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By R. M. Brick

Segregation can occur only in cast alloys that solidify over a range of temperatures with a difference in composition of liquid and solid phases within this range (ignoring monotectic systems and chemical reactions as in rimming steels). Thus a pure binary eutectic alloy should show no segregation unless undercooling occurs for one of the solid constituents of the eutectic; e.g., chill-cast Al-I2 per cent Si alloys. The phasial condition implicitly described above—solidification over a range of temperatures with a compositional difference between solid and liquid—is found in nearly all solid solutions or combinations of solid solutions and eutec-tics, Metastable conditions of solidification of these types of alloys cause coring; i.e., a difference in composition between the center of a dendrite and its periphery. This composition gradient can be detected usually only by microscopic examination of etched structures; it is a "micro" effect. The gradient of more immediate industrial concern is that between the center of a cast section and the surface layers. This gross (macro) effect is usually deter-minable only by sampling of the casting at different points, with chemical analyses of each sample. If the compositional difference is of the same type as in coring, the first parts to freeze being enriched in higher-melting-point constituents, and vice versa, the effect is called normal segregation. When what is apparently the first part of the casting to solidify shows a higher concentration of low-melting-point constituents, the effect is called inverse segregation. These macro effects are quite separate from the micro effect, coring, yet the latter must be described first because it is an essential part of the picture. Coring Solid Solution, Ni-Cu The nickel-copper phase diagram is reproduced in Fig. Ia, in which the solid lines represent the equilibrium liquidus I, 3, 7 and solidus 2, 5, 8, and where the vertical I, 4: 8 represents a 55 per cent Cu alloy. Upon moderately rapid solidification, the first dendritic axes of composition 2 (see Fig. Ib) start to form at a temperature somewhat under I. Solidification continues by growth of the dendritic nuclei, but at temperature 4 the increment solidifying is of composition 5. The rapidity of this crystal growth prevents diffusion of nickel and copper atoms from adjusting the composition of the entire dendrite at 5, which it would be under equilibrium conditions. The average composition of a specific dendrite, or the entire solid phase, at temperature 4 might be that indicated

Jan 1, 1945

By Eugene F. Poncelet

Glass squares compressed on edge by steel jaws in poor contact with them developed jagged "partial-contact" cracks caused by the formation of local tensile stresses. Compressed by steel jaws in perfect contact, they developed smooth "release cracks" during release of the pressure, caused by the formation of local tensile stresses during the release of the pressure. All these cracks were parallel to the pressure. A Microflash photograph of a disintegrating specimen under sufficient pressure reveals a network of fractures roughly normal to each other, also "release cracks" and a disintegration cloud. The Griffith theory is amended to account for the formation of a first crack. A new theory, based on the theory of thermal agitation and wave propagation, is proposed to account for the progress, velocity and forking of cracks. The network of fractures is shown to have been caused by reflection at a free boundary of pressure pulses emanating from a first crack. Postulating equal distribution of energy in the pulses emitted on either side by a crack in particles, the smaller fragments are shown to continue fracturing preferentially while some of the coarser fragments remain as residual pieces. As comminution of the smaller fragments proceeds, the solid is reduced to a collection of residual particles of smaller and smaller sizes, accounting for the disintegration cloud. Experimental Procedure Apparatus A crushing device was built, consisting of a steel frame and two polished, hardened steel jaws to crush plate-glass samples. This device was placed between the plates of a hydraulic press (Fig. I). For centering the pressure, the upper jaw was guided vertically and provided with a rounded top. Later it was replaced by a steel jaw ground out of a 2½-in. steel ball, the lower surface being ground to an optical flat (Fig. 2). Four rollers were used to eliminate side thrust. Screws and centering blocks served to center the specimen in the crushing device. Hard steel shims placed under the shoulder of the upper jaw limited the "follow through'' of the jaw after failure of the specimen. Stress distribution was first examined with a polariscope mounted on an optical bench, using monochromatic light. It was found convenient to mount polaroid, quarter wave and monochromatic plates directly on the device itself. A Microflash unit* was used as light source for the photographs. A gold-paint pattern was fused on the plate-glass specimens and connected into the spark-

