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By Oscar Weiss

An aerial magnetometer survey was carried out by the author's geophysical organization over the Vrede-fort dome, where Witwatersrand beds are wrapped around a granite plug 25 to 30 miles in diameter. The well-known magnetic shales of the Lower Witwatersrand system (to be referred to as LWW) give strong negative anomalies over the out-cropping portion of the dome. This is unusual as these same shales cause positive anomalies over large areas near Johannesburg and along a strike of 130 miles between the East Rand and Klerksdorp. It is suggested that the negative polarization is caused by heat and stresses connected with the doming. This negative polarization of sedimentary beds, which usually cause positive anomalies, is a good example of how "magnetic lows" can be caused by "structural highs." Significant magnetic anomalies should be tested by gravity and seismic methods irrespective of the sign of the anomalies. South of the line X — Y (see Fig 2 and 5) the gravity anomalies are smaller over the LWW beds and magnetic anomalies suddenly become weaker and even change signs by becoming positive. This peculiar phe- nomenon is explained by faulting which truncated the nearly vertical LWW shales at depth. In this manner the mass of the LWW beds has been reduced together with the weakening of the negative magnetic anomalies by positive poles which occupy the truncated end. Furthermore, by uplifting the beds between f1 and f2 (Fig 2) positive polarization becomes predominant, thus causing positive magnetic anomalies. General The Vredefort dome is one of the internationally known geological structures, which, among others, has attracted the attention of numerous American geologists. It was for this latter reason that our aerial magnetic results over this structure were selected by us for publication in the United States of America. A full description of the exposed geology has been published by Nell and readers are referred to this paper, which is subject to only slight modifications inasmuch as the subdivision of the Witwatersrand system (to be referred to as WW system) is concerned. The Vredefort dome is about 60 miles southwest of Johannesburg. The WW system, after being exposed in the vicinity of Johannesburg, plunges with southerly dips beneath the Vent-ersdorp and Transvaal systems. Along a section southwest from Johannesburg, as shown diagrammatically in Fig 4, we see no outcrops of the WW system until the Vredefort dome, where the Upper and Lower WW system are wrapped around an almost circular arc of a granite mass. Here the whole WW system is overturned around the perimeter of a huge granite plug 25 to 30 miles in diameter. Less than half of the circumference of this dome is exposed; the rest is covered by Karroo dolerites and sediments. The determination of the exact shape of the concealed part of the dome has been a matter of considerable interest and obviously geophysical methods were eminently suited for obtaining this information. A good start was made with a gravimeter survey carried out by the Geological Survey of the Union of South Africa.2 Our own

Jan 1, 1950

By T. Leffers, A. Grum-Jensen

The development of texture in copper and brass (15 pct Zn by weight) rolled at room temperature and in copper rolled at -196°C has been followed by determination of pole figures for various degrees of reduction. The concurrent development in microstructure has been investigated by transmission electron microscopy. For low deformations, the texture in brass, and in copper rolled at -196°C, is the same as the texture in copper rolled at room temperature. The difference in texture does not show until 50 pct reduction. At the same reduction at which the difference in texture appears, mechanical twinning starts in brass and low-temperature rolled copper. Nevertheless, Wassermann's twinning theory is found to be incompatible with the present resulls. All fcc metals and alloys develop, by heavy rolling, one or the other of two types of texture, classified for convenience as copper type and brass type, or possibly a '(mixed" texture representing an intermediate stage between the two types. The pure fcc metals, except silver, develop copper-type texture by rolling at room temperature. Silver and many alloys, including brass with more than 10 pct Zn, develop brass-type texture.' By rolling at low temperatures a transition in texture from copper type to brass type has been observed for copper of commercial purity.2'3 It is generally accepted that there is a correlation between the type of texture developed and the stacking fault energy. Metals and alloys having fcc structure develop brass-type texture when rolled at room temperature if the stacking fault energy is low, whereas those with higher stacking fault energies have copper-type texture.2 Thus, the difference in stacking fault energy must cause a difference in deformation mechanism responsible for the difference in texture. Of the numerous theories advanced concerning the nature of this difference in deformation mechanism, four seem to be of current interest. Smallman and Greeen,2 Dillamore and Roberts,4 and Dillamore5 refer to the fact that cross slip more easily takes place in a material with a higher stacking fault energy and suggest that the copper-type texture is developed by deformation with extensive cross slip whereas the brass-type texture is developed by deformation without cross slip. Haessner6 has advanced the theory that the copper-tye texture is developed by a combination of normal {111} slip and slip on other planes, mainly 1100). Thus his theory, like the theory above, proposes an additional deformation mode for the formation of the copper-type texture. Contrary to this, wassermann7 and Ahlborn et al.8 believe that the copper-type texture is obtained by normal slip. In their opinion mechanical twins will change a copper texture into a brass texture. For this reason it is suggested that the brass-type texture is developed when, in addition to normal {111}(110) slip, mechanical twinning is present. None of these theories are, however, supported by direct experimental evidence. In a recent experiment Hu et al.9 have followed the development of rolling texture in copper and brass. The texture of copper and brass was found to be es-

