the chemical analyses were made spec-trographically on two of these ingots, rather than on the one used in this investigation. The analyses were made at 1 in. intervals along the ingot, in duplicate. Over the purest 5 in. of the ingot, which were most important in this investigation, there was found an average composition of <0.00004 pct Cu, <0.0003 pct Fe, <0.0001 pct Si, and <0.0001 pct Mg. In addition, the following elements were not detected spectrographically even in the more impure end of the bar: manganese, zinc, nickel, chromium, titanium, vanadium, lead, tin, boron, beryllium, bismuth, gallium, zirconium, cadmium, antimony, cobalt, and molybdenum. The original ingot was given several cold reductions, with intermediate anneals in order to refine the grains. Owing to the extreme length resulting and the ease of deforming the material plastically, it was cut into eight equal lengths and identified as shown in Fig. 1, with the highest numbered section at the purer end (that enriched with peritectic formers). Section 6 was used in the exploratory work and was found to be of exceptionally high purity, giving more rapid rates of room temperature re crystallization than any previous aluminum studied at the Alcoa Research Laboratories. This fact suggested that the entire midsection of the ingot might be of very high purity. Accordingly, section 4 was chosen for the next study. A portion of it was rolled to cold reductions of 10, 25, 40, 60, 75, and 90 pct at room temperature, and the re-crystallization of each specimen was followed by X-ray pinhole transmission photographs. The other portion received the same treatment, except that both the specimens and the rolls were maintained at 160°F in the process of rolling. The latter ortion was retarded in its recrystallization as compared to the former, probably due to the stress relief effect of the warm rolling. Both of these portions of the fourth section were found to recrystallize at a considerably slower rate than did the sixth section.

Jan 1, 1957

By Meguru Nagamori

DURING the smelting of the sulfide ores of copper, nickel, and certain other metals, a matte phase is formed. For a better understanding of the physico-chemical properties of mattes, binary systems such as Cu-S, Ni-S, Fe-S, and so forth, should be studied, especially in the vicinity of liquid compounds such as Cu2S, Ni3S2, FeS, and so forth. These compounds are relatively stable in the solid state although they can exhibit appreciable deviations from stoichiometry. With small deviations from stoichiometry there are large changes in the activity of both sulfur and metal this is a characteristic of both solid and liquid sul-fides near the stoichiometric compositions. In the vicinityof molten Cu2S,1 for instance, the activity of sulfur increases about 100 times for a 0.012 increase in the mole fraction of sulfur and, correspondingly, the activity of copper decreases greatly. In this sens the minor deviations from stoichiometry should be carefully taken into account in studies of such metal-sulfur melts. Metal-sulfur melts may be considered to have properties intermediate between metallic solutions and molten salts, i.e., neither entirely metallic nor entirely ionic. The radius of the ion sZ- is 1.84 as compared with 1.04? for a single bond covalent s.2 It is therefore inferred that when the sulfur is more ionic its partial molar volume is larger, although metal-metal, metal-sulfur, and sulfur-sulfur interactions may bring about further complexities. Thus, it is to be expected that the molar volumes, which are derived from density-composition relations, will help in resolving the structure of the melts. In this study the maximum bubble pressure method with bubbling gases of H2, H2S, and Ar, .was employed to measure the density. EXPERIMENTAL Materials. Silver of 99.95 pct purity was melted in an alumina crucible and hydrogen gas was then bubbled through the liquid for the deoxidation. In preparation of Cu2S, electrolytic copper powder (>99.9 pct Cu) was mixed with precipitated sulfur and heated to 1200°C in an alumina crucible under a hydrogen atmosphere. Mixtures having the approximate compositions FeS and Ni3S2 were prepared by heating reagent grade electrolytic iron or reduced nickel powder with precipitated sulfur under a hydrogen atmosphere. The H2S gas was of 98.5 pct purity, the impurities being mostly CO2 and CS2 which hardly contaminate the melts. Apparatus. The crucible system is shown schematically in Fig. 1. To minimize the variation of melt composition during a density measurement, the apparatus was designed in such a way that either Ar, H2, H2S, or mixtures of these gases could be used as the bubbling gas. When the melt had a high partial pressure of sulfur, H2S gas was used. When the partial pressure of sulfur was so low that oxygen might dissolve in the melt, the use of H2 was preferred. In intermediate cases, argon or mixtures of H2-H2S were used. Density of Dibutylphtalate. Dibutylphtalate was used as the manometer fluid. Relative to distilled water, the density of the dibutylphtalate, pdib g per cc, was measured and found to be: pdib (25°C) = 1.046 i 0.002. With the use of the temperature coefficient reported by Kemppinen and Gokcen,3 the following value was

