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EVERY intelligent and practical investigator of minerals says that copper ore is found in various regions of the world and that among others Italy is very rich in it. But very little is mined there, perhaps because of a cowardly Italian avarice which has the power to make us lazy and indolent in carrying out those lofty and fine designs which should reasonably make us proceed swiftly, or perhaps because we are not prone to attempt extraordinary profit but only undertake those enterprises in which we are certain of a return on our investment. The reason for this might also be found in the meager possibility of success, which, since these things are not easily attempted because they are enormous undertakings of doubtful outcome, cools the spirit of men and in place of enthusiasm introduces the fear of loss, the fear of having to sacrifice not only time but also the work and money invested; then they think of the difficulty [II] of discovery, of the impossibility of full ownership, and of the necessity of excavating the mineral marrow from the hardest bones of the mountains with the brawn and efforts of men. To this is added the fear common to many that in attempting such things they may be called fools by certain ignorant and dissolute persons, and it seems better to them to be praised for becoming rich through usury and by many other infamous and illicit methods than to lay themselves open to the danger of censure from such as these. But there are those who deserve still greater censure, particularly princes and all rich and powerful persons, and theirs is an even more useless error than that of those who refrain for the above reasons. If the occasion and means present themselves for both attempting and continuing such a profitable and laudable affair as mining ores and if they hesitate solely because of cowardice or because they give ear to the bayings of ignorant hounds, or if because of their own willfulness they wish to remain prisoners of a detestable and ugly avarice, then this is their own loss.

Jan 1, 1942

By A. I. Krynitzky, Henry S. Rawdon

The most commonly used material for terminals in spark plugs is commercial nickel wire, because of its relatively high temperature of melting, excellent heat conductivity, and slow rate at which the metal is oxidized, even upon continued heating at high temperatures. The grade commonly used for this purpose averages 97 per cent. nickel, the remainder being manganese, cobalt, iron, copper, with traces of other impurities always found in commercial nickel. A peculiar and interesting type of deterioration that occurs in these nickel terminals during the service life of the spark plug was recently brought to the attention of the Bureau of Standards. Commercial spark plugs vary greatly in their size and shape and the terminals differ considerably as to their relative size, shape, number, and arrangement with respect to one another. Although this defect was studied in detail in only one form of spark plug, the deterioration is a characteristic of the material, i.e., of nickel wire, rather than of the particular type of spark plug in which it was noted and studied. The mechanical features of the plugs, however, have a considerable bearing on the time required for the deterioration to become serious. The results of this study of the deterioration of nickel terminals in service should be of value to the makers of all types of spark plugs in which the terminals are made of this metal. CharacteR of Deterioration of WIres During Service Macroscopic Appearance and Properties of Changed Wire.—The nickel terminals in which the deterioration was studied were taken from spark plugs having a central terminal with the ground or side terminals attached firmly at both ends to the shell of the plug. In some of the plugs, two side terminals were used, one on each side of the central one. Although both terminals were found to have deteriorated to some extent, the attack of the central one was quite negligible compared to that of the side ones. These latter wires had developed, in service, transverse cracks that, in many cases, were as sharp and definite as a knife-cut. After a separation occurred, the breach widened by loss of material from the

Jan 1, 1921

By J. W. Faust, H. F. John

Generalized conditions for rod or ribbon growth by the twin plane re-entrant edge mechanism are given. It was shown that this mechanism can result in growth of twinned platelets from dilute metal solutions. The platelrts 01 the fee metals are faceted by (111) planes and contain two or more twin planes. Microsegregation traces were revealed in silver grown from a thallium solution. VOGEL has already set down conditions for dendritic growth;1 however, this was the normal single-crystal dendritic growth experienced during solidification. In this work it is desired to set down the crystallographic conditions that will lead to rod or ribbon growth with smooth facets. These are as follows. a) The growth must be crystallographically limited (i.e., faceted growth). b) In order to have directed growth, some mechanism must allow easier nucleation than two-dimensional nucleation. That mechanism is afforded by the re-entrant edges at twin planes.213 Thus there must be twin planes present in the rods or ribbons. c) The growth direction must lie in the twin plane. If not, the twin plane will grow to the face or side of the ribbon and the site of easy nucleation will be lost. d) The growth direction must be parallel to at least one plane of the faceting planes, and no set of the faceting planes can be perpendicular to the growth direction. A corollary to these conditions involves the number of twin planes necessary to maintain the indestructible re-entrant edge. The number depends on the crystal structure of the material. An analysis of the data available shows that a material whose faceting planes form an open figure requires at least one twin plane while materials whose faceting planes form a closed figure require at least two twin planes in order to form the indestructible re-entrant edges for extended growth. The conditions and an assessment of the possibility of rod or ribbon growth are given in Table I for several crystal systems. As can be seen the fee, diamond and zinc blende, or-thorhombic, rhombohedral, and one form of the hexagonal lattice systems can yield this type of growth, but not the bcc metals nor the hexagonal