Jan 1, 1969

By C. E. Birchenall, F. N. Rhines, L. A. Hughes

A. J. Shaler—I should like to congratulate the authors on the presentation of this paper, which we have been awaiting a long time. The view they have taken of the sintering process, namely that voids are comparable to particles of a second phase capable of dissolving to a slight extent in the metal phase, is an interesting but dangerous one. Pines has given a first-order solution of the problem and Has predicted a decrease in the concentration of pores near the surface. The authors of the present paper have experimentally demonstrated the second-order effects, that is, the diffusion of the space phase between voids of different sizes, and also the movement of atoms from highly curved parts of a void to less curved regions of the same void. I have recently calculated the rate of vapor-phase transport within odd-shaped pores in copper at 850 °C and found that probably at that temperature volume flow is the more rapid shape-changing mechanism. The authors of the present paper have found that at 1000°C, vapor-phase transport is dominant. There is no disagreement here, I think. The dominant phenomenon can easily be different' in different temperature ranges and with different pore shapes: I used a cylinder going to a sphere, not a tricuspid going to a "triple cuspidor." But there is some danger in the other art of the explanation, that is, in the study of the diffusion of vacancies from a pore to its neighbors and to the outside. A vacancy is very different in dimension from an atom. When it moves, it carries a field of elastic strain. This has to be taken into account. A concentration gradient of vacancies can cause them to diffuse. But in the absence of such a gradient, they can be made to diffuse by a field of stress. What happens in some of our experiments, and it is most noticeable in the shrinkage of synthetic cylindrical pores, like the tubes we have been working with, may be broken down into the following steps. (1) The presence of a surface establishes a vacancy concentration gradient, as Dr. Kuczynski and the present authors have shown. (2) Vacancies then diffuse in order to decrease this gradient. (3) In so doing, they cause an elastic field to be built up in such a direction as to oppose the diffusion, so that it slows down until it reaches a steady-state rate. (4) The steady-state flow is due to the fact that the surface tension acting on curved surfaces applies a stress to the system which itself mechanically causes vacancy diffusion. What I have said is that the diffusive types of flow of the authors and of Dr. Kuczynski are transient phenomena which soon stop if the pores are large. We are then left with a mechanical problem only, and our researches have not yet disclosed just what the mechanism of flow is; it may be a slip process, or it may take place by a vacancy diffusion of the type Nabarro has de-

Jan 1, 1951

By R. W. Fenn, H. A. Lepper, W. R. Hibbard

A. J. Shaler—I should like to congratulate the authors on the presentation of this paper, which we have been awaiting a long time. The view they have taken of the sintering process, namely that voids are comparable to particles of a second phase capable of dissolving to a slight extent in the metal phase, is an interesting but dangerous one. Pines has given a first-order solution of the problem and Has predicted a decrease in the concentration of pores near the surface. The authors of the present paper have experimentally demonstrated the second-order effects, that is, the diffusion of the space phase between voids of different sizes, and also the movement of atoms from highly curved parts of a void to less curved regions of the same void. I have recently calculated the rate of vapor-phase transport within odd-shaped pores in copper at 850 °C and found that probably at that temperature volume flow is the more rapid shape-changing mechanism. The authors of the present paper have found that at 1000°C, vapor-phase transport is dominant. There is no disagreement here, I think. The dominant phenomenon can easily be different in different temperature ranges and with different pore shapes: I used a cylinder going to a sphere, not a tricuspid going to a "triple cuspidor." But there is some danger in the other art of the explanation, that is, in the study of the diffusion of vacancies from a pore to its neighbors and to the outside. A vacancy is very different in dimension from an atom. When it moves, it carries a field of elastic strain. This has to be taken into account. A concentration gradient of vacancies can cause them to diffuse. But in the absence of such a gradient, they can be made to diffuse by a field of stress. What happens in some of our experiments, and it is most noticeable in the shrinkage of synthetic cylindrical pores, like the tubes we have been working with, may be broken down into the following steps. (1) The presence of a surface establishes a vacancy concentration gradient, as Dr. Kuczynski and the present authors have shown. (2) Vacancies then diffuse in order to decrease this gradient. (3) In so doing, they cause an elastic field to be built up in such a direction as to oppose the diffusion, so that it slows down until it reaches a steady-state rate. (4) The steady-state flow is due to the fact that the surface tension acting on curved surfaces applies a stress to the system which itself mechanically causes vacancy diffusion. What I have said is that the diffusive types of flow of the authors and of Dr. Kuczynski are transient phenomena which soon stop if the pores are large. We are then left with a mechanical problem only, and our researches have not yet disclosed just what the mechanism of flow is; it may be a slip process, or it may take place by a vacancy diffusion of the type Nabarro has de-

Jan 1, 1951

By W. C. Winegard, E. L. Holmes

The effects of the solute elements lead and bismuth on grain growth in zone -refined tin have been investigated. At low temperatures, viz. below 160°C. or at high concentrations, viz. greater than 0.03 at. pct, the temperature dependence of grain growth was found to be constant. A correlation was found to exist between the rates of grain growth in the presence of solute impurities and the factor [C Ir - 1]2 , where C is the solute concentration, r is the radius of solvent atom, and r' is radius of solute atom. It is shown that the Liicke and Detert theory does not give a satisfactory explanation of the results obtained. INVESTIGATIONS of grain growth in zone-refined lead and tin and some effects of solute elements on grain growth in these metals have been reported by Bolling and winegardly2 and Holmes and winegard? The present investigation is an extension of the previous work, and was undertaken to provide additional results which might make it possible to discover the mechanism whereby the rate of grain growth is affected by the presence of foreign solute atoms. The experimental procedure was exactly the same as that described previously.3'4 Figs. 1 and 2 show the results obtained with lead and bismuth additions over the same temperature range, viz. 167" to 220°C, as that used for the investigation of grain growth in zone-refined tin.3 Fig. 3 shows the results obtained for zone-refined tin and for this tin with lead solute additions over an extended temperature range. DISCUSSION OF RESULTS As mentioned previously,3 the character of grain growth in the particular zone-refined tin used in these experiments appears to change as the temperature of annealing falls below about 160°C. The grain growth became somewhat irregular and was characterized by a jaggedness of many of the grain boundaries. The reason for this change is not known, but may be due either to residual impurity effects or possibly an oxide precipitation. It was obvious that normal grain growth only occurred in the zone-refined tin through the high-temperature range 167" to 220°C, and so the effects of solute atoms on grai11 growth over the two temperature ranges will be discussed separately. a) Effect of Impurity on Grain Growth in the Temperature :Range Above 167°C. It is apparent from Figs. 1 and 2 that, for low concentrations of solute, the rates of grain growth tend towards a common value as the melting temperature of tin is approached. As the concentration of lead is increased, the rate of grain growth close to the melting temperature is also reduced, and at high concentrations the temperature dependence of the rate of grain growth appears approximately constant. It should be noteil that the effect of bismuth is greater than that of the same concentration of lead, but both these solutes have a smaller effect on the rate of grain growth than silver, as seen from an earlier investigation of Holmes and Winegard. It should