Jan 1, 1970

By D. R. Spink

In the preparation of zirconium and hafnium metals, there are many indications that impurity levels control the physical and chemical properties of the metal. The purpose of this work was to develop methods of producing pure raw materials that could be reduced to highly pure metals. Early work by the Carbomcndum Metals Co. and others indicated that certain fused salts were highly efficient in the removal of impurities from gaseous zirconium tetrachloride. We have developed workable fused salts along with a continuous and higly efficient scrubber design which can be used to produce very pure zirconium tetrachloride. Metal made from the purified tetrachloride has been shown to approach crystal bar metal in purity. Scrubber designs are discussed with recommended materials of construction. VARIOUS methods have been used to purify zirconium (and hafnium) tetrachloride. Most of these methods involve thermal degassing initially (the removal of more volatile compounds at temperatures below that where zirconium tetrachloride exhibits a significant vapor pressure) followed by a sublimation step (which conveniently leaves the nonvolatiles behind.) While these procedures effect definite purification, such processing is batchwise and does not result in optimum purification. Early work by The Carborundum Metals Co. and others indicated that fused salts were highly efficient in the removal of impurities from gaseous zirconium tetrachloride. The objective of this work was to develop a continuous fused-salt scrubbing process that would yield high-purity zirconium and hafnium tetrachlorides. The term "fused salt" refers to the molten state of ionic compounds and as used here, specifically refers to alkali metal and alkaline earth halides. Fused salts, because of their many valuable properties, are becoming increasingly im- portant industrially. These valuable properties of the fused salts are: 1) stability at elevated temperatures; 2)low vapor pressure; 3) low viscosity; 4) ability to dissolve many different materials; and 5) good elctctrical conductivity. All but the last property enhances the use of fused salts as scrubbing agents for zirconium and hafnium tetrachlorides. Fused-salt scrubbing may be defined for our purpose as the intimate contact between a gaseous compound and a molten salt with the purpose of removing impurities from the gaseous compound. In this case, the gaseous compound is zirconium tetrachloride which submlimes at 331°C. When this gas is contacted with a molten salt, impurities such as aluminum, iron, and titanium are removed and the resulting product is considered fused-salt scrubbed. Zirconium and hafnium are sold to a purity specification. Generally speaking, normal production without scrubbing is capable of meeting specifications. There are, however, several considerations That make the knowledge of methods of additional purification highly desirable. These are: 1) the control of product analysis; 2) the production of a pure product for special applications; 3) the salvaging of off-specification material; and 4) the use of raw materials with higher impurity levels than 1 he present raw materials. You will note that items 1 and 2 are somewhat complementary to each other and that item 4 assumes that The present process has impurity removal limitations. To better understand the part that fused-salt scrubbing of zirconium tetrachloride plays in the manufacture of zirconium, Fig. 1 contains an illustrated flow sheet of the industrial production of zirconium metal. In referring to Fig. 1, we can point out the specific benefits derived from our ability to purify zirconium tetrachloride. Purification of the crude (hafnium-containing) zirconium