Jan 1, 1965

By Stefan S. Kapusniak, Nichol Riggott, Stephen F. Smith

Stability investigations have been carried out in a number of major coal mining tunnels in the U.K. using various instrumentatcon techniques. The paper describes these instrumentation methods and presents results from studies in several tunnels. Both long and short term stability aspects are discussed. Prediction of tunnel stability is examined in relation to tunnel support requirements. Computer simulation techniques are used along with actual underground measurements to identify tunnel design parameters for influencing choice of support and prediction of long term stability.

Jan 1, 1984

By H. T. Hildage

Although Greater New York does not bear any resemblance to a great mining district, the mining operations that are being conducted in and about the city are both extensive and interesting in character. With regard to the extent, it may be mentioned that, at present, there is more dynamite used in New York than in any mining district in the United States; that there are under construction about 38 miles of tunnel, and that 66 miles more are projected, most of which must be constructed .in the near future; that since 1903 at least 2,000,000 tons of earth has been removed in underground work, in addition to about 3,500,000 tons that has been removed in open-cut in connection with tunnel-work, and many times this quantity that has been removed in excavating foundations for buildings not connected with tunnel-work; and that there are to-day probably more than 5,000 men engaged in mining-work in and about New lrork City. These undertakings include almost every operation connected with underground work, from exploration by means of trench and boring, to the sinking of large shafts and the driving of large tunnels through every kind of ground from hard rock to soft, semi-fluid silt and quicksand. It is proposed in this paper to give a general description of some of the methods and appliances used in the opening-up of a " mine " in a large city, and a brief description of some of the &'mines" now being developed in New York, connecting as far as possible the methods described with the particular work for which they were designed, in order to give a general idea of the

Jan 1, 1908

By W. O. Brown

A laboratory investigation was conducted to determine quantitatively the extent to which connate water was contacted and displaced by invading flood water. In these experiments the connate water in unconsoli-dated sand packed columns was completely displaced by injecting water. The nature of this displacement was similar to that previously described for single-phase miscible fluid displacement studies, and thus the presence of a non-wetting immiscible phase did not appreciably change the nature of the displacement. The effects of water injection rate, column length, and oil viscosity on connate water displacement were investi-gated. It is concluded that the connate water in a reservoir is the water which actually displaces oil from the pores of the rock during a water flood. During a water flood the connate water forms a zone which separates the invading flood water from the continuous oil phase. The size and shape of connate water bank is chiefly dependent oil the oil viscosity and the column length. INTRODUCTION Water flooding is one of the most widely used techniques for the secondary recovery of oil. Presently, however, it is still not possible to recover all the oil in a reservoir by water flooding. The research described in this paper was conducted as part of a study to determine the conditions under which 100 per cent oil recovery could be attained by water flooding. The particular objective of this work was to determine if any chemical agent, regardless of its nature, placed in the flood water could be effective in influencing the mechanism of displacement of the oil by water. It has been known for many years that water does not displace all the oil in a reservoir because a portion of the oil is "trapped" and held immobile by capillary forces. This oil is trapped within the pores of a water-wet rock when it becomes broken into discontinuous globules. Initially, when oil is present at high saturations within the pores of a water-wet rock, the connate water forms rings around the points of contact of the sand grains and may even completely fill small cavities between grains, whereas the oil occupies the larger void spaces between the grains.' Under these conditions, the oil in these spaces is in the form of irregular but continuous filaments, the diameters of which depend on the geometry of the sand pores. The filaments are formed by the oil contained in the small cells which are formed between the sand grains and are connected to their neighboring cells by channels or tunnels formed by pendular rings of water. At a high oil saturation, the oil filaments conform approximately to the shape and size of the cells and their connecting tunnels. Starting with this distribution, as the water saturation is increased the water layers in the small cavities and on the surface of the grains grow. As this occurs, the water rings grow and the diameters of the oil filaments decrease. When an oil filament is reduced to a critically small diameter, the filament breaks, and its tunnel fills completely with water. Any oil which remains within a cell after all its connecting tunnels have been water-filled is trapped as a discontinuous globule. Once the oil has become trapped, the capillary forces oppose distortion of the globules and may prevent their being squeezed through the water-filled tunnels. Only a very small pressure gradient is sufficient to keep oil moving as a continuous filament. On the other hand, once the filament has broken into discontinuous oil droplets a relatively large force is required to distort the surface of a drop and move it through a water-