Jan 1, 1962

By J. L. Meijering

Oxidation hardening of cylindrical and spherical specimens first decreases with depth below the surface, but then increases again as the center is approached. This is in agreement with the view that this change in hardness is mainly determined by the change in velocity of the oxidation boundary, which affects the dispersion of the oxide. WHEN a thick slab of silver containing 0.3 pct Mg by weight is internally oxidized, the hardness measured on a cross section is found to decrease considerably with distance from the surface.&apos; This phenomenon has been attributed to the diminution of the velocity of the oxidation boundary. The smaller this velocity is, the more slowly the free-oxygen concentration rises towards the concentration in equilibrium with the oxygen gas. And a small 0 concentration favors dissociation and thus conglomeration of the oxide. For instance, the hardness decreases more rapidly during long annealings in nitrogen than in air.&apos; Measurements by Gregory and Smith3 on sections through internally oxidized Al-silver wire showed a smaller variation in hardness, probably because the wire diameter was only 0.9 mm. Wood4 found a drop in hardness with depth in internally oxidized Al-copper strip, and also—by electron microscopy—the concomitant increase in Al2O3 particle size. Under certain circumstances internal oxidation leads to formation of rather irregular inner oxide films in the midst of dispersed oxide. This special sort of conglomeration—discussed in Ref. 5—is also favored by greater depth below the surface.3,5 In this paper hardness measurements in large diameter cylindrical and spherical specimens are described. Here the oxidation velocity* goes through ness initially decreases with depth but increases again towards the center. Normally, the diffusion coefficient D1 of oxygen is very large compared to D2, that of the dissolved metal. If, furthermore, the atomic fraction c2 of the latter is much larger than the O-solubility cl- but c2D2 << c1D1- the velocities in question are easily calculated2 to be: for the cylinder and for the sphere. Here p is the radial coordinate of the oxidation boundary and R the specimen radius, which in dilute silver alloys is constant, as no external oxidation occurs. These equations have been derived for a divalent solute; for nondivalent solutes c2 has to be multiplied by half the valency. The equations are not valid near the center. For which can be considered as a standard case,2 the Eqs [I] and [2] begin to yield U-values which are appreciably too high for p/R = 0.05 and 0.15, respectively. But at the v-minima they are still very good approximations. These minima lie at p = emlR= 0.37R in the cylinder and p = 1/2 R in the sphere. Other factors besides the velocity v will also influence the hardness. The oxide concentration cox is constant in a flat strip, apart from a narrow region in the middle,2 but in cylindrical and spherical specimens cox decreases steadily with depth. When C1 << c2 and c1D1 >> c2D2 one can calculate

Jan 1, 1961

By E. Stamboliadis

Dithiophosphates are reaction products of phosphorous pentasulfide with various organic compounds such as phenols, alcohols, mercaptans, dioalcohols, amines, and nitrides. The products with alcohols are commercially known as "aerofloats" and these are investigated in this presentation. It appears that the formation of insoluble metal dithio phosphates is responsible for their collecting properties with minerals." In this aspect they are very similar to xanthates.3 The solubility of metal dithiophosphates depends on the number of carbon atoms in the organic chain of the corresponding alcohol. An empirical mathematical model is presented here. It allows one to predict the number of carbon atoms necessary to ensure that a certain metal dithiophosphate will form at a selected pH value of the water solution. The Nature of Dithiophosphates Dithiophosphoric acid is the product of the reaction of phosphorus pentasulfide with an alcohol, as shown in the following equation: [P2S3 + 4 ROH - 2 (RO)2 PS2H + H2S (1)] where R stands for a hydrocarbon chain. The acid so produced can be neutralized by a base to produce the corresponding salt as shown in the following: [(RO), PS2H + NH- (RO)2 PS, NH,. (2)] In this aspect dithiophosphates are similar to xanthates, the only difference being the substitution of the tetravalent carbon atom in the xanthate polar group by a pentavalent phosphorus atom in the dithiophosphate group. This difference implies at least two characteristics: (1) that there are two hydrocarbon chains associated with the polar group so that an increase in the number of carbons of the single chain is expected to have a pronounced effect on the flotation properties, and (2) that the bond between the sulfur and the central atom is stronger than in the xanthate group. This probably leads to a decrease in both the polarizability of the electronic cloud of the sulfur and the interaction with cations.3 However, what is lost in the dithiophosphates by having a weak polar group can be gained by an increase in the number of carbons as will be seen later. Taking into account the size of the atoms involved in a dithiophosphate molecule, as listed in Table 1, It is possible to draw an approximate diagram of its structure as shown in [Fig. 1]. It is assumed here that the length of the single hydrocarbon chain is equal to that of the corresponding alcohol. Preparation and Purification Acid dithiophosphates can be prepared, as previously mentioned, in accordance with Eq. 1. The rate of this reaction is too slow at room temperature and can be improved by increasing the temperature to about 60° or 80°C7 or by evacuating the system. In our investigation evacuation was performed by a water aspiration pump. The dithiophosphoric acid so produced is liquid and dissolves in the alcohol. At the end of the reaction the product is filtered from the remaining P2S3; and dissolved in petroleum ether. By blowing anhydrous ammonia gas into the ether phase the ammonium salt forms as a white precipitate and can be sepa-