Jan 1, 1947

By Eugene F. Poncelet

Glass squares compressed on edge by steel jaws in poor contact with them developed jagged "partial-contact" cracks caused by the formation of local tensile stresses. Compressed by steel jaws in perfect contact, they developed smooth "release cracks" during release of the pressure, caused by the formation of local tensile stresses during the release of the pressure. All these cracks were parallel to the pressure. A Microflash photograph of a disintegrating specimen under sufficient pressure reveals a network of fractures roughly normal to each other, also "release cracks" and a disintegration cloud. The Griffith theory is amended to account for the formation of a first crack. A new theory, based on the theory of thermal agitation and wave propagation, is proposed to account for the progress, velocity and forking of cracks. The network of fractures is shown to have been caused by reflection at a free boundary of pressure pulses emanating from a first crack. Postulating equal distribution of energy in the pulses emitted on either side by a crack in particles, the smaller fragments are shown to continue fracturing preferentially while some of the coarser fragments remain as residual pieces. As comminution of the smaller fragments proceeds, the solid is reduced to a collection of residual particles of smaller and smaller sizes, accounting for the disintegration cloud. Experimental Procedure Apparatus A crushing device was built, consisting of a steel frame and two polished, hardened steel jaws to crush plate-glass samples. This device was placed between the plates of a hydraulic press (Fig. I). For centering the pressure, the upper jaw was guided vertically and provided with a rounded top. Later it was replaced by a steel jaw ground out of a 2½-in. steel ball, the lower surface being ground to an optical flat (Fig. 2). Four rollers were used to eliminate side thrust. Screws and centering blocks served to center the specimen in the crushing device. Hard steel shims placed under the shoulder of the upper jaw limited the "follow through'' of the jaw after failure of the specimen. Stress distribution was first examined with a polariscope mounted on an optical bench, using monochromatic light. It was found convenient to mount polaroid, quarter wave and monochromatic plates directly on the device itself. A Microflash unit* was used as light source for the photographs. A gold-paint pattern was fused on the plate-glass specimens and connected into the spark-

Jan 1, 1947

By T. N. Dixon, J. E. Briggs

A study was made of numerical techniques for solving the large sets of simultaneous equations that arise in the mathematical mode ling of oil reservoir behavior. It was found that noniterative techniques, such as the Alternating Direction Implicit (ADI) method, as well as some other finite difference approximations, produce oscillatory or unsmooth results for large time steps. Estimates of time step sizes sufficient to avoid such behavior are given. A comparison was made of the Point Successive Over-Relaxation (PSOR), Two-Line Cyclic Chebyshev Semi-Iterative SOR (2LCC), and iterative ADI methods, with respect to speed of solution of a test problem. It was found that, when applicable, iterative ADI is fastest for problems involving many points, while 2LCC is preferable for smaller problems. INTRODUCTION With the advent of high speed, large memory, digital computers, there has been an increasing emphasis on the development of improved methods for simulating and predicting reservoir performance. Two-dimensional, three-phase reservoir models with various combinations of PVT effects, as well as gravity and capillary forces, are common throughout the industry. Such models are also available through consulting firms, to anyone desiring to use them. Three-dimensional models will probably be practical in only a few years. We conducted a study of some of the numerical methods used for solving the large sets of simultaneous equations that arise in such models. A typical set of equations for a reservoir model is shown below:

Jan 1, 1969

By AIME AIME

A COMMITTEE of the American Railroad Association, consisting of Samuel Rea, president of the Pennsylvania System, Chairman; F. D. Underwood, president of the Erie Railroad; A. T. Dice, president of the Philadelphia & Reading Railroad; E. J. Pearson, president of the New York, New Haven & Hartford Railroad; and C. H. Markham, president of the Illinois Railroad (who was represented at the meeting by J. F. Porterfield of his system), met at the headquarters of the American Institute of Mining and Metallurgical Engineers, New York, on April 6 to assist in the Coal and Coke Committee's attempt to solve the bituminous coal problem. There was a full discussion of the questions of seasonal freight rates and the purchase by the railroads during the slack months of their winter's supply of coal. As the question of fuel supply for the railroads is in the hands of the Railroad Association, as well as the coal operators, it was vital that it should be represented at this important conference. The situation from the point of view of the mine operators was presented very thoroughly. No seasonal rates were considered necessary for the year 1920, and, as this matter requires considerable thought, it will be given thorough study and worked out in detail at a subsequent meeting.

Jan 1, 1920

By Franklin H. Wilson

COPPER base alloys containing various amounts of aluminum and silicon are of considerable commercial interest. In particular the alloy containing 7 pct aluminum and 2 pct silicon shows an attractive combination of high strength with excellent machinability. Since there is no evidence in the literature that this ternary system has been studied since the recognition by Smith1 and Anderson2 in 1939 of the kappa phase of the binary copper-silicon system, the determination of the equilibrium phase relationships in the copper corner of the ternary diagram has been undertaken to provide a fundamental basis for understanding the behavior of these alloys. Phase boundaries have been determined by the micrographic examination of quenched samples while points on the liquidus surface have been obtained by thermal analysis. The results, of sufficient precision to serve their major purpose of providing a guide for the control of the manufacture of alloys in the region covered, are presented in a series of both isothermal and vertical sections of the diagram. ALLOYS STUDIED For a rough survey of the copper corner of this ternary system the compositions listed in Table I (Series A) were employed. The results of examinations of these alloys indicated that the compositions listed in Table 2 (Series B) would further clarify regions of greater complexity. All alloys were prepared as 1200 g heats, the copper being melted under charcoal, and then first silicon and then aluminum were added. An [ ] excess of 0.05 pct silicon was allowed to cover deoxidation losses. Two small bars 5/8 by 1 ¼ by 1 ¼ in. were cast using Durville type casting equipment. Analyses were made on all alloys using material which was hot-rolled at 800 or 850°C and annealed 17 hr at 650°C. All analyses were found to be within 0.05 pct of the nominal composition. Since the precision of analysis is not much better than this, the points of both isothermal sections and vertical sections at fixed aluminum and silicon contents have been plotted at the compositions indicated by the nominal composition.