Jan 1, 1958

By St. John, JOHN Ancel

AT THE New York meeting of the Institute of Metals Division in February, 1927, Jeffries and Tarasov presented a paper on Tungsten and Thoria,1 in which the experimental facts were interpreted in accordance with the prevailing point of view that the thorium is present as the oxide, thoria. In discussing that paper the writer of this article stated that his own investigations, which had been unavailable to Messrs. Jeffries and Tarasov, showed that the so-called "thoriated" tungsten filament failed to disclose any sign of the oxide when subjected to X-ray diffraction analysis, but did give plenty of evidence of the presence of metallic thorium and, in certain cases, of a material believed to bean alloy of tungsten in thorium. Since these results were completely at variance with the results reported in the paper under discussion and with other papers which had preceded it from time to time in the past, it was felt that further discussion should be withheld until the new evidence could be presented adequately. Arrangements were therefore made to present that evidence at this meeting. MATERIAL EXAMINED The material examined was high-emission filament such as is used in radio tubes, supposed to contain about 0.75 per cent. thoria. The actual analysis was not stated.

Jan 1, 1927

By H. W. Graham

The young metallurgist of today who thinks casually of the technical literature of the steel industry might conclude that little has been published concerning the Bessemer process. This conclusion is true as relating to the last decade or two, but there is a fairly voluminous Bessemer literature in the period of 1860 to 1910. Since that time, however, an entirely new level of metallurgical knowledge of steelmaking has been reached; and the present paper is simply an effort to look broadly from this new level and to bring the recorded history of the process up to date. It is an effort to appraise the acid Bessemer method of steelmaking in the light of today's technical knowledge thereof. In this paper matters of history will be dealt with only insofar as they contribute to an understanding of today's situation. Attention will be directed to the apparent causes of past developments in seeking to perceive the true direction of trends now in existence and effective as bearing upon future developments. The paper will discuss the economics of the Bessemer process, but only to the extent that will bear upon the metallurgist's understanding of his responsibility. The problem of the quality of Bessemer steel will be reviewed and examples will be given of the technical data upon which the reasoning of the paper is based. Matters of engineering design, mechanical maintenance, operation and metallurgical investigation will be surveyed. Comparisons will be made between the Bessemer and open-hearth processes for the sake of clear and ready understanding. Production First of all it is considered logical and informative to show how much Bessemer steel has been and is being produced, and the relation of that production to the tonllage made by the open-hearth process. Table 1 shows the tonnages made by the two processes in representative years. It is to be noted that these figures are in net tons of 2000, lb., whereas previous to 1940 the Institute figures were compiled in gross tons. id open-hearth production and steel going into castings are included, since separated data are not available for the early years of the period covered. The ratio shown in Table I is merely the Bessemer tonnage for a given year divided by the open-hearth tonnage of the same

Jan 1, 1941

By H. W. Graham

The young metallurgist of today who thinks casually of the technical literature of the steel industry might conclude that little has been published concerning the Bessemer process. This conclusion is true as relating to the last decade or two, but there is a fairly voluminous Bessemer literature in the period of 1860 to 1910. Since that time, however, an entirely new level of metallurgical knowledge of steelmaking has been reached; and the present paper is simply an effort to look broadly from this new level and to bring the recorded history of the process up to date. It is an effort to appraise the acid Bessemer method of steelmaking in the light of today's technical knowledge thereof. In this paper matters of history will be dealt with only insofar as they contribute to an understanding of today's situation. Attention will be directed to the apparent causes of past developments in seeking to perceive the true direction of trends now in existence and effective as bearing upon future developments. The paper will discuss the economics of the Bessemer process, but only to the extent that will bear upon the metallurgist's understanding of his responsibility. The problem of the quality of Bessemer steel will be reviewed and examples will be given of the technical data upon which the reasoning of the paper is based. Matters of engineering design, mechanical maintenance, operation and metallurgical investigation will be surveyed. Comparisons will be made between the Bessemer and open-hearth processes for the sake of clear and ready understanding. Production First of all it is considered logical and informative to show how much Bessemer steel has been and is being produced, and the relation of that production to the tonllage made by the open-hearth process. Table 1 shows the tonnages made by the two processes in representative years. It is to be noted that these figures are in net tons of 2000, lb., whereas previous to 1940 the Institute figures were compiled in gross tons. id open-hearth production and steel going into castings are included, since separated data are not available for the early years of the period covered. The ratio shown in Table I is merely the Bessemer tonnage for a given year divided by the open-hearth tonnage of the same