Jan 1, 1962

By Roscoe E. Bell

BETWEEN 1945 and 1948 the author made studies of the western phosphate industry and its potentialities. These included an appraisal of the opportunities for western development of the industry, studies of production costs, of market potentials, of transportation economics, and of industry location. This paper will be directed toward pointing up the factors which have an important bearing on the establishment of fertilizer plants in the western area. Industry Location Factors: There are, of course, an infinite number of possible organizational setups which might require consideration. However, the phosphate industry is simple enough so that studies of the most probable alternatives can be made conveniently. The salient factors which require special consideration in such a study are: (I) the location of the raw materials, (2) the location, size, and character of the present and potential markets, (3) the location of energy sources and materials required for fertilizer processing, (4) the location and capacity of present manufacturing facilities, (5) the cost of assembling the materials and energy needed in manufacturing, and (6) the cost of distributing the manufactured product. Raw Material Supplies: Rock phosphate is the raw material for the manufacturing of phosphate fertilizer. In the United States the important known deposits of this material are located in three general areas (fig. 1). The western deposits, comprising about 60 pct of the nation&apos;s supply, are in the four-state area—Idaho, Wyoming, Utah, and Montana. The Florida deposits comprise roughly 38 pct of the national supply. The Tennessee deposits, comprising about 2 pct of the national supply, have been the most important source until recent years. The western deposits, which are virtually undeveloped, have not been used to any extent to meet the nation&apos;s need for phosphate rock and phosphate fertilizer. Fertilizer Markets: The large national markets for fertilizer are in the midwestern and eastern United States (fig. 2). The principal far-western markets are along the Pacific Coast, especially in California. Until recent years the western markets have been extremely limited, whereas the markets in the eastern United States have long been established and manufacturing facilities have been provided to meet these needs (fig. 3). In recent years the western markets have expanded very rapidly, continuing to grow throughout the war years and postwar period at a similar rate. The question always arises as to whether this is a temporary war-swollen market which will shrink back to its original size as soon as the present agricultural price levels drop. In order to answer this question consideration must be given to the character of the market (fig. 4). I have considered seventeen western and midwestern states in the western market area where transportation costs from the western deposits are equal to or lower than those from Florida. They include all states west of a line drawn through Chicago, Kansas City and the western boundary of New Mexico. In the mewar period this was a small market totaling only 37,000 tons of P,O, annually. The 1946 total for this same area was approximately 200,000 tons. Considerably more fertilizer would have been used in 1946 had adequate supplies been available. Estimates of future markets are difficult to make, but we do have some indices that are useful. The

Jan 1, 1951

By B. S. Lement

No appreciable stabilization of the austenite-martensite reaction occurs in a 15 pct Cr-0.7 pct C steel unless some martensite is initially present. Stabilization is induced by interrupting the subcool below M,; however, disappearance of the stabilization effect as manifest by burst formation of martensite may occur on continued holding at the final subzero reaction temperature. The higher the temperature of intermediate cycling after the initial subcool, the more permanent is the stabilization effect at the final reaction temperature. Appreciable conditioning of retained austenite occurs on reheating to about 500°C. These phenomena are explainable on the basis of the reaction-path theory. A RECENT investigation&apos; carried out by the authors has shown that isothermal transformation of austenite to martensite definitely takes place in a 15 pct Cr-0.7 pct C steel and that appreciable amounts of martensite can form in this fashion. Investigations2-" arried out on other steels and iron alloys make it seem probable that isothermal formation of martensite is a phenomenon of fairly general occurrence. The reaction-path theory of Cohen, Machlin, and Paranjpe5,7 explains isothermal transformation on the basis of thermal activation of strain embryos which generate martensite plates with a velocity approaching that of sound. On the other hand, the nucleation and growth theory of Fisher, Hollo-mon, and Turnbull8 egards isothermal transformation as due to growth of athermally formed martensite nuclei. The experimental evidence obtained thus far favors the reaction-path theory in that the martensite reaction seems to be nu-cleation-controlled rather than growth-controlled. Stabilization is another phenomenon of importance with respect to the austenite-martensite reaction. According to the reaction-path theory, stabilization is a result of relaxation of strain embryos. It is postulated that strain embryos are present at the austenitizing temperature in the form of dislocations or lattice imperfections in the austenite which vary in the extent to which the lattice is displaced along the strain reaction path leading to martensite. On quenching from the austenitizing temperature, athermal martensite starts to form as soon as the M. is reached, because the activation energy of the transformation which decreases with decreasing temperature is lowered to below the level of the highest energy strain embryos. Martensite plates are generated during the cooling below M, from embryos possessing energies above the activation energy corresponding to the temperature at which the cooling is stopped. The distribution of lower energy embryos is changed because of the elastic and plastic strains produced in the remaining austenite as a result of the transformation. This effectively increases the number of strain embryos at all levels of energy below the activation energy and tends to stimulate further martensite formation either iso-thermally or on subsequent cooling. However, if the temperature at which the cooling is stopped is high enough for relaxation of strain embryos to occur, some degree of stabilization against further transformation may be induced. Whether stabilization will be observed on subsequent cooling will depend on the extent of decrease of activation energy with temperature. If the activation energy decreases sharply with temperature, it is possible that transformation will appear to continue with decrease in temperature in spite of the loss of embryos by relaxation. However, with a more gradual decrease in activation energy, stabilization will be manifest by no further transformation on cooling over a measurable temperature range until the