Jan 1, 1977

By C. W. Spencer, F. G. Hochgraf, R. F. Cheney

Columnar grained specimens of nickel, containing 0.25 pct Si and 0.22 pct Mn, have been exposed to liquid bismuth in the temperature range 670° to 1050°C. Under isothermal conditions the liquid penetration rate is constant. The activation energy for the process is 22,000 cal per g-atom. Small amounts of plastic deformation, introduced into specimens prior to exposure, increase the penetration rate. The slou. step in liquid film penetration is associated with a reaction which occurs at or near the leading edge of the film. Either transfer of nickel across the liquid-solid inteqace or diffusion in the grain boundary ahead of the liquid film is suggested. Aliquid metal, if brought into contact with the surface of an unstrained solid metal, will usually penetrate to some extent into the grain boundaries of the solid. Under isothermal conditions the extent of penetration after any particular time of exposure is related to the relative magnitudes of the interfacial tensions concerned.1,2 If the liquid-solid interfacial tension is less than one-half the grain boundary tension the liquid may penetrate at a relatively rapid rate for an indefinite distance into the grain boundary surfaces. If the liquid-solid interfacial tension is greater than one-half the grain boundary energy, liquid penetration occurs at a continually decreasing rate so that after the liquid has penetrated to a relatively short distance below the surface the process essentially ceases.3 Many observations of a qualitative nature concerning inter crystalline attack by liquid metals have been reported, for example, liquid bismuth upon copper,&apos; liquid mercury upon brass,4 and liquid mercury upon nickel.&apos; Scheil and Schessl determined the rate of penetration of liquid bismuth into the grain boundaries of hot rolled copper rod? At constant temperature, penetration rate was found to be independent of the depth penetrated, the rate in- creasing with increasing temperature corresponding to an activation energy of 20,000 cal per g-atom for the process. It was suggested that at lower temperatures the liquid travelled mainly along lines of three grain intersections while at temperatures greater than 1000°C essentially all grain boundary surfaces were covered. Recently, in a study of copper bicrystals having a common [loo] axis it was found that at 649°C bismuth penetrated 22, 25, and 63 deg boundaries while it did not penetrate 2, 12, 15, and 72 deg boundaries.&apos; Elbaum reported that liquid gallium penetrates aluminum grain boundaries to a depth of 0.6 cm after 11 hr at 27°c.8 Assuming that the rate controlling step in the process was diffusion down the liquid film to the specimen surface, a diffusion coefficient of 10-5 cm2 per sec was calculated. This paper reports a study of the penetration of bismuth-nickel liquids into the grain boundaries of a nickel alloy, containing 0.25 pct Si and 0.22 pct Mn as principal alloying elements. The phase diagram

Jan 1, 1962

By J. E. Burke

RECENT investigations have elucidated many of the phenomena of the grain growth process, but have also revealed some conflicting and unexplained results. Beck and his co-workers1,2,3 have shown that grain growth continues with continued heating at one temperature until the average grain size approaches the thickness of the specimen, Plotting the logarithm of the average grain diameter, D, against the logarithm of the annealing time, t, they find the straight line relationship given by the equation: [D=Ktn [11] with possible small deviations at short annealing times. K and n are constants at constant temperature. On the other hand, Walker4 finds that, in alpha brass, the rate of growth falls off more rapidly than indicated by Eq I after long annealing, so that an equilibrium grain size is approached. Burke5 showed, using Walker&apos;s data, that time and temperature for grain growth are apparently related through an activation energy, H, according to the relationship: [t, Hr i &apos;_ III t„ = R \T, - ~) [2]] where t1 and t2 are the annealing times necessary for the average grain size to increase from Do to D at temperatures T1 and T2 and R is the gas laws constant. In the case quoted, H had the value 60,000 cal per mol. The apparent validity of this relationship, at least up to 700°C, and the approximate value of H were later confirmed by Beck.&apos; The results obtained by Beck, Kremer, Demer and Holzworth2 for aluminum and aluminum-magnesium alloys could not be satisfied by such a relationship, since the slope of the isothermal curves increased with increasing temperature. These data indicate and Beck, Holzworth and Hu6 later demonstrated experimentally that the only apparent factor controlling the rate of grain growth at constant temperature is the grain size. While many of the phenomena have been elucidated, a reasonably quantitative explanation of the process is lacking. There exists uncertainty even as to the primary driving force for grain growth, although there is a considerable body of indirect evidence that the interfacial energy of the grain boundary is responsible.7,8,10 Making implicit use of this assumption, several authors14,15 have pointed out that grain boundaries should migrate toward their center of curvature. Harker and Parker&apos; have advanced this concept furthest, and show that one can expect grain boundary migration to occur only when the grain faces are curved, or when they meet at non-equilibrium angles. When the face is curved toward a grain A, for example, the atoms in the surface of grain B, on the other side of the boundary, are on the average more surrounded by the atoms of their lattice than the atoms on the surface of grain A. Because of thermal motion, the atoms at the interface will sometimes be attached to grain A and

Jan 1, 1948

By I. J. Logan, Warren L. Baker

By 1950 or soon thereafter facilities will be available in foreign countries for the production, transportation, and refining of about 4,305,000 bbl per day of crude oil—a volume not far short of current United States output. This is indicated by announced plans for foreign expansion, - some of the work being already under way. The projected potential production is about 1,500,000 bbl per day or 50 pct above the record-setting foreign production of 2,810,000 bbl daily in 1946. The scheduled new foreign facilities are equivalent to almost one third of the present facilities of the United States. Fears that so much additional foreign oil may flood world markets and disrupt the domestic industry of the United States are not justified. The projected foreign expansion apparently has been planned on a sound business basis, with careful consideration of the world&apos;s actual need for all the projected additional production. Materially increased world demand for petroleum promises to absorb the increased supplies without ill effect upon the domestic industry. Even by applying conservative estimates of both foreign and domestic demand, it is indicated that world requirements can absorb the projected larger foreign output and still permit continued increase in United States production. World demand would have to increase only 5.7 pct per year in the 1947 to 1950 period to absorb the prospective supply. Such an increase may be conservatively projected, in view of past and current trends. Introduction Recent announcements of plans for expanding petroleum facilities in the Middle East and Venezuela foreshadow an unusually sharp increase in foreign production in the immediate future. Therefore, the next few years will bring far-reaching changes in world petroleum affairs, with foreign petroleum production and other activities assuming much greater importance than formerly. Tabulation of figures on development already under way or planned indicates that in the next several years facilities will be available for producing, transporting and refining twice the prewar production of foreign fields and about 50 pct or nearly 1,500,000 bbl a day above their record-level output of 1946. To say that foreign fields may be producing such an enlarged quantity by 1950 is, of course, a statement of great significance to everyone connected .with the oil industry and especially to those of the American petroleum industry. A production of 1,500,000 bbl daily is equal to the combined yield of the states of Oklahoma, Kansas, Illinois, Louisiana, Arkansas, Mississippi and New Mexico. This means that within the next several years foreign petroleum facilities will undergo a new expansion equivalent to one third of the present facilities of the United States. To think of such an expansion in foreign production is to raise at this meeting the question of what this prospective foreign development means for the United States, the American petroleum industry in general, and the American engineer and technologist in particular. It is only logical to question whether or