Jan 1, 1941

By M. Bevis, A. G. Crocker

A. G. Crocker and M. Bevis (Battersea College of Technology)— Richman and Richman and conard17 have recently published the very interesting results of their studies on the plastic deformation of Fe-Ni-C martensites and of an Fe-5 wt pct Be alloy. Other work on the range of Fe-Be alloys containing between 16 and 27 at. pct Be has also been reported by Richman." One of the fascinating features of this work is that the materials investigated deform primarily by means of twinning and that several twinning modes are operative in addition to the well-established (112 ) mode of bcc materials The composition planes of these unusual twins were determined using a single-surface analysis and reported as (0131, "{045)" or "{089)", and "{2,3,10)" or "(127)". (It is now thought1' that the "{0,1,13)" habit reported for the Fe-Ni-C alloys'' is more likely to be near "{127)". Although the full twinning elements of these unusual twinning modes could not be determined directly from the experimental results, the authors attempt to deduce the elements by considering twin intersectionslQ and by using the projection technique of Jaswon and Dove.' The basic assumption of their approach is that the (013) habits are truly rational planes but that the other habits are irrational and merely approximated to by the indices quoted above. They thus deduce that the twinning mode describing the (013) habit is either Type I or compound and that the modes describing the other habits are Type 11. This deduction must however be false as all twinning modes in cubic structures obeying the classical orientation relationships of deformation twinning must be compound. Type-I and Type-I1 modes can occur in all of the other crystal systems (indeed in the triclinic system compound modes are not allowed), but in the cubic system only compound modes can arise. This fact, which does not appear to be well-known, fol- lows immediately from the relations between the four twinning elements defining a twinning mode. Thus for a Type-I mode which is uniquely defined by the rational twinning elements K1 = hi and tj2 = vi (i = 1, 2, 3), the Kz qd 771 elements are given by: where the summation convention of the tensor calculus has been adopted. For cubic materials the metrics cij Iand cij reduce to the unit tensors 6ij and 6ij so that we have It is clear from these equations that both ki and ui must take on integral values; i.e., Kz, and ql must be rational, if hi and vi are integers, i.e., if K1 and 77~ are rational. Thus for cubic materials a Type-I mode must degenerate into a compound mode and the same result also arises for Type-II modes. The apparently irrational habits observed by the authors can thus not be explained in terms of Type-I1 twinning if the classical laws of deformation twinning are to be obeyed. An alternative explanation of the irrational habits is that they may arise from twinning modes with four irrational twinning elements. These modes, which do not obey the classical orientation relationships associated with deformation twinning, have been shown to arise as the result of double twinning processes in magnesium,22 but may also describe a simple shear on an irrational plane in an irrational direction. Indeed double twinning processes in bcc

Jan 1, 1963

By Walter Renton Ingalls

In addition to the localities in which tin-ores have been found in Mexico, mentioned in my paper on the a Tin-Deposits of Durango," presented to the Institute in March, 1895,* the following should be recorded. I am indebted to Captain Henry Freeman, of Durango, for the notes as to these occurrences. In the Sierra de la Candela, west of the Sierra de Sail Frailcisco and El Promontorio (the Llano de Guatimape intervening between the two ranges), cassiterite is found in veins and stream-beds. The veins are narrow, and the ores have the same characteristics as those of Potrillos. They were exploited by miners from Coneto in 1882-86, the more extensive work having been done on the northern side of the mountains. In the Sierra de las Palomas, on the western edge of the Otinapa, ranch, about 25 miles W.N.W. from the Diablo mine in the Cacaria district, there are several small veins, of which the ore, gangue and country-rock are similar to those of the Cerro de los Remedios, near the city of Durango. The latter are essentially the same as the Potrillos veins. In the Cerritos del Olote, in the Murphy grant, about 50 miles W.S.W. from Durango, there are old mines, now partially filled. The veins are narrow and poor; the ore is highly ferruginous; the country-rock is rhyolite, with some granite; immense quantities of chalcedonic rubbish are strewn along the course of the veins. In the Cerro Blanco, overlooking the pueblo of Mezquital, 48 miles south of Durango, tin-ore is mined by the natives.