Jan 1, 1954

By S. A. Falconer

This paper deals with the practical application of the Dutch State Mines cyclone separator for fine-coal cleaning. The more important operating variables are discussed, and results of a number of continuous-scale tests on various fine coals with a 6-in. cyclone separator are given. Descriptions of the Cyanamid Pilot Plant and the 50 tph Cyclone Separator Plant at the Emma Washery in Holland are included. TODAY, as never before, the coal producers of this country are faced with the necessity for obtaining maximum yield of marketable coal of all sizes down to and including the finest. Particular interest is being displayed in a more effective means of recovering the finer sizes which in the past so often have been discarded to waste or treated by inadequate equipment. The reasons for this interest are easily understood. Rising mining costs have resulted in the increased use of mechanized equipment underground for full seam mining. This, in turn, means more refuse in the run-of-mine and also more fines in the feed going to the cleaning plant. Stringent antistream pollution laws now make it necessary at least to impound the fines, and usually it is a paying proposition to recover the coal from these fines before sending them to the storage area. Finally, the market and price of the finer sizes has increased, but at the same time specifications have tightened and the demand is for higher grade products. During the past four years a great deal of publicity has been given to this new process and apparatus for treating fine sizes of ores as well as coal. Excellent discussions of the apparatus itself and the theoretical aspects of the basic operating principles involved in its operation have been presented by M. G. Driessen,1-3 M. R. Geer and H. F. Yancey,4,5 J. W. Hyer6 and more recently by D. A. Dahlstrom8 as well as others.7,9-11 In view of this, it has been decided to include in the present paper only a brief description of the cyclone separator and its operating principles. This paper deals primarily with some of the more practical commercial aspects of the process and equipment required for its operation; the variables in the operation of the cyclone, their effect and means for control; and the results obtained with a 6-in. semicommercial size separator on a variety of fine coals, bituminous and anthracite, using finely ground magnetite for the separating medium solids. A description is included of the commercial-size cyclone separator pilot plant installed by the Dutch State Mines at its Emma mine in Holland, where finely ground slate is utilized as medium solids. Field of Application: The Dutch State Mines cyclone separator operates most efficiently on ores and coal in the size range of % in. to about 48 mesh. On some types of feed, effective separation can be made on sizes as small as 100 mesh, but up to the present, this may be considered exceptional. Depending upon the type of medium used, the specific gravities of separation can be varied within wide limits, up to as high as 2.70, if magnetite is used as medium. Early Development: The development of the Dutch State Mines cyclone as a separator, or cleaner, was the outgrowth of early experimental work by Dries-sen&apos; and others in Holland, just prior to World War 11, in the course of which was discovered the effectiveness of the cyclone in reclaiming and thickening the dense medium used in the "Loess" process of