Jan 1, 1948

By Warren L. Baker, I. J. Logan

By 1950 or soon thereafter facilities will be available in foreign countries for the production, transportation, and refining of about 4,305,000 bbl per day of crude oil—a volume not far short of current United States output. This is indicated by announced plans for foreign expansion, - some of the work being already under way. The projected potential production is about 1,500,000 bbl per day or 50 pct above the record-setting foreign production of 2,810,000 bbl daily in 1946. The scheduled new foreign facilities are equivalent to almost one third of the present facilities of the United States. Fears that so much additional foreign oil may flood world markets and disrupt the domestic industry of the United States are not justified. The projected foreign expansion apparently has been planned on a sound business basis, with careful consideration of the world&apos;s actual need for all the projected additional production. Materially increased world demand for petroleum promises to absorb the increased supplies without ill effect upon the domestic industry. Even by applying conservative estimates of both foreign and domestic demand, it is indicated that world requirements can absorb the projected larger foreign output and still permit continued increase in United States production. World demand would have to increase only 5.7 pct per year in the 1947 to 1950 period to absorb the prospective supply. Such an increase may be conservatively projected, in view of past and current trends. Introduction Recent announcements of plans for expanding petroleum facilities in the Middle East and Venezuela foreshadow an unusually sharp increase in foreign production in the immediate future. Therefore, the next few years will bring far-reaching changes in world petroleum affairs, with foreign petroleum production and other activities assuming much greater importance than formerly. Tabulation of figures on development already under way or planned indicates that in the next several years facilities will be available for producing, transporting and refining twice the prewar production of foreign fields and about 50 pct or nearly 1,500,000 bbl a day above their record-level output of 1946. To say that foreign fields may be producing such an enlarged quantity by 1950 is, of course, a statement of great significance to everyone connected .with the oil industry and especially to those of the American petroleum industry. A production of 1,500,000 bbl daily is equal to the combined yield of the states of Oklahoma, Kansas, Illinois, Louisiana, Arkansas, Mississippi and New Mexico. This means that within the next several years foreign petroleum facilities will undergo a new expansion equivalent to one third of the present facilities of the United States. To think of such an expansion in foreign production is to raise at this meeting the question of what this prospective foreign development means for the United States, the American petroleum industry in general, and the American engineer and technologist in particular. It is only logical to question whether or

Jan 1, 1948

By B. M. Larsen

In endeavoring to put the art of the steelmaker on a more scientific basis, as a means of securing closer control of the product, we must be severely critical of the basis of any theory we use. In particular, we must be careful to distinguish between factors that are primary and those of only secondary impartance. The concentration relations that determine the slag-metal equilibria, which are usually more or less closely attained, are of course of primary significance, but a, dear picture of the whole process requires that the actual rates of the several reactions be taken properly into account. At the high temperature of the steelmaking furnace, all reactions might be thought to be very rapid, but some of them in fact are not; the essential causes of this condition are important to a proper understanding of the process. This paper aims to present, and to justify, the viewpoint that the most significant reaction is the oxidation of carhon in the metal, the progress of which determines the oxygen pressure levels in slag and metal and produces stirring effects, all of which influence the course of the process as a whole. Reaction Rates at Steelmaking Temperatures General experience in reaction rates makes it almost certain that at steelmaking temperatures equilibrium is attained practically instantaneously when the reactants are well distributed in a single liquid phase —that is, in the so-called homogeneous reactions. The actual slowness of some of the reactions in the open-hearth furnace must therefore be attributed to a relatively slow rate of diffusion within the slag or metal phase, which limits the rate at which the reactants can meet each other in the liquid steel or at its surface. That the reactions can be made to go with great rapidity, by proper mixing and stirring of the reacting phases, is indicated by the following illustrations: 1. In the Bessemer process there is intimate contact between air and the whole mass of metal, and the reactions are complete in a few minutes. 2. Perrinl has demonstrated that by pouring liquid steel into slag contained in a deep ladle, and thereby producing almost a slag-metal emulsion, the phosphorus or oxygen content of the steel is adjustcd immediately. 3. Barret, Holbrook and Wood2 observed a quite rapid rate of desulphurization when powdered calcium carbide was stirred vigorously into liquid iron. 4. When a spoonful of liquid steel is poured into a. mold containing aluminum wire, the formation and precipitation of alumina occurs in the fraction of a second required to freeze the surface layer of the tiny ingot. The first three examples all show that any means of increasing the effective surface between slag and metal and promoting intimate mixture of the reacting phases, thereby obviating the limitation imposed by diffusion, will enhance the speed of the steelmaking process.