Jan 1, 1898

By M. Bevis, A. G. Crocker

A. G. Crocker and M. Bevis (Battersea College of Technology)— Richman and Richman and conard17 have recently published the very interesting results of their studies on the plastic deformation of Fe-Ni-C martensites and of an Fe-5 wt pct Be alloy. Other work on the range of Fe-Be alloys containing between 16 and 27 at. pct Be has also been reported by Richman." One of the fascinating features of this work is that the materials investigated deform primarily by means of twinning and that several twinning modes are operative in addition to the well-established (112 ) mode of bcc materials The composition planes of these unusual twins were determined using a single-surface analysis and reported as (0131, "{045)" or "{089)", and It is now thought1' that the "{0,1,13)" habit reported for the Fe-Ni-C alloys'' is more likely to be near "{127)". Although the full twinning elements of these unusual twinning modes could not be determined directly from the experimental results, the authors attempt to deduce the elements by considering twin intersectionslQ and by using the projection technique of Jaswon and Dove. The basic assumption of their approach is that the (013) habits are truly rational planes but that the other habits are irrational and merely approximated to by the indices quoted above. They thus deduce that the twinning mode describing the (013) habit is either Type I or compound and that the modes describing the other habits are Type 11. This deduction must however be false as all twinning modes in cubic structures obeying the classical orientation relationships of deformation twinning must be compound. Type-I and Type-I1 modes can occur in all of the other crystal systems (indeed in the triclinic system compound modes are not allowed), but in the cubic system only compound modes can arise. This fact, which does not appear to be well-known, fol- lows immediately from the relations between the four twinning elements defining a twinning mode. Thus for a Type-I mode which is uniquely defined by the rational twinning elements K1 = hi and given by: where the summation convention of the tensor calculus has been adopted. For cubic materials the metrics and reduce to the unit tensors and j so that we have It is clear from these equations that both ki and ui must take on integral values; i.e., Kz, and ql must be rational, if hi and vi are integers, i.e., if K1 and are rational. Thus for cubic materials a Type-I mode must degenerate into a compound mode and the same result also arises for Type-II modes. The apparently irrational habits observed by the authors can thus not be explained in terms of Type-I1 twinning if the classical laws of deformation twinning are to be obeyed. An alternative explanation of the irrational habits is that they may arise from twinning modes with four irrational twinning elements. These modes, which do not obey the classical orientation relationships associated with deformation twinning, have been shown to arise as the result of double twinning processes in magnesium,22 but may also describe a simple shear on an irrational plane in an irrational direction. Indeed double twinning processes in bcc

Jan 1, 1963

By J. Washburn, R. Drouard, E. R. Parker

Temperature dependence of the rate of recovery in zinc single crystals after a simple shear deformation at low temperature was investigated. Some tentative suggestions regarding the annealed and strain-hardened states of a crystal are discussed. RECOVERY may be defined as the gradual return of the mechanical and physical properties of strain-hardened metal to those characteristic of the annealed material; an increase in temperature increases the rate of recovery. The annealing process in strain-hardened polycrystalline metals is complicated by the inhomogeneity of strain which always exists in aggregates. Polygonization in bent regions of the crystals and growth of new almost strain-free grains starting at points of severe local distortion1-:' make it almost impossible to isolate and study the recovery process. Homogeneously strained single crystals, however, do not polygonize or re-crystallize and hence they can be used advantageously to study recovery. In such crystals strain hardening is completely removed by recovery alone. Since recovery is a process whereby certain lattice disturbances introduced by plastic flow are gradually reduced, a knowledge of the rate and temperature dependence of this process for various conditions of prestrain might be helpful in formulating a model of the strain-hardened state. For simplicity it seemed desirable to limit the type of prestrain to the simplest obtainable, i.e., simple shear strain. In the experiments to be described, recovery was studied by observing changes in the stress-strain curve of prestrained zinc single crystals held for various times at temperatures above that employed for straining. Single crystals were grown from the melt by a modified Bridgeman technique from Horse Head Special zinc 99.99 pct pure, and from spectrographically pure zinc 99.999 pct pure. They were grown as 1 in. diameter spheres and acid-machined' to the final specimen contour. The test section was a cylinder about 1/8 in. high and 3/4 in. in diameter. The conical sections adjacent to the test section were cemented into the grips so the load could be transmitted to the crystal as uniformly as possible. The specimens were oriented so that in testing the maximum shear stress was applied along one of the slip directions, [2110], in the (0001) plane. Details of the production and testing of such specimens have been presented.' Each test was carried out according to the following schedule: 1—The crystal was strained at — 50°C until it reached a maximum shear stress, ,,,. The strain rate was approximately 5 pct per min in all cases. 2—After straining, the crystal was unloaded before the temperature was changed. Unloading required about 3 min. 3—The temperature of the specimen was then increased from — 50°C to the temperature, T, of recovery. This change in temperature was completed in a time of less than 2 min. The specimen remained at temperature, T, for a time, t, which differed for the various specimens. 4—Thereafter the temperature was again reduced to — 50 °C in approximately 3 min. 5—While at —50°C, the stress-strain curve after recovery was obtained. 6—The specimen was then unloaded and annealed for 1 hr at 375 °C in a helium atmosphere to bring about complete recovery. Cooling to room temperature after anneal required 90 min. 7—The same crystal could be re-used for another test because the plastic properties after annealing closely duplicated those of the original crystal. The specimen was immersed during the test in a bath of methyl alcohol which, through a system of tubes, could be pumped through either of two heat exchangers to regulate the temperature; this was accomplished by circulating the liquid through coils immersed in a bath of acetone and dry ice for cooling or in a bath of warm water for heating. Test temperatures were thus maintained constant within ±1°C. The — 50°C temperature was low enough so that no measurable recovery occurred during unloading and reloading. The stress-strain curve continued after recovery along a path below, but approximately parallel to, the path of a curve obtained in an uninterrupted test. Fig. 1 shows some of the results from a specimen of 99.999 pct Zn. The amount of downward displacement of the curve due to recovery was a