Jan 1, 1951

By S. A. Falconer

This paper deals with the practical application of the Dutch State Mines cyclone separator for fine-coal cleaning. The more important operating variables are discussed, and results of a number of continuous-scale tests on various fine coals with a 6-in. cyclone separator are given. Descriptions of the Cyanamid Pilot Plant and the 50 tph Cyclone Separator Plant at the Emma Washery in Holland are included. TODAY, as never before, the coal producers of this country are faced with the necessity for obtaining maximum yield of marketable coal of all sizes down to and including the finest. Particular interest is being displayed in a more effective means of recovering the finer sizes which in the past so often have been discarded to waste or treated by inadequate equipment. The reasons for this interest are easily understood. Rising mining costs have resulted in the increased use of mechanized equipment underground for full seam mining. This, in turn, means more refuse in the run-of-mine and also more fines in the feed going to the cleaning plant. Stringent antistream pollution laws now make it necessary at least to impound the fines, and usually it is a paying proposition to recover the coal from these fines before sending them to the storage area. Finally, the market and price of the finer sizes has increased, but at the same time specifications have tightened and the demand is for higher grade products. During the past four years a great deal of publicity has been given to this new process and apparatus for treating fine sizes of ores as well as coal. Excellent discussions of the apparatus itself and the theoretical aspects of the basic operating principles involved in its operation have been presented by M. G. Driessen,1-3 M. R. Geer and H. F. Yancey,4,5 J. W. Hyer6 and more recently by D. A. Dahlstrom8 as well as others.7,9-11 In view of this, it has been decided to include in the present paper only a brief description of the cyclone separator and its operating principles. This paper deals primarily with some of the more practical commercial aspects of the process and equipment required for its operation; the variables in the operation of the cyclone, their effect and means for control; and the results obtained with a 6-in. semicommercial size separator on a variety of fine coals, bituminous and anthracite, using finely ground magnetite for the separating medium solids. A description is included of the commercial-size cyclone separator pilot plant installed by the Dutch State Mines at its Emma mine in Holland, where finely ground slate is utilized as medium solids. Field of Application: The Dutch State Mines cyclone separator operates most efficiently on ores and coal in the size range of % in. to about 48 mesh. On some types of feed, effective separation can be made on sizes as small as 100 mesh, but up to the present, this may be considered exceptional. Depending upon the type of medium used, the specific gravities of separation can be varied within wide limits, up to as high as 2.70, if magnetite is used as medium. Early Development: The development of the Dutch State Mines cyclone as a separator, or cleaner, was the outgrowth of early experimental work by Dries-sen&apos; and others in Holland, just prior to World War 11, in the course of which was discovered the effectiveness of the cyclone in reclaiming and thickening the dense medium used in the "Loess" process of

Jan 1, 1951

By J. R. Morison, M. P. O’Brein, J. W. Johnson, S. A. Schaaf

The force exerted by unbroken surface waves on a cylindrical object, such as a pile, which extends from the bottom upward above the wave crest, is made up of two components, namely: 1. A drag force proportional to the square of the velocity which may be represented by a drag coefficient having substantially the same value as for steady flow, and 2. A virtual mass force proportional to the horizontal component of the accelerative force exerted on the mass of water displaced by the pile. These relationships follow directly from wave theory and have been confirmed by measurements in the Fluid Mechanics Laboratory of the University of California, Berkeley. The maximum force exerted by breakers or incipient breakers is impulsive in nature, reaching a value much greater than that produced by unbroken waves but enduring for only a short time interval. This impulsive force represents the ultimate development of the accelerative force and is produced by the steep wave front and large horizontal acceleration at the front of a breaker. This impulsive force greatly exceed. the drag force computed from the particle velocities of the breaker. The reader is cautioned that these preliminary results are applicable only to single piles without bracing and are likely to be modified somewhat where multiple piles are driven, one within the influence of the other or where multiple piles are connected by submerged bracing. This paper is essentially a preliminary report submitted at this time because of the current importance of wave forces in the design of offshore structures. An extended series of additional experiments is planned for the near future. Theoretical Relationships For the sake of simplicity of treatment, the theory will be developed from the equations for waves of small amplitude. The horizontal displacement of a water particle is described by the equation 2p cosh — (d + z) H L 2pt X =----------------------sin ----- . , (1) 2 2pD T sinh------ L The horizontal component of the orbital velocity is obtained by differentiation with respect to time as 2p cosh — (d + z) pH L 2pt u = ------------------- cos— .... (2) sinh- L The acceleration of the water particles at any position is obtained by again differentiating with respect to time as 2p cosh — (d + z) 9 u -2vH L 2pt -----=----------------------------sin ----- . . (3) 3 t T2 2pd T sinh------ L where H = wave height — ft L = wave length — ft d = still water depth — ft z = depth below the still water measured negatively downward — ft. T = wave period — sec t = time — sec The force exerted on a differential section, dz, in length is pD2 s u pD 1 dF= [CM (p/4) st + Cn/2 u2] dz • • (4) where D = pile diameter — ft p = water mass density — slugs/ft3 C, = coefficient of mass C,, = coefficient of drag Substituting for a s u/s t arid u2 from Eqs. (3) and (2), the force per unit length at any position z is dF p2 pD H2 &apos; / = — [- fM sin ? ± fD cos2 ? ] . . . (5) dz 2T2 fM D fD 2pt Cm = pA/H:CD = A2;? = T [+ cos2 ? for 0 < ? < p/2 cosh— (d+z) 3p L — < o < 2p Sin L -cos2 ? for p/2 <? <3p/2 The sin 9 term (inertia) i- negative for 0 < 0 < p and positive for p < ? < 2p. Values of A and A&apos; appear in Fig. 1

