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By Jose A. Ruiz

INTRODUCTION For heterogeneous non-catalytic solid-gas reactions carried out in fluidized bed reactors, nominal bed temperature is an average value between gas and solid. For highly exothermic reactions, actual particle temperature can be up to hundred degrees above termocouple temperature, since heat dissipate at slower rate than heat generation during some steps of transformation. These micro instabilities at particle level can displace thermodynamic equilibrium from the desired phase to others. This effect is important when relatively narrow range of phase stability exists, like in sulphation roasting of sulphides, where bed discharge contains, in addition to the desired sulphate others metastable phases such as basic sulphate and ferrite. For example, for copper-iron sulphide concentration roasted below 680°C, no cupric ferrite is formed, as shown by Jakob et al., therefore the separate Kellogg's stability phase diagrams Cu-S-O represent the roasting (Fig.l). At temperature above this one, like 760°C for example, phase stability changes from CuSO4 to the basic sulphate Cu0•CuSO4. Solid state reaction between Cu0•CuSO4 and Fe203 also occurs to form cupric ferrite, Cu0•Fe2O3, therefore the Cu-Fe-S-O Kellogg's phase diagram of Fig. 1 (continuous line) represents this condition of roasting. Although both Cu0•CuSO4 and Cu0•Fe2O3 are metastable phases under normal operating conditions of sulphation roasting(1-10% SO2, 1-10% 02 and 680°C, points A and B,Fig. 1) sulphation of these species and particularly ferrite are slow and limited due to diffusional control. This explain why reactors discharge contains several phases: CuSO4, Cu0•CuSO4, CuO•Fe203 plus small amounts of CuS and FeS due to the baclonixed conditions of fluidized bed reactors. The presence of cuprous ferrite due to reducing conditions inside individual particles also occurs, but in very limited extent at the reaction interface, as it is demonstrated by the low soluble iron levels of calcines. On the other hand, the presence of cupric ferrites can be explained only due to the higher temperature achieved by particles, since below 680°C cupric ferrite formation does not take place. [ ] This phenomena also occurs for others non-ferrous metal sulphides concentrates roasted under sulphation conditions, such as 7n, Co and Ni. Therefore the prediction of discharge composition of fluidized beds is not possible based only on kinetics and mechanistics models alone or purely thermodynamical considerations, since all factors should be integrated to describe the overall phenomena. SINGLE PARTICLE TRANSFORMATION Assuming a first order reaction with respect to the gas and zero for solid, such as

Jan 1, 1984

By Warren E. Wilson

The transportation of solids in pipe lines is a matter of deep concern in many fields of engineering. Much experimental and theoretical work has been done in an effort to devise means of designing pipe lines that will satisfactorily transport given solid loads, but there remain many unanswered questions in this field. The present discussion will be confined to a rather narrow portion of this field and will endeavor to point out certain factors that may well be considered when comparing the relative economy of various installations. The data have been presented previously but a new interpretation was prompted by a suggestion in a paper by Professor O'Brien,' of the University of California, that the friction work per pound of dry material should be considered in determining the relative efficiency of various installations. This method of considering relative economy in various pipe lines leads to some rather unexpected conclusions, especially with reference to the economy of large pipe sizes. A previous suggestion by the writer concerning the economy of a rather peculiar type of installation is strengthened. It is not believed that the considerations set forth herein apply directly in the case of dredge lines, where economy is largely a matter of a high rate of pumping in order to reduce the unit overhead charge. However, it is believed that some value may be gained from these considerations in cases involving the disposal of a fixed amount of solids per unit time with a minimum expenditure of energy and at a low cost for replacement of worn pipes. Such situations are not uncommon in the disposal of mill tailings and the disposal of solids deposited from irrigation waters. It was found that data leading to general conclusions for various pipe sizes were not available but certain definite trends are indicated and methods of analyzing available data are presented in the hope that they may be of assistance in preparing engineering estimates on designs of pipe lines of the type described above. Energy Requirements Carrying out the idea contained in Professor O'Brien's paper concerning the method of computing energy required to transport solids, the following analysis leads to some rather interesting conclusions. Let us represent: Solids load in terms of mass per unit time by w Ratio of mass of suspended solids to total mass of mixture flowing by p Volume rate of flow of mixture by Q Length of pipe by L Slope of energy grade line by s Mass per unit volume of solids by m8. Mass per unit volume of liquid by mi Mass per unit volume of mixture by 11 We then have as an expression for the solids load: w = pqmm The work done per unit mass, p, on the mixture to move it along the pipe the

Jan 1, 1947

By Warren E. Wilson

The transportation of solids in pipe lines is a matter of deep concern in many fields of engineering. Much experimental and theoretical work has been done in an effort to devise means of designing pipe lines that will satisfactorily transport given solid loads, but there remain many unanswered questions in this field. The present discussion will be confined to a rather narrow portion of this field and will endeavor to point out certain factors that may well be considered when comparing the relative economy of various installations. The data have been presented previously but a new interpretation was prompted by a suggestion in a paper by Professor O'Brien,' of the University of California, that the friction work per pound of dry material should be considered in determining the relative efficiency of various installations. This method of considering relative economy in various pipe lines leads to some rather unexpected conclusions, especially with reference to the economy of large pipe sizes. A previous suggestion by the writer concerning the economy of a rather peculiar type of installation is strengthened. It is not believed that the considerations set forth herein apply directly in the case of dredge lines, where economy is largely a matter of a high rate of pumping in order to reduce the unit overhead charge. However, it is believed that some value may be gained from these considerations in cases involving the disposal of a fixed amount of solids per unit time with a minimum expenditure of energy and at a low cost for replacement of worn pipes. Such situations are not uncommon in the disposal of mill tailings and the disposal of solids deposited from irrigation waters. It was found that data leading to general conclusions for various pipe sizes were not available but certain definite trends are indicated and methods of analyzing available data are presented in the hope that they may be of assistance in preparing engineering estimates on designs of pipe lines of the type described above. Energy Requirements Carrying out the idea contained in Professor O'Brien's paper concerning the method of computing energy required to transport solids, the following analysis leads to some rather interesting conclusions. Let us represent: Solids load in terms of mass per unit time by w Ratio of mass of suspended solids to total mass of mixture flowing by p Volume rate of flow of mixture by Q Length of pipe by L Slope of energy grade line by s Mass per unit volume of solids by m8. Mass per unit volume of liquid by mi Mass per unit volume of mixture by 11 We then have as an expression for the solids load: w = pqmm The work done per unit mass, p, on the mixture to move it along the pipe the

Jan 1, 1947

By Tracy C. Jarrett

In 14-karat gold alloys, as in 10-karat gold alloys,3