Jan 1, 1941

By B. M. Larsen

In endeavoring to put the art of the steelmaker on a more scientific basis, as a means of securing closer control of the product, we must be severely critical of the basis of any theory we use. In particular, we must be careful to distinguish between factors that are primary and those of only secondary impartance. The concentration relations that determine the slag-metal equilibria, which are usually more or less closely attained, are of course of primary significance, but a, dear picture of the whole process requires that the actual rates of the several reactions be taken properly into account. At the high temperature of the steelmaking furnace, all reactions might be thought to be very rapid, but some of them in fact are not; the essential causes of this condition are important to a proper understanding of the process. This paper aims to present, and to justify, the viewpoint that the most significant reaction is the oxidation of carhon in the metal, the progress of which determines the oxygen pressure levels in slag and metal and produces stirring effects, all of which influence the course of the process as a whole. Reaction Rates at Steelmaking Temperatures General experience in reaction rates makes it almost certain that at steelmaking temperatures equilibrium is attained practically instantaneously when the reactants are well distributed in a single liquid phase —that is, in the so-called homogeneous reactions. The actual slowness of some of the reactions in the open-hearth furnace must therefore be attributed to a relatively slow rate of diffusion within the slag or metal phase, which limits the rate at which the reactants can meet each other in the liquid steel or at its surface. That the reactions can be made to go with great rapidity, by proper mixing and stirring of the reacting phases, is indicated by the following illustrations: 1. In the Bessemer process there is intimate contact between air and the whole mass of metal, and the reactions are complete in a few minutes. 2. Perrinl has demonstrated that by pouring liquid steel into slag contained in a deep ladle, and thereby producing almost a slag-metal emulsion, the phosphorus or oxygen content of the steel is adjustcd immediately. 3. Barret, Holbrook and Wood2 observed a quite rapid rate of desulphurization when powdered calcium carbide was stirred vigorously into liquid iron. 4. When a spoonful of liquid steel is poured into a. mold containing aluminum wire, the formation and precipitation of alumina occurs in the fraction of a second required to freeze the surface layer of the tiny ingot. The first three examples all show that any means of increasing the effective surface between slag and metal and promoting intimate mixture of the reacting phases, thereby obviating the limitation imposed by diffusion, will enhance the speed of the steelmaking process.

Jan 1, 1941

By Hjalmar W. Johnson

It has long been accepted that blastfurnace practice varies to some degree with the coke used. While the qualities desirablc in iron have been known for some time, the qualities in coke that produce such iron have not been established. There are no objective standards for blast-furnace coke, which is usually described in general terms, as good or bad. Many experienced operators believe that coke cannot be measured objectively except by using it in the furnace, noting the result, and labeling the coke according to furnace operations. This is admittedly unscientific, and besides is useless for the two main purposes for which a measure of coke quality is needed: (I) to produce the best possible coke from the coals and equipment on hand; (2) to test new coals and determine their value for blast-furnace coke. In seeking such an objective measure, much work has been done on tumbler tests, shatter tests, sizes of coke, porosity, specific gravity, reactivity or combustibility and other tests, but as yet very little has been published in which conclusive correlations have been established between such objective measures and furnace operation. In our study of the problem during the past 8 years we have developed no new measures of coke quality, but we have collected data that are presented here in the hope that they may assist in further work, so that at some future time there may be developed such positive measures. The purpose of this paper is to show that there are variations in coke and that such variations do influence the operation of blast furnaces. At the same time we must remember that there are variations in blastfurnace operation and it may be the blast furnace that is at fault. This correlation of coke properties with blast-furnace operation will be worked out in the following steps: . Discussion of a period when a change in the coke resulted in an increase in efficiency on one furnace and a decrease in efficiency on another. 2. Adaptation of the inefficient furnace to the available coke so that normal efficiency was restored. 3. The use of radial distribution: a discussion of the effect of size of ore layer in adapting blast-furnace operation to the coke. 4. An example of a change in size of coke and the detrimental influence on the pro duction of one furnace. 5. An example of a change in size of coke, together with manufacturing data, to show why it changed, the conclusion being that coke is a product with an optimum value. 6. Illustration of the fact that coke has different optimum values on two furnaces, with discussion on adaptation of operation so the optimum values will be the same. 7. Limitations of the use of screen tests as an objective measure of coke quality. 8. Importance of uniformity in coke. Functions of Coke and Qualities Required to Perform These Functions Coke has three important functions in a blast furnace: (I) to furnish most of the

Jan 1, 1942

By Hjalmar W. Johnson

It has long been accepted that blastfurnace practice varies to some degree with the coke used. While the qualities desirablc in iron have been known for some time, the qualities in coke that produce such iron have not been established. There are no objective standards for blast-furnace coke, which is usually described in general terms, as good or bad. Many experienced operators believe that coke cannot be measured objectively except by using it in the furnace, noting the result, and labeling the coke according to furnace operations. This is admittedly unscientific, and besides is useless for the two main purposes for which a measure of coke quality is needed: (I) to produce the best possible coke from the coals and equipment on hand; (2) to test new coals and determine their value for blast-furnace coke. In seeking such an objective measure, much work has been done on tumbler tests, shatter tests, sizes of coke, porosity, specific gravity, reactivity or combustibility and other tests, but as yet very little has been published in which conclusive correlations have been established between such objective measures and furnace operation. In our study of the problem during the past 8 years we have developed no new measures of coke quality, but we have collected data that are presented here in the hope that they may assist in further work, so that at some future time there may be developed such positive measures. The purpose of this paper is to show that there are variations in coke and that such variations do influence the operation of blast furnaces. At the same time we must remember that there are variations in blastfurnace operation and it may be the blast furnace that is at fault. This correlation of coke properties with blast-furnace operation will be worked out in the following steps: . Discussion of a period when a change in the coke resulted in an increase in efficiency on one furnace and a decrease in efficiency on another. 2. Adaptation of the inefficient furnace to the available coke so that normal efficiency was restored. 3. The use of radial distribution: a discussion of the effect of size of ore layer in adapting blast-furnace operation to the coke. 4. An example of a change in size of coke and the detrimental influence on the pro duction of one furnace. 5. An example of a change in size of coke, together with manufacturing data, to show why it changed, the conclusion being that coke is a product with an optimum value. 6. Illustration of the fact that coke has different optimum values on two furnaces, with discussion on adaptation of operation so the optimum values will be the same. 7. Limitations of the use of screen tests as an objective measure of coke quality. 8. Importance of uniformity in coke. Functions of Coke and Qualities Required to Perform These Functions Coke has three important functions in a blast furnace: (I) to furnish most of the