Jan 1, 1948

By W. G. SWART

THE best estimate on reserves of iron ore in the Lake Superior district is that made, in 1920, by Mr. R. C. Allen, amounting to 2,947,225,000 tons of assured and probable ore. This includes direct- shipping or so-called merchantable ores, and those capable of beneficiation by demonstrated processes. De- ducting from this the 287,000,000 tons shipped since 1920, leaves a present reserve of approximately 2,500,- 000,000 tons, or; about 50 years' supply. The assured ore in this estimate is given as 1,560,500,000 tons, which checks Mr. Lake's estimate of 1,528,948,000 tons, or about 30 years' supply. This is not a long time in the life of the steel industry, and it can be readily appreciated that the matter is important enough to war- rant the attention it is beginning to receive. The first question that engages our attention is, What is merchantable ore? In 1902 the average of all Mesabi shipments was 56.07 per cent iron and 4.35 per cent silica. Twenty-five years later it had dropped to 51.99 per cent iron, with silica up to 7.92 per cent. It has remained around these figures for' ten or twelve years and, except for a probable rise in silica, can stay there for an indefinite period. Most of these figures I am giving cover the Mesabi Range. Including the other ranges does not change the figures greatly, and the Mesabi Range commands the situation, since it produces about 65 per cent of the total annual tonnage and, according to Mr. Allen, contains 81 per cent of the assured reserves, 50 per cent of the probable reserves, and 66 per cent of both the assured and the probable reserves.

Jan 1, 1926

By George W. Sheary

Situated 45 miles west of Philadelphia and 50 miles southwest of Bethlehem Steel Company's Bethlehem plant, the integrated Grace mine facilities produce 4000 tpd of high-quality iron ore pellets. Startup of the Grace mill was in November 1958, and iron concentrates were shipped until March 1960, when the pellet plant went into operation. The underground mine, when fully developed, will hoist about 9000 tpd, including development rock. The crude ore, which has an iron content of approximately 42%, is magnetically cobbed and crushed in closed circuit with 3/4-in. slotted vibrating screens. The ore is washed and screened in the mill and the plus 1/4 in. screen product is again cobbed prior to feeding to the rod mills. Grinding is done in rod mills, and in ball mills that are in closed circuit with 30 in, cyclones, to 1% on 100 mesh and 65% minus 325 mesh. The ground ore is magnetically concentrated by three-drum permanent type finisher magnets to 67% Fe. The magnetite concentrate is pumped from the mill to a 50 ft thickener in the pellet plant. The thickened magnetite concentrate is relayed to the filters through a two-stage pump arrangement. The filter cake is fed by belt from filter concentrate bins to mixer-muller belts where it is intimately mixed with bentonite and a slight amount of water for moisture control. The fluffed concentrate then drops into balling cones. The green pellets from the balling cones are fed in a prescribed feed pattern to shaft furnaces through the use of shuttle car mechanisms. The green pellets are dried, heated to 2500°F and cooled to 1200°F as they descend through the furnace and into pellet coolers where the pellets are further reduced in temperature to 250°F. Heat is recovered in the cooling process through the use of air-to-air heat exchangers. The cooled pellets discharge on a rubber conveyor belt and are transferred to 6000-ton pellet railroad loading bin. The final pellet product consists of 90% plus 1/4 in. material (after tumble testing1) and contains 66% Fe plus 3% silica.

Jan 5, 1962

By THOMAS J. CLIFFORD

IN 1926, finer grinding began to be a feature of the milling practice of the Southeast Missouri lead district. Nothing since the adoption of flotation has caused greater changes and greater improvement in results. The trend toward finer grinding, with the consequent discarding of tailing at finer sizes, and consequent lower assays in lead, continued to progress until 1931, when the abnormally low price of lead brought a halt: that is, the better metallurgical results obtained would not offset the increased costs due to higher power and necessary maintenance. Since 1931 a slight tendency toward the discard of coarser tailing has taken place. , In 1926, larger rod mills i.12 ft. 1 in. by 6 ft. 6 in.) than any previously used in the district were installed in cue plant, and a new primary crushing plant, of greater capacity was built. This combination demonstrated immediately the better metallurgical results obtainable by finer grinding and all the mills now running have adopted the practice.