Jan 1, 1950

By S. Shapiro, G. Krauss

RECENT investigations1 3 of the products of marten-sitic transformation in Fe-Ni and Fe-Ni-C alloys have made use of light microscopy to describe mar-tensitic fine structure. The application of conventional metallographic techniques to this problem was possible because of the similarity of distributions of parallel striations developed by etching polished surfaces to distributions of transformation twins which are positively identified in thin films by transmission electron microscopy. The surface striations frequently are not well-defined, and could also be due to, for example, rows of etch pits which are not resolved by the light microscope. This note describes the etching effects revealed by examination of surface replicas of mar-tensite in the electron microscope. The application of a replica technique both extends the observations of fine structure made with the light microscope and allows the results of conventional metallography to be used with more confidence. Samples of an Fe-33 wt pct Ni alloy were used for this study because of the detailed knowledge of the fine structure of martensite which has been developed&apos;-4 for alloys of about this composition. Samples transformed to martensite at -120°C, and transformed samples heated to 340°C to effect a small amount of reversal of martensite to austenite, were examined. Surfaces were first prepared for replication by elec-tropolishing in a chromium oxide-acetic acid electrolyte at a current density of 0.1 amp per sq cm and a temperature of 15°C or a perchloric acid-acetic acid electrolyte at a current density of approximately 2 amps per sq cm and a temperature of 15°C. The polished surfaces were then etched for 4 to 7 sec by immersion in a solution of equal parts HC1, HNO,, and H20. Application of the etchant for this period of time produced discrete attack of certain features without loss of resolution due to overlapping of areas most susceptible to etching. The etched surfaces were replicated by 1) preshadowing with Pt-Pd alloy at an angle of 20 to 30 deg, 2) depositing a thin carbon film, and 3) stripping the film and shadowing material by immersion in a 5 pct nital solution. Two types of etching effects were observed by examination of the surface replicas in the electron microscope: l) continuous striations centered at the bottom of long grooves or the tops of pyramidal elevations on the sample surface, and 2) high densities of fine etch pits. Examples of both types of features are shown in Figs. 1 to 4. The striations are in each case continuous and have the same characteristic configurations as do transformation twins in martensite. Fig. 1 shows that the density of grooves decreases toward the edge of a martensite plate and Fig. 2 shows a region where the striations are of varying length. Similar examples of transformation twin arrangements determined by transmission electron microscopy of thinned foils of martensite have been shown in the literature,&apos;~ and, based on these similarities, the striations and their associated grooves or mounds are considered to be evidence for the presence of transformation twins. The transf~rmation twins in martensite are on the order of l00 A thick, much too fine for resolution by the light microscope. It appears that orientation-dependent etching of the matrix martensite about the twins results in grooves or surface elevations which