Jan 1, 1954

By Sir Lowthian Bell

WITH the exception of air and water, it is open to question whether there is any form of matter which the human race could less easily spare than iron. Short of going the length of asserting that, without this metal for an anchor or steel for the compass, the adventurous navigator could never have crossed the wide Atlantic, we may credit the locomotive' and the steamer, and hence iron, for that sequence of events which has peopled North America with the

Jan 1, 1891

By A. S. Argon, G. East

From their study of the anisotropy of grain boundary mobility in aluminum, the authors conclude that tilt boundaries have a higher mobility than twist boundaries because the atomic misfit at the pure-twist boundary is relatively small compared to the misfit at a tilt boundary for a given amount of misorientation. If this is true, then one would expect a twist boundary to have a lower grain boundary energy than the corresponding tilt boundary. Fig. 6, taken from the work of Gjostein and Rhines,10 shows that this is indeed the case for [001]-cu tilt and twist boundaries in the high-angle region, thus lending support to the authors' conclusion.

Jan 1, 1968

By W. C. McBee, B. W. Jong, T. A. Sullivan

A sulfur concrete technology has been developed by the US Bureau of Mines, where chemically modified sulfur is used with suitable mineral aggregates to produce construction materials that are resistant to corrosion by acids and salts. This report presents a summary of the basic technology and results of testing the materials under actual operating conditions in 50 corrosive environments in 40 commercial plants. After four years of testing, there was essentially no evidence of material degradation or loss of strength. Regular concrete materials were attacked and, in some cases, completely destroyed under the same conditions. Testing is continuing to establish ultimate longevity and durability of the sulfur concretes. The materials are finding widespread applications in metallurgical, chemical, and fertilizer processing plants.

Jan 1, 1986

By H. L. Luo, P. Duwez, C. C. Chao

BY rapidly cooling alloys from the liquid state, it is possible to obtain solid solutions beyond the equilibrium concentrations, provided that the components are miscible in the liquid state. Typical such cases include CU-Ag,1 Pt-Ag,2 CU-Rh,3 nickel-base alloys with silicon, germanium, and tin,4 and cobalt-base alloys with silicon, germanium, tin, aluminum, and gallium.5 In the present note it is shown that terminal solid solutions can be appreciably extended in A1-Mg alloys. The alloys whose compositions are given in Table I were prepared by induction melting in tantalum crucibles under an argon atmosphere. Both aluminum and magnesium were 99.99 pct pure. Weight losses after melting were less than 0.2 pct for the aluminum-rich alloys and less than 0.4 pct for the magnesium-rich alloys. From these weight losses it was estimated that the compositions of the ingots after melting were accurate within 0.3 at. pct for aluminum-rich alloys and within 0.5 at. pct for magnesium-rich alloys. As indicated in Table I, the compound AuCd10 in which there is an ionic contribution to the bonding. The authors thank Dr. J. H. Westbrook of the Research Laboratory, General Electric Co., for arranging the supply of materials and for his interest. This investigation was supported by the U.S. Atomic Energy Commission under Contract AT(30-1)-1002, Scope I. some of the alloys were also chemically analyzed and the results confirmed the limits of uncertainty based on weight losses. Rapid quenching from the liquid state was achieved by techniques previously described.8,7 The principle of these techniques consists of propelling a small globule of liquid alloy (about 20 mg) onto a copper substrate. The thin foils easily detached from the copper substrate were analyzed by X-ray diffraction using a Debye-Scherrer camera 114.6 mm in diameter and either nickel-filtered copper Ka or iron-filtered cobalt Ka radiation. Since the back-reflection doublets were resolved, the wavelengths used in the computatioas were CuKal = 1.54050A and CoKa1= 1.78892A. Lattice parameters were obtained by extrapolation of the Nelson-Riley function, and the tables compiled