Jan 1, 1942

By P. R. Sperry

Aluminum alloy 3S was examined to determine the relationship between the applicable phase diagram and the microstructures produced under conditions tending toward non-equilibrium as well as equilibrium. The only phases present in the alloy were aluminum, (Mn,Fe)A16, aAI(Mn,Fe)Si, and silicon. It was found that the alloy behaved essentially as though it belonged to the Al-Mn-Si system. The effects of various solidification rates and of various homogenization treatments were studied. Particular attention was given to a nonuniform precipitate distribution which reflected the solute distribution in the cast aluminum solid solution. Some possible explanations for the solute distribution based on characteristics of the Al-Mn-Si or AI-Mn systems were discussed. ALUMINUM alloy 3s (aluminum plus 1.25 pct Mn) is one of the oldest and the most widely used of the wrought aluminum alloys. In spite of this fact, there are some aspects of the metallography of 3s which have not been revealed or which have not been brought to the attention of the metallurgist working with the alloy. The purpose of this investigation was to demonstrate in general how some of the fundamentals of equilibrium phase diagrams may be applied to the study of an alloy and to show specifically the origin of certain metal-lographic features of aluminum alloy 3s. It is hoped that this information can serve as a basis for solving specific problems relating microstructure to such things as mechanical properties, recrystallization, grain growth, and surface finish. Literature Survey Considering that alloy 3s contains only one alloying addition, manganese, it seems reasonable that it would have characteristics pertaining to the A1-Mn system. However, those characteristics might well be altered by the impurities in the commercial alloy, especially iron and silicon. Therefore, not only the simple binary but also more complex systems had to be reviewed. One characteristic of the A1-Mn system worthy of mention is its sluggishness, which leads to conflicting solubility data1,&apos;2 and makes it relatively easy to supersaturate the solid solution and shift the eutectic composition during rapid solidification.3&apos;4 Another characteristic is the strong influence which small amounts of impurities, especially iron, exert in lowering the solid solubility of manganese. Undissolved manganese is ordinarily present in an intermetallic phase, MnAl,, having an orthorhombic crystal structure. A metastable precipitating phase designated as "G" has been reported but small amounts of iron and silicon suppress this phase entirely." Raynor has established that MnA1, can dissolve a considerable amount of iron by a substitution of iron for manganese atoms up to 50 atomic pct.&apos;" Consequently, in the Al-Mn-Fe liquidus diagram, the eutectic valley separating the primary aluminum and (Mn,Fe)Al, fields is fairly close to a constant Mn + Fe content." This is an important consideration in regulating the composition of 3s and also other aluminum alloys with high manganese additions."

Jan 1, 1956

By David B. Burrows, Rlkl Kobayashi, Norman L. Carr

The viscosity of hydrocarbon mixtures, whether in the gas or liquid phase, is a function of pressure, temperature, and phase composition. This paper presents methods for the prediction of the viscosity of the gas or less dense fluid phase over the practical range of pressure, temperature, and phase compositions encountered in surface and subsurface petroleum production operations. The correlation necessary to predict the effect of pressure on viscosities is presented in Part I. Serious discrepancies in high pressure gas viscosity data in the literature are discussed. The application of the correlation to predict absolute viscosities is discussed in Part 11. Auxiliary correlations are presented to enable calculations of viscosities from a knowledge of the pressure, temperature, and gravity of the gas phase. INTRODUCTION A knowledge of the viscosity of hydrocarbon fluids is needed to study the dynamical or flow behavior of these mixtures through pipes, porous media, or more generally wherever transport of momentum occurs in fluid motion. Since flow is predominantly in the laminar region in petroleum reservoirs, the influence of fluid viscosity on this flow is especially important. As early as 1894, Onnes1 and Onnes and de Haas&apos; noted that the viscosities of homologs under corresponding states could be correlated. The theorem of corresponding states has been further developed and applied to the viscosity of pure, nonpolar gases under pressure by Comings, Mayland, and Egly.3 It was demonstrated that the viscosity ratio could be expressed rather closely as a function of reduced pressures and temperatures, 1.e.: µ/µ1 = f( TR2 PR) ........(1) temperature, absolute units where: TR =------------------------------ ------ critical temperature. absolute units _pressure, absolute units critical pressure, absolute units µ = viscosity of gas at reduced temperature TR and reduced pressure PR µ1 =. viscosity of gas at atmospheric pressure and at temperature TR Serious discrepancies in the viscosity of pure hydrocarbon gases at high pressures have been called to Our attention by Comings, and and Egly. They made a careful analysis of the following methods commonly used to measure gas viscosities: 1. Oscillating disc viscometer4,5 2. Rolling ball viscometer6,7 3. Capillary tube viscometer12 On the basis of their analysis of the problem and their experimental data on the viscosities of methane, ethylene, carbon dioxide, and propane, they preferentially selected data obtained by the capillary tube viscometer to develop their viscosity correlation. Since then a need has existed to verify the experimental technique of Comings, Mayland, and Egly for the determination of viscosities at high pressure; to extend the data to mixtures of hydrocarbons; and to extend the range of their correlation to include higher pressures. Using the correlation procedure of Comings, May-land, and Egly, the prediction of gas viscosities is resolved into the correlation of the effect of pressure, temperature, and composition on the viscosity of hydrocarbons and their mixtures and the prediction of viscosities of mixtures of hydrocarbons and other natural gas components at one atmosphere pressure.