Jan 1, 1934

By Frank A. Howard

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

Jan 1, 1948

By P. M. Blair, D. W. Peaceman

The shape and position of the gas-oil transition zone during downdip displacement of oil by gas has been calculated using flow equations which include the effects of gravity, relative permeability, capillary pressure and compressibility of the fluids. The calculations treat the problem in two space dimensions, and results are compared with data from a laboratory model tilted at 30° and 60° from the horizontal on displacements near and above the maximum rate at which gravity segregation prevents channeling of the gas along the top of the stratum. The good agreement between calculated and experimental results demonstrates the validity of the tecbnique as well as that of the flow equations. INTRODUCTION Knowledge of the fluid distribution and movement in an oil reservoir is important in producing operations and estimation of reserves. The history of the oil industry has included steady progress in improving the accuracy of calculations which provide the required knowledge. The earliest method of calculating reservoir performance consisted of material-balance equations based on the assumption that all properties were uniform throughout a reservoir.l For many reservoirs such a simple formulation is still the most useful. However, when large pressure and saturation gradients exist in a reservoir, the assumption of uniform values throughout may lead to significant error. To reduce these errors, Buckley and Leverett2 introduced a displacement eqation which considers pressure and saturation gradients. Methods available at that time permitted solutions to the Buckley-Leverett equation in one space dimension; these solutions have been very useful in solving many problems related to the production of oil. However, the one-dimensional methods are not adequate for systems in which saturations vary in directions other than the direction of flow. An example of such a system is the case of gas displacing oil down a dipping stratum in which the gas-oil contact becomes significantly tilted. Of course, the Buckley-Leverett displacement method cannot predict the tilt of the gas-oil contact. Recent improvements3,4 of the one-dimensional Buckley-Leverett method achieve some success in predicting the tilt of the gas-oil contact at sufficiently low flow rates. However, at rates high enough that the viscous pressye gradient nearly equals or exceeds the gravity gradient, even these improved one-dimen,sional methods incorrectly predict the shape and velocity of the contact. Further progress in estimating such fluid movements in a reservoir appears to require consideration of the problem in more than one space dimension. The recent two-dimensional method of Douglas, Peaceman and Rachford5 appears adaptable to calculate changes with time of the saturation distribution in a vertical cross-section of a reservoir. The movement of saturation contours should represent the moving fluid contacts and include the effects of crossflow due to gravity, as well as variations in the rock and fluid properties. The nonlinear nature of the equations used in the method has prevented proof of the validity of the solutions. Douglas, Peaceman and Rachford made some comparisons with experiment but did not include cases in which gravity was important nor cases involving displacement by the nonwetting phase.For these reasons, a test of the two-dimensional method for a case in which these factors are included would be very desirable. The test selected was a comparison of calculated results with those from a carefully controlled laboratory experiment on a model with measured physical properties. The model selected was one in which gas displaced oil down a tilted, rectangular sand pack. The model can be thought of as representing a vertical cross-section taken parallel to the dip of a reservoir. The displacement thus simulates gas displacing oil downdip that might result from gas-cap expansion or gas injection. This report outlines the calculation method used

By F. C. Langenberg

IT is the purpose of this paper to present a limited amount of experimental data obtained on the Charpy impact machine. Several concrete examples will be given showing the relation existing between the results obtained upon the Charpy impact machine and the behavior of the parts tested when in service. Although it is pointed out by G. Charpy and A. Cornu-Thenard1 that it is first necessary to determine a satisfactory working process before studying the correlation between the results of these tests and the behavior of the parts tested in service, this ideal course cannot be strictly adhered to. If a certain part repeatedly fails in service and the available tests give no indication of its cause, advantage must be taken of any possible means that will solve the problem; therefore, even though the reliability of the results obtained by the Charpy impact machine have been questioned by many, it was necessary to use this instrument without giving careful consideration to its possible sources of error. It would seem that the conclusions arrived at by Charpy and Cornu-Thénard justify the assumption that the precision obtained by this machine is comparable to that obtained by, the other more common forms of testing. The second general conclusion arrived at by them, namely, that the impact test upon notching does not offer any direct correlation to the ordinary tests, is also borne out by many hundred determinations made in the laboratories at Watertown Arsenal. This statement, however, should be qualified as follows: Other ordinary tests include the static tensile test from bars taken in a longitudinal .direction and the Brinell hardness. The author agrees that no law is yet known for the computation of the energy absorbed in the rupture of bars of the same material but of different dimensions. Although Charpy and Cornu-Thénard do not refer in their valuable article to the use of the Charpy machine in industrial practice, it should be stated that this instrument has been in constant use in the laboratory at Watertown Arsenal for several