Jan 1, 1967

By N. J. Grant, C. F. Flo, F. B. Cuff

An investigation of the Ti-Cr system has shown the presence of a complete series of solid solutions in the ß phase, with a minimum in the solid us near 50 pct Cr. An intermetallic compound, TiCr2, forms during cooling from the ß solid solution. There is a eutectoid reaction at the low chromium side of the system. IN view of the recognition of the potentialities of titanium and its alloys as important structural materials there has arisen a need for a systematic investigation of various titanium binary diagrams. Of these, the Ti-Cr system was of particular interest because of the improved properties imparted to titanium by small chromium additions. A literature survey disclosed a partial constitution diagram that had been suggested by Vogel and Wenderott,¹ This diagram, shown in Fig. 1, is the result of work done on the Fe-Cr-Ti ternary system. Alloys containing less than 43 pct Cr were not investigated. In addition to this, a study of alloys in the Ti-Cr system was reported by McPherson and Fontana.² Adenstedt3 furnished a number of dilato-meter curves obtained from specimens containing 5, 10, and 15 pct Cr. Very recently, McQuillan4 submitted a proposed diagram covering the complete range of compositions between titanium and chromium. This diagram was in general agreement with the one described here. Experimental Procedure Sponge titanium (99.7 pct) and electrolytic chromium (Bureau of Mines analysis: 99.03 pct Cr, 0.40 pct Fe, 0.53 pct O2) were used for the initial determination of the system. Subsequent refinement of points, particularly for the low chromium side of the diagram, was accomplished by using iodide titanium and high purity chromium (National Research Corp. analysis: 0.050 pct C, 0.045 pct O2). The Ti-Cr alloys were prepared by melting 25 g charges in an enclosed, water-cooled copper crucible using a movable tungsten electrode. The atmosphere was helium, prepurified by first passing it through a drying agent and then through sponge titanium heated to 850°C. Particular care was taken to avoid any large scale segregation resulting from insufficient mixing of the components. Each charge was melted and kept molten for approximately 1 min, allowed to cool, inverted, remelted, and kept molten for an additional minute. In order to ascertain the amount of impurity pickup (oxygen and nitrogen) during the melting procedure, three iodide titanium specimens were melted in sequence and then checked for increased hardness. The specimens in the as-cast condition showed a relatively large hardness increase over the hardness of the as-received iodide titanium. The scattering on these readings was large. However, after the specimens had been homogenized at 840 °C for 2 hr and slowly cooled, the measured increase in hardness over the as-received titanium was small with a corresponding decrease in scatter. The reason for this hardness change is that in heat treating these specimens below the transformation temperature (885°C) there was a conversion from the as-cast structure to the more nearly equilibrium structure of the annealed specimen. The alloys were analyzed for chromium content and although the actual percentage was invariably low the deviation from the nominal composition never exceeded 0.6 pct Cr.

Jan 1, 1953

By D. J. DeLazaro, W. Rostoker, R. E. Riley, M. Hansen

KNOWLEDGE of the isothermal transformation behavior and the TTT chart method of graphically summarizing such information has been of invaluable aid to the ferrous metallurgist in understanding and developing heat treatments intended to provide specific mechanical properties. It is to be expected that similar lines of study directed to titanium-base alloys will be as profitable. This paper summarizes, on conventional TTT charts, the isothermal transformation products and pertinent reaction rate data for binary alloys of titanium containing 1, 3, 5, 7, 9, and 11 pct Mo, respectively. The results so presented were derived from metal-lographic examination. Some X-ray diffraction work was done to clarify certain points of question. Ti-Mo System To the authors&apos; k.nowledge, TTT charts have only been used to describe the reaction rates of eutectoidal decompositions. It would seem that the kinetics of decomposition of any unstable solid solution might be conveniently described in this manner. The equilibrium diagram of the Ti-Mo system&apos; is shown in Fig. 1. The similarity with the Fe-Ni system will be recognized. Additions of molybdenum serve to stabilize the /3 phase to increasingly lower temperatures. The solubility of molybdenum in the a phase is restricted to less than 1 pct at 600°C. Under normal conditions. a homogeneous ,8 structure quenched to a, temperature in the a f & field will reject a of invariant composition. The rate at which this occurs depends on the degree of undercooling and the degree of supersaturation of /3. The structural character of the rejected phase may also be expected to be related to the undercooling. Materials and Experimental Methods A sponge titanium was used which has a nominal impurity content as reported in Table I. The nominal composition of the molybdenum used is also included. The alloys were prepared in 150 g melts by arc melting in an evacuated water-cooled copper crucible of the type reported in an earlier paper.&apos; The pancake-type ingots were forged to 1/4x1/4 in. bars and homogenized for 24 hr at 1000°C in evacuated Vycor bulbs. Specimens Vi in. thick were cut from these bars for heat treatment. The heat treatment cycles followed an invariant procedure. The specimens were soaked at 1000°C for 20 min under a helium protective atmosphere prior to quenching into a lead bath held at a temperature corresponding to a chosen degree of undercooling. After a prescribed period of time at this temperature, the specimen was removed and water quenched. A series of specimens so treated for progressively longer periods served to establish the times for initiation and completion of the decomposition of the /3 phase at a particular temperature. Although heat treatment of unprotected specimens in a lead bath does permit surface contamination by lead diffusion, this method is necessary to insure sufficiently rapid quenching rates. As long as the bath treatments were of less than 1 hr duration. the contaminated surface was not unduly deep and could be removed without excessive grinding. Metal-lographically, the contaminated zone could be readily distinguished from the pure binary alloy. Transformation Characteristics of Ti-Mo Alloys Metallographic examination showed that a supersaturated p phase may decompose by one of two processes. Alloys containing 1 to 9 pct Mo, when quenched in water from the homogeneous /3 field,