Jan 1, 1955

By W. D. Potter, E. T. Peters

Single-crystal films of boron have been prepared by thermal reduction of purified BCl3 with subsequent deposition of boron onto oriented silicon substrates. The structural properties of films prepared under various experimental conditions have been determined by light microscopy and "grazing-" angle electron-diffraction analysis. An orientation relationship is proposed for silicon and a-rhombo-heclral boron which can be described as: (111)Si (112)B; [110]Si [110]B ElEMENTAL boron is known to have a high energy gap* and consequently has potential value as a high- *Energy gaps of 1.35 to 1.55 ev1-3 and 2.0 ev4 are reported for ß-rhombohedra1 and a-rhombohedra1 boron, respectively. temperature semiconductor.5 Exploitation of this property, however, has been hampered by the unavailability of pure, single-crystal boron. Two recent symposia6,7 have treated the subjects of purification, crystallization, crystal structure, and properties of boron and provide a foundation for further investigation in these areas. The structure, lattice constants, and observed ranges of stability for four reported polymorphs of boron8°12 are listed in Table I. The rhombohedral structures are generally accepted as true polymorphs whereas the tetragonal structures are believed to be transient. Most currently available single crystals of boron are grown by Czochralski and floating-zone methods. Unfortunately, these crystals generally contain numerous defects and are highly strained as a result of the polymorphic transformations and thermal contractions which accompany cooling. Recently, Armington, Potter, and Tanner13 have reported the formation of single-crystal films of boron on silicon single-crystal substrates through thermal reduction of BC13 by hydrogen. Boron E. T. PETERS, Junior Member AIME, is Senior Scientist, ManLabs, Inc., Cambridge, Mass., and W. D. POTTER is Research Chemist, Air Force Cambridge Research Loboratories, L. G. Hanscom Field, Bedford, Mass. formed at temperatures near 1000°C was identified as the a-rhombohedra1 form, consistent with expectation. The present paper describes a continuation of this work with specific reference to characterization of the structural features of the deposited boron films. The ultimate goal of this program is to produce large-area single-crystal films of a-rhombohedra1 boron to be used for electrical and optical studies by other workers. PREPARATION OF BORON FILMS The experimental procedure of preparing thin films is similar to that described by Theuerer14 for the epitaxial growth of silicon by thermal reduction of SiC14 and has already been described as applied to the preparation of boron thin films.13 Briefly, a mixture of BCl3 vapor and dry hydrogen is passed over a heated silicon substrate. Thermal reduction of the BC13 allows deposition of boron on the substrate. The substrates were {111}-oriented, single-crystal silicon. Square specimens 0.63 cm on an edge by 0.1 to 3.0 mm thickness were prepared by

Jan 1, 1965

By R. G. Vardiman, M. R. Achter

THERE has been interest recently in the conditions under which dislocation pipe diffusion may be observed. In order to extend the measurements to temperatures below Tm/2, where pipe diffusion becomes more important, a chemical sectioning technique was developed for silver single crystals which makes possible the removal of layers of 100A or less. The procedure is briefly as follows. Silver single crystals of 99.995 pct purity were cut in the form of discs t by 4 in., electropolished, and electropolated with Ag110 to about 1000A thickness. The thickness was determined by calibrating the activity with the weight of heavier platings, up to 10,000A. Both diffused and undiffused samples were sectioned in a two-step process. Reaction with a solution of iodine in alcohol formed a thin, even layer of AgI, which was then dissolved in a KCN solution. The reaction rate of the iodine solution varied slightly over a period of time, so that the thickness of the stripped layers, while quite even and regular for a given specimen, ranged from 65 to l00W for different specimens. This variation was checked by using a thickly plated standard with each run. Layer thickness was determined from undiffused samples by the point where the layer activity drops to half the maximum. This maximum intensity also provides, with appropriate corrections, the initial concentration per layer co. Because of the small penetration distances, it is necessary to use the exact solution of Fick&apos;s law for a source of finite thickness.&apos; For a plating of thick- where c is the concentration at depth x. flj the error function, D the apparent diffusion coefficient, and t the time. The diffusion coefficient was obtained from the concentration-penetration data by extrapolating to x = 0 where c/co = erf h/2(Dt)1/2 Enough points were taken to impart confidence in the accuracy of the intersection, generally about ten layers. Four temperatures were used as in Table I. For best accuracy, t and h were chosen to give values of the parameter (Dt)1/2/h between 1.0 and 1.7. A typical concentration-penetration curve is shown in Fig. 1. The diffusion coefficients calculated from Eq. [I] are plotted in Fig. 2. For comparison, the high-temperature data of Tomizuka and sonder 2 which go down to 630°C are plotted as the solid line 2(a) from their expression D = 0.40 exp (-44,090/RT). Also for comparison, the lowest temperature point of Hoffman and Tumbull3 is plotted. It is apparent that our data diverge appreciably from the high-temperature extrapolation by 373°C. A better straight line fit for the low-temperature portion is obtained by subtracting the extrapolated volume diffusion coefficient from the apparent. or measured coefficient, and plotting the difference, curve (h) of

Jan 1, 1970

By W. A. Bruce

This paper presents the essentials of a mathematical method of studying the pressure behavior of an oil reservoir as the fluids are withdrawn. Methods are shown Whereby the behavior of a reservoir can be used to predict the future relationship between withdrawals and pressure. The oil reservoir is considered as a small part of a large porous continuum, which contains for the most part water. The expansion of this water resulting from a decrease of pressure in the oil zone causes a movement of water that is an important factor in the relationship between fluid withdrawals and reservoir pressure. Examples are given to illustrate the methods of pressure prediction for a circular reservoir containing undersaturated crude, the pressure distribution over a field that has a uniform production rate, the effect of a fault line near a field, the mutual interference of near-by fields, and the perturbing influence of a gas cap. Applications of the analysis to well-spacing problems are shown. Introduction The pressure-prediction methods to be described here are based upon the conception of an oil pool as a small part of a large porous continuum, containing for the most part water. The formation containing this water may be thought of as extending over an area of many square miles and having one or more small bodies of oil or gas trapped in high spots or reservoirs. It will be treated as having the genera1 aspect of a thin, flat sheet with an over-all tilt to the horizontal and with numerous small high spots, tight zones, and irregularities This porous continuum will be treated as being much more extensive than the oil or gas zones, but will be recognized as terminating at such large boundaries as a general fault, outcrop, unconformity, or pinch-out. Throughout the greater part of this limited porous continuum it is likely that there is a hydraulic connection. If this is true, the removal of fluid in one place will cause a disturbance that eventually will travel to all parts of the continuum. This picture has led to the recognition of water as the major fluid in the porous continuum and in many cases the expansive nature of this water as the main driving force producing the oil. The next step is the solution of the general problem of compressible liquid behavior in porous media. The works of Hurst I and Muskat2 introduced the idea of using heat-flow mathematics to consider the problem of compressible liquid flow in a porous medium. Before their reports, it had been thought sufficient to use the incompressible fluid-flow work of S1ichter.3 Law Muskat4 pointed out in detail how far the incompressible-fluirl assumption, deviated from fact even for water, of which the compressibility is about 3 X 10-6 volumes per unit volume per pound per square inch. He showed that this deviation increased with increases of distance. For example, the incompressible-fluid formula might show good agreement with the

Jan 1, 1943