Jan 8, 1919

By F. G. Tahmoush, N. J. Grant, E. P. Abrahamson

The effect of grain size on the brittle -ductile transition temperature of pure iron and three dilute Fe-W alloys has been investigated by slow bend tests. The brittle-ductile transition temperature for pure iron increased with increasing grain sizes from 8000 to 500 grains per sq mm where the transition temperature then decreased with further increase in grain size. The dilute additions of tungsten lowered the transition temperature for fine grain sizes, suppressed a reversal of the curve in the coarse grained portion, and raised the transition temperature for this region. The frequency of twin occurrence increased with increasing grain size and decreasing temperature. The object of the present investigation was to re-examine the effect of grain size on the brittle -ductile transition of pure iron and several dilute Fe-W alloys. Current literature normally presents a simple relationship between grain size and the brittle-ductile transition temperature, namely, that the transition temperature increases with increasing grain size. Heslop and etch' have studied the transition temperature of mild steel by V-notch Charpy impact tests for the grain size range between 200 and 6000 grains per sq mm. The result was a linear plot of In 1-1/2 vs brittle-ductile transition temperature, where 1 is the grain diameter. Recent experiments by sipos2 revealed the possibility of a reversal in the slope of the grain size vs transition temperature plot for pure iron; however, his investigation was limited in scope, and the data obtained were insufficient to permit a definitive curve. The present investigation was undertaken in an effort to confirm or extend the grain size effect observed in iron by Sipos. PROCEDURE All alloys were vacuum induction melted, using 99.95 pct Fe containing 0.03 pct 0 and 0.004 pct C. Four ingots were made, ranging from pure iron to iron with 0.035 pct W. The chemical composition of each alloy, after processing, is given in Table I. The four alloys were prepared as 45 lb heats and cast into 4 in. diam by 16 in. molds. They were then extruded into 3/4 in. rods at 1800oF. Specimens for chemical analysis, taken from various positions along the rods, revealed no variation in tungsten content along the length. The extruded rods were reduced to 0.156 in. diam stock by a series of cold swaging operations involving intermediate vacuum annealing treatments. This procedure yielded a final cold reduction in area ranging from 10 to 90 pct. The swaged rods were chemically cleaned, cold pressed to a cross section of 0.10 by 0.18 by 1.0 in. long (2.54 by 4.73 by 25 mm). The specimens were wrapped in iron foil and vacuum sealed (10-4 mm Hg) in quartz. Various heat treatments at temperatures from 700" to 1300oC were utilized to produce grain sizes from 8000 to 1 grain per sq mm. Grain sizes were determined by measuring the average area of grains in a polished section. In specimens with grain size greater than 20 grains per sq mm, the total number of grains in the cross section was counted and then divided by the area to yield grains per sq mm. Grain size was measured both for longitudinal and transverse cross sections. The average of the two measurements was plotted vs transition temperature. An Instron Table Model testing machine was used to determine the transition temperature of specimens tested in three point horizontal bending. The specimen was supported by two 1/4 in. dowels one in. apart. Bending was accomplished with a push rod, the end of which had an 1/8 in. radius. The head speed was 50 in. per min. Temperatures were established through the use

Jan 1, 1963

By AIME AIME

IN ORDER to carry on its work most effectively, the Committee on Industrial Organization (now known as the Committee on Industrial Relations) consists, of .a number of sub-committees, each composed of a chairman and members who are especially fitted to carry out the work designated by its title. With only one or two exceptions, all of these committees made reports at the New York meeting of the Institute, in February of this year, abstracts of which follow.

Jan 1, 1920

By S. A. TAYLOR

THERE is probably no other mineral industry of which the public has as much information and misinformation as it has of the coal industry. Unfortunately, however, the general public's knowledge of the coal industry, outside of the particular kind of coal it is accustomed to, by reason of use, is largely made up of information received from newspaper and popular magazine articles, in which the mine workers are depicted as overworked and mistreated men, and the coal operators as "coal barons." Those who have any specific knowledge of exact conditions in the coal industry know how unjust and un- fair such an opinion of the coal industry is, not only to the miner but to the operator as well. Many reporters and writers of magazine articles are misled by statements regarding the condition of the miners that are exaggerated and not founded on facts and, if an investigation of the conditions of the miner's work, his habitation and surroundings were fairly made, it would at least compel more truthful statements by those who write for public reading. That such an investigation would not reveal anything that was wrong, or anything to be censured or cured, no one, I think, would maintain, but I do think that any fair investigation of the facts would show that conditions in and around the newer and later-developed coal mines and communities would compare favorably with those of manufacturing districts, and that where the mines and com- munities are old and not very attractive places to work, or live in, they carry with them other considerations, compensating for these conditions, and cannot be remedied by reason of a lack of sufficient coal to warrant economically any costly changes.

Jan 1, 1926

By Colin G. ink

OUTSTANDI'NG in progress among the less familiar 'metals during 1936 is the electrolytic production of 99.9 per cent manganese meta1 readily and many quantity. Strictly speaking, manganese should not' be classed as 'a rare metal, since there is 800 times as much manganese in the earth's crust as there is zinc or lead. But manganese' as a metal is rare, just as titanium metal is rare though titanium is five times as abundant in the earth's crust as manganese.