Jan 1, 1964

By A. W. Adamson

A model for transport processes in liquid mixtures is discussed which supposes that the elementary act involves a position exchange between two species and that the exchange is so confined by the solvent cage as to occur nearly isosterically. The rate-determining step, thus, is likened to a bi-molecular reaction and is so treated, using absolute rate theory. The cage model has been applied to diffusion, thermal diffusion, sedimentation and viscosity, but only the first and last of these phenomena are emphasized in the present paper. The model leads to semi-empirical relationships between the absolute value for a digusion coefficient and the activation energy for diffusion, between mutual and self-diffusion coefficients and for the variation of the viscosity of a binary mixture with composition. These are discussed in relation to experimental data for various systems, including hydrocarbon mixtures. It is shown that the proposed viscosity equation and seven other commonly used ones all may be regarded as special cases of a single general relationship; a brief critical analysis is made of the basis of selection of one or the other for data fitting or interpolation. INTRODUCTION AND GENERAL THEORY The present paper covers a brief discussion of a cage model for transport processes in liquid mixtures and how this model may be useful in treating the diffusional behavior and the viscosity of such systems. Since diffusion requires the more detailed treatment, it will be taken up first, and the model then applied to viscosity. There are two types of diffusion coefficients that may be measured experimentally, apart from thermal diffusion quantities. The first is the mutual or binary diffusion coefficient, D which may be defined in terms of Fick's first law. This states that the permeation, or flux P, is proportional to the concentration gradient. In the usual experiment, P is measured relative to a frame of reference fixed with respect to the medium (e.g., the diaphragm in a diffusion cell); as a consequence, the same value of D is obtained regardless of whether P and C refer to Component 1 or to Component 2; i.e., there is only one independent mutual diffusion coefficient for a binary system. In addition to D there will be various self-diffusion coefficients. defined in terms of the gradient in labelled species i and its permeation in an otherwise uniform medium. The thermodynamic approach to mutual diffusion supposes that the actual driving force is the gradient of the chemical potential, i.e., that In the case of a dilute solution of solute, Eqs. 1 and 3 lead to the Einstein equation, If the solution is ideal and the friction coefficient is taken to be then the familiar Stokes- Einstein equation results. Mutual and self-diffusion coefficients can not be related on general thermodynamic grounds; it is necessary to invoke some additional assumptions, i.e., a model; several such have been proposed. Hartley and Crank' supposed the existence of separate, intrinsic diffusion coefficients (Dl and D2) for each component, essentially corresponding to the two self-diffusion coefficients. The two flows can not be independent, however, but must be coupled through the usual restriction that there be no net volume flow. For an ideal solution. one then obtains' Glasstone, et al' treated diffusion in terms of absolute rate theory, but their approach otherwise resembled the previously mentioned one in that each species was considered to move with respect to the general medium in a manner determined by its individual jump distance and specific rate constant. For other than dilute solutions, a coupling of flows leading to an equation such as Eq. 6 would again be present. However, as required by Eq. 6, one does expect that the self-diffusion coefficient for the solute and the mutual-diffusion coefficient for the system become identical at infinite dilution. Lamm4 recognized that there should be three distinctive interactions in a two-component system-1-1, 1-2 and 2-2 — and, therefore, proposed three rather than two fundamental friction coefficients. Mutual diffusion resulted from 1-2 interactions only, and self-diffusion resulted from 1-2 plus either 1-1 or 2-2 interactions. Again, a collective coupling between all motions was imposed to meet the condition of no net volume flow. Laity' has shown how to convert the Onsager equations to a form very similar to Lamm's. Cage Model For Diffusion Work in this laboratory on diffusion in aqueous sucrose solutions made it apparent that three, rather than two, interactions were indeed needed," but considera-