Jan 1, 1953

By J. Geertsma

In order to obtain a better insight into the pressure-volume relationship of reservoir rocks a theory of pore and rock bulk volume variations is presented. The theory is independent of the shape of the pores but is restricted to isotropic porous media built up of continuous homogeneous matrix material. The main conclusion obtained from this theory is that only three elastic constants and three viscous constants are required for describing pore and rock bulk volume variations if the porosity is explicitly introduced into the treatment. In addition, reasonable approximations are introduced for various types of reservoir rock, e.g., sandstones, limestones, and shales, which lead to further simplifications of the basic formulas. In consequence there is then a further reduction in the number of deformation constants which have to be determined experimentally. It is shown how measurements of these remaining deformation constants can be performed most conveniently. Finally the application of the theory to reservoir studies is discussed and the translation of experimental results obtained in the laboratory into reservoir behavior is considered. INTRODUCTION The decline of fluid pressure in connection with the withdrawal of fluid from an underground reservoir gives rise to a change in volume of both reservoir fluids and reservoir rock. The volume variation of the reservoir rock results in a decrease of both the pore volume and the total volume of the fluid-filled formation. Whereas the variation in volume of the reservoir fluids with pressure is usually known from PVT analysis, that in the volume of the porous medium is rarely measured, as it is considered of minor importance in reservoir engineering. Nevertheless, certain experimental results&apos; suggest that in a number of cases the neglection of the variation in pore volume may introduce errors into material balance calculations of reservoirs producing above the bubble point. Only a few experimental results on the compressibility of porous rocks have been published. The compressibility of pure quartz and of calcite can be found in a paper by Adams and Williamson&apos;. Botset and Reed&apos; carried out some experiments on the compressibility of loose sands, while Carpenter and Spencer&apos; measured the compressibility of a number of consolidated sandstones, which data were supplemented by Hughes and Cooke5. Hall&apos; finally reported a number of experiments designed to study the influence of the porosity on the compressibility of oil-bearing formations, from which it appeared that, particularly in the low porosity range, the compressibility of the pore volume is important enough to be taken into account. Difficulties, however, arise in applying these experimental results to field cases. This is partly due to the fragmentary nature of the published data. Yet even if more complete data were available, the need for a theoretical background would be strongly felt. Such a background can be partially found in studies carried out by Biot,6,7 who published a theory of elastic deformations of porous materials and their influence on fluid displacement within the pores, by Lubinski8, who studied the stress distribution in an elastic porous medium neglecting pore compressibility, and by Gass-mann" who mathematically analysed the elasticity of packings of spheres. The contributions of Biot intro-duce a number of deformation constants which are impractical for reservoir rocks from an aspect of experi-mental determination. The theory developed by dass-mann is correct but difficult to read. It appeared, how-

Jan 1, 1958