Jan 1, 1937

By W. A. Klikoff, I. Fatt

The concept of fractional wet wattability is examined. Fractional water wettability of a reservoir rock is defined as the fraction of the internal surface urea that is in contact with water. Capillary pressure and relalive permeability of unconsolidated sand are shown to be functions of fractional wettability. INTRODUCTION The petroleum industry has long recognized that wettability of reservoir rock has an important effect on multiphase flow of oil, water and gas through reservoirs. As early as 1928 the American Petroleum Institute sponsored a study of wettability as part of API Project 27 at the U. of Michigan.' Despite 30 years of research, there is still little exact knowledge of the wettability of reservoir rocks. There are two parts to the wettability problem. After agreeing to a uniform nomenclature in regard to wettability,' the first question to be answered is, "What is the in situ wettability of a given reservoir rock?" If this can he answered the next question is, "What part does wettability play in determining the characteristics of multiphase fluid flow through the rock?" This paper represents an oblique attack on the problem of wettability. No attempt is made here to answer the basic question of wettability in situ. instead the consequences of the concept of fractional wettability are examined. Multiphase flow in sandpacks is shown to he highly influenced by fractional wettability. Jennings' has given 3 definition of wettability and the other terms used in discussing wettability. These terms must be applied to the physical situation existing In reservoir rock. A survey of the pertinent literature from 1928 to 1956 indicates that the concept of a contact angle was applied to reservoir rock in the same way it would be applied to a flat, homogeneous surface. Attempts were made to state quantitatively the wettability of a reservoir rock in terms of a contact angle which was presumably constant at all points on the very rough and heterogeneous interior surface of a porous rock. Calhoun, et al,3-6 prepared synthetic consolidated and un-consolidated porous media in which they claimed there was a known uniform contact angle. They then showed the effects on the capillary pressure and relative permeability characteristics of varying this angle. The API Project 47 at the U. of Texas' and others' have made extensive studies of an indirect approach to the contact angle through the use of heat of wetting data. Even if successful. however, this approach also states the wettability of porous rock in terms of a contact angle which is uniform over the entirc surface. If the angle varies from one part to another on the internal surface, there is no way of determining from the measurements the area distribution of contact angles. In 1956 Brown and Fatt5 suggested that the concept of a contact angle, as applied to reservoir rock, be abandoned. This suggestion was made because it is known that the internal surface of most reservoir rocks is composed of many different minerals, cach with a different surface chemistry and a different capacity to adsorh surface active materials from reservoir fluids. Furthermore, the operation of a contact angle in determining the form of a fluid-fluid interface is difficult to picture in the very complex geometry of a pore. Brown and Fatt proposed that the wettability of reservoir rock be stated in terms of the fractional internal surface area that is in contact with water or oil. All surfaces on which there is water are called water-wet; surfaces on which there is oil are called oil-wet. The fractional water wettability is then stated as a number which represents the fraction of the internal surface that is in contact with water. A symmetrical statement can be made for the fractional oil wettability. The concept of a fractional wettability as previously stated has in its favor the recognition of the heterogeneous mineral composition of most reservoir rocks. Another point in its favor is that fractional wettability can be measured quantitatively with relative ease. Hol-brook and Bernard10 se a simple dye adsorption test to obtain fractional wettability of reservoir rocks. Amott11 uses a combination of imbibition and displacement to arrive at a wettability index of reservoir rocks which seems related to fractional wettability in the range 0.25 to 0.75 fractional water wettability. Jennings" has shown the changes in relative permeability that take place when a porous material is changed from unity to zero fractional water wettability. He also shows that reservoir rocks in their natural state, but at room temperature and atmospheric pressure, have relative permeability characteristics which would indi-

For handling rough rock, the shovel-train system is unexcelled. The ideal application is a physically large, but not excessively deep, open-pit mine from which the coarsely blasted ore and waste must be transported distances in excess of three miles. If, in addition, a high production rate is to be maintained, railroad haulage will probably afford a lower cost per ton transportation than will any other haulage method. Relatively gentle grades must be employed- usually 3% for uphill hauls and 4% for downhill hauls. The greater the differences in elevation the greater are the railroad track grade space requirements. By way of illustration, a 3% ramp out of a pit only 300 ft deep must be almost two miles long. Mainline track locations should be selected carefully so that the frequency of movements during the life of the mining operation is minimized. This applies both to ore and to waste haulageways. Such moves are not only expensive but difficult to execute without adversely affecting production rates. The large mine affords greater opportunities for judicious location of semi-permanent trackage.