By H. J. Morel-Seytoux

The influence of patten, geometry on assisted oil recovery for a particular dispIacement mechanism is the object of investigation in this paper. The displacement is assumed to be of unit mobility ratio and piston-like. Fluids are assumed incompressible and gravity and capillary effects are neglected. With these assumptions it is possible to calculate by analytical methods the quantities of interest to the reservoir engineer for a great variety of patterns. Specifically, this paper presents (1) very brieily, the methods and mathematical derivations required to obtain the results of engineering concern, and (2) typical results in the dorm of graphs or formulae that can be used readily without prior study of the methods. Results of this work provide checks for solutions obtained from programmed numerical techniques. They also reveal the effect of pattern geometry and, even though the assumptions of piston- like displacement and of unit mobility ratio are restrictive, they can nevertheless be used for rather crude but quick, cheap estimates. ,These estimates can be refined to account for non-unit mobility ratio and two-phase flow by correlating analytical results in the case M = 1 and the numerical results for non-piston, non-unit mobility ratio displacements. In an earlier paper1 it was also shown that from the knowledge of closed form solutions for unit mobility ratio, quantities called "scale factors" could be readily calculated, increasing considerably the flexibility of the numerical techniques. Many new closed farm solutions are given in this paper. INTRODUCTION BACKGROUND Pattern geometry is a major factor in making water-fIood recovery predictions. For this reason many numerical schemes have been devised to predict oil recovery in either regular patterns or arbitrary configurations. The numerical solutions, based on the method of finite difference approximation, are subject to errors often difficult to evaluate. An estimate of the error is possible by comparison with exact solutions. To provide a variety of checks on numerical solutions, a thorough study of the unit mobility ratio displacement process was undertaken. To calculate quantities of interest to the reservoir engineer (oil recovery, sweep efficiency, etc.), it is necessary to first know the pressure distribution in the pattern. Then analytical procedures are used to calculate, in order of increasing difficulty: injectivity, breakthrough areal sweep efficiency, normalized oil recovery and water-oil ratio as a function of normalized PV injected.

Jan 1, 1967

By Alex Boozenny

The results of potential measurements between 1) a titaniurn electrode in NaCl-TiCl, melts and a graphite-cizlorine reference electrode and 2) a titanium electrode in NaC1-Nu "melts and a graphite-chlorine reference electrode show that the following relationship expresses the equilibrium relationship between the TiCl, and the dissolved metallic sodium concentrations, expressed in mole fraction units, in dilute NaCl welts at 850°C. The results of potential measurenments between a graphite electrode in NaCl-TiCl, melts that were saturated with TiCl, and a graphite-chlorine reference electrode, when combined with the standard free energy data given in literature, gave the following expression for the equilibrium relationship between the TiCl, and TiCl, concentrations, expressed in mole fraction units, in dilute NaCl melts at 850°C. These relationships are for melts in equilibrium with pure titanium. In impure systems, less sodiurn and more TiCI, can be copresent with a given concentration of TiCl,. AFTER 10 years of existence, the titanium metal industry still relies on the original Kroll and the sodium reduction processes for the only important means of converting titanium-bearing ores to titanium metal via production of titanium tetrachloride as an intermediate. Through years of modification and development these two processes have evolved to a point where any further major economic advances in the field of titanium metal production must be achieved through implementation of processes which are distinct departures from simple magnesium or sodium reduction of titanium tetrachloride. Concurrently with the refinement of the Kroll and sodium reduction processes, industries and government have sponsored research and development in the field of producing titanium by electrolysis of oxides,' carbides,' and halides3'4 in fused salt media. However, the incomplete understanding of the physical chemistry of fused salt systems has in many cases hindered the development of promising new titanium production processes to the point where they will have a clear advantage over the processes presently employed. Fortunately the volume of information on fused salt physical and electrochemistry is increasing at an accelerating pace. The first approaches tbward investigating the electrochemical behavior of fused salt systems have been the measurements of equilibrium potentials of metals immersed in melts containing their halides.' Some work on the kinetics of fused salt electrochemical processes has been reported.'09" Some descriptions of the structural composition of fused salt systems are also available. The work described herein is a continuation of the study of metal electrode potentials in fused salts. Specifically, this contribution to the growing store of fused salt chemistry information presents a description of the equilibrium relationships between the concentrations of titanium dichloride, titanium trichloride, and metallic sodium in fused sodium chloride. The investigation of the titanium dichloride-titanium trichloride equilibrium relationships is not completely new. Kellog and Krye and Melgren and opie15 have presented the results of chemical analysis of salts containing titanium chlorides. Flengas and lngrahaml' have published the results of an investigation of these equilibrium relationships obtained by measurement of electrode potentials in a fused NaCl-KC1 mixture. The investigation described herein differed from that of Flengas and Ingraham principally in the use of straight NaCl as the solvent in place of the more costly and more difficult to purify mixture. This investigation was conducted in three parts. First, the equilibrium potentials of titanium in sodium chloride containing known concentrations of titanium dichloride were measured. A graphite-chlorine electrode was employed as reference. Second, the equilibrium potentials of titanium immersed in sodium chloride containing known concentrations of elemental sodium were measured. Third, the equilibrium potentials of graphite immersed in titanium tetrachloride-saturated sodium chloride containing known concentrations of titanium trichloride were measured. The results of these three related investigations are presented in the above order. The results are combined with the thermodynamic properties of titanium chlorides and sodium chloride, obtained from literature, to give the titanium dichloride-titanium trichloride-elemental sodium equilibrium concentration relationships. In the test, whenever a melt contains titanium chlorides in predominantly divalent form, the melt

Jan 1, 1962