Jan 10, 1967

By Y. Baskin

Solid-solubility relationships in the Pseudobinary systems UAS-UP, UAs-US. UAS-UC, aid UAs-UN were investigated. The first two systems exhibit complete mutual solubility, whereas the component compounds in the other two systenzs are immiscible. The above information, together with solid-solubility data joy six additional pseudobinary systems , were analyzed for compliance wilh the Hurrze-Rothery rules for rnetallic systems. The relative size difference of the component nonmetal atoms was found to be the dopainant jactor determining the extent of solid solubility between the NaC1-type uranium compounds. The anionic and covalent radii of the nonmetal atoms appear to be inadequate for these systems, but compuled radii based on rare earth compounds yield consistent results for the uranium compounds. THE actinide elements, like metallic elements of the transition and rare earth series, readily form binary compounds with nonmetallic elements of groups IV, V, and VI of the periodic table. Of particular importance are the NaC1-type equiatomic compounds with carbon, nitrogen, sulfur, phosphorus, and arsenic. The uranium members of this family of compounds have high melting points, are essentially stoichiometric, and exhibit various amounts of mutual solubility. Thus, they are of interest for investigating the factors governing the extent of solid solubility. Previous investigators have determined the solid-solubility limits in the pseudobinary systems between the compounds UC, UN, US, and UP. Anselin et a1 .' reported complete miscibility in the system UC-UN. Baskin and shalek 2 and Allbutt et a1.3 reported that UP and US exhibit complete mutual solubility. Shalek and white4 reported partial miscibility in the system US-UC. At 1800°C the maximum solubility of UC in US is 40 mol pct, but that of US in UC is 4 rnol pct. shalek5 found limited solubility in the system US-UN; the maximum solubility of UN in US is 11 rnol pct at 1800°C, while that of US in UN is only 0.3 mol pct. White and askin 6 found very limited miscibility in the system UP-UC at 1800°C. Approximately 7 mol pct UC is soluble in UP, but there is no solubility of UP in the monocarbide. Phase relations in the pseudo-binary system UN-UP were investigated by askin.' Approximately 0.7 mol pct UN is soluble in UP at 1800°C, while UP is immiscible in UN. The present study was carried out to explore the extent of terminal solubility in the systems UAs-UC, UAs-UN, UAs-US, and UAs-UP. This information, combined with existing data, provided a sufficient basis on which to determine the factors governing solid solubility in pseudobinary systems containing NaC1-type uranium conpounds. I) EXPERIMENTAL 1) Materials. The compounds UC and UN were obtained from the Kerr-McGee Corp. and United Nuclear Co., respectively. The US, UP, and UAs were synthesized by reacting finely divided uranium with H2 S, pH3, or AsH3 gas at low temperature (300° to 500°C), followed by homogenization in a vacuum at moderately high temperatures (1400° to 1700°c).8-10 The materials were essentially stoichiometric, with the exception of UC, which exhibited a C/U ratio of 1.05. Oxygen was the major contaminant in these compounds, ranging from 0.05 wt pct in US to 0.30 wt pct in UC, and it was generally combined with uranium to form UO2. The UO2 content in these materials was usually of the order of 1 wt pct, and did not exceed 2 wt pct. Furthermore, no evidence was found for a high-temperature reaction between uranium dioxide and any of the compounds. Chemical analyses of equilibrated compositions in the systems UAs-UP and UAs-US showed that the non-metal atom to uranium ratios averaged about 1.01, and that the oxygen contents ranged from 0.06 to 0.22 pct. However, the small deviations from stoichiome-try or the presence of minor oxygen impurities do not invalidate the conclusions to be drawn from this study. 2) Experimental Procedures. The component compounds in powdered from were blended in the desired proportions for 5 hr in the ball mill that consisted of stainless-steel balls in a plastic container. Chemical analyses indicated very little metallic pickup from the blending operation and virtually no increase in oxygen content. The pellets were pressed in a 0.270-in.-diam steel die under 40,000 psi pressure. One wt pct of stearic acid dissolved in CCl 4 served both as a binder and as a die lubricant. Chemical analyses revealed that the stearic acid left no carbon residue in the sintered samples. The pellets were sintered in vacuum in an unsealed tantalum crucible. The temperature, measured with a calibrated optical pyrometer, was maintained at 1800" + 30°C for 3 hr. This was sufficient time for attaining equilibrium as no change occurred in either the lattice parameters or the sharpness of the X-ray patterns when samples were annealed for longer periods of time. The pellets were cooled with the furnace. Debye-Scherrer powder patterns were taken at room temperature with a 114.59-mm-diam Norelco powder camera and CuKor radiation (CuGI = 1.5405A). Unit cell dimensions were determined from a Nelson-Riley extrapolation to the high-angle reflections. The values for were precise to k 0.001A. 11) RESULTS X-ray and met allographic investigation revealed that complete mutual solid solubility exists in the pseudobinary systems UAs-UP and UAs-US. The lattice parameter vs composition plots, Fig. 1, show a

Jan 1, 1968

By M. C. Udy, F. W. Boulger

AN incomplete phase diagram for the U-Ti systern was determined earlier 1 and more recently, a tentative diagram was presented for the uranium-rich end of the system.' In the present re-examination of the whole system of U-Ti alloys, high purity materials were used. Melting stock for the alloys was high purity uranium, containing about 0.09 pct C as the only appreciable impurity, and high purity iodide-process titanium purchased from New Jersey Zinc Co. Both metals were cold rolled to about 1/6 in. thickness, sheared to about I/' in. squares, and cleaned by pickling. The alloys were arc melted under a helium atmosphere in a water-cooled copper crucible. A thoriated-tungsten electrode was used. The furnace chamber was evacuated, then flushed with helium, prior to each melting. It was finally filled with stagnant helium at one atmosphere pressure. Each alloy was remelted three times after the original melting, to insure homogeneity. The alloy button was turned bottom side up before each re-melting operation. Some 22 alloys were examined. Their compositions were spaced at appropriate intervals between 100 pct Ti and 100 pct U. Analyses were made on chips taken after fabrication. The major contaminant was carbon, which varied from 0.03 to 0.08 pct. It appeared in the microstructure as titanium carbide. Alloy compositions were calculated to a carbon-free basis for consideration on the diagram. Tungsten and copper, possible contaminants from the melting operation, were generally less than 100 parts per million each. Fabrication All alloys were forged and rolled to bars approximately V8 in. square. They were clad either in SAE 1020 steel or in a 5 pct Cr-3 pct Al-Ti-base alloy, depending on the fabrication temperature. A temperature of 1800°F (980°C) was used for alloys near the compound composition. This necessitated using the titanium-base alloy, since iron reacts with titanium at this temperature, producing a low melting alloy. Other alloys were fabricated at 1450°F (790°C), using steel jackets. No iron-titanium reaction occurred at this temperature. The jackets were welded in place in an argon atmosphere. Those alloys sheathed in steel were declad and then reclad between rolling and forging operations. On the other hand, those clad with the titanium alloy were cut to a roughly rectangular shape prior to clading and were then carried through both the forging and rolling operations without opening. Those alloys near the compound composition were found to be cracked when the clading was removed. The cracked materials had been plastically deformed, however, and at least some of the cracking had OCcurred during cooling. Heat Treatment The rolled bars, after being declad and shaped to remove surface contamination, were all given an homogenizing treatment of 160 hr at 2000°F. (Samples were taken for analysis following the declading and shaping operations.) All were heat treated at the same time in one furnace, but each was sealed in a purified argon atmosphere in an individual Vycor glass tube. Argon pressure was such that it was approximately atmospheric at temperature. One end of each tube contained titanium chips and this end was heated to 1200°F (650°C) for 10 min prior to the heat treatment. This purged the atmosphere of residual reactive gases. The balance of the tube was warmed during the purge to liberate adsorbed moisture and gases, which also reacted with the hot chips. The bars were furnace cooled from the homogenization treatment. Specimens of each alloy were water quenched after 2 hr heating at 1000°, 1200°, 1400°, 1600°, 1800°, and 2000°F (540°, 650°, 760°, 870°, 980°, and 1095°C). In addition, some were treated at intermediate temperatures of 1300°, 1500°, and 1700°F (705", 815", and 925°C) and at 2150°F (1175°C). Specimens, about '/s in. cubes, were cut from the bars, sealed in individual Vycor tubes, and heat treated as described. All specimens heat treated at the same temperature were processed together. Samples were quenched by breaking the Vycor tube rapidly under water. Metallographic Examination Specimens were mounted in bakelite and ground wet on 180 grit paper held on a 1750 rpm disk. They were then ground wet by hand, using 240, 400, and 600 grit papers. The rough grinding was continued long enough to get well below the surface. Specimens were mounted separately because of the variation in the rate of etching between alloys. The specimens were polished with rouge on a 4 in., 1725 rpm wheel covered with Miracloth. Alloys on the titanium side of the compound composition were etched with a solution of 2 pct hydrofluoric acid in water saturated with oxalic acid. A few crystals of ferric nitrate were added as a bright -ener. Specimens were immersed 5 sec, polished to remove the etch, then re-etched. With the higher titanium alloys, it was often necessary to start the etch on the polishing wheel, because of the formation of a passive film. In some instances, a plain 2 pct hydrofluoric etch was satisfactory. For the alloys on the uranium side of the compound, a distinction between the compound and the uranium phase developed after standing a short time in air. This could be hastened by the application of heat, such as obtained by placing the specimen on a radiator. A deep etch was necessary to develop details in the uranium-rich phase, such as the Widmanstaetten pattern sometimes obtained by quenching y uranium. A 2 pct hydrofluoric acid solution was used for this deep etching.

Jan 1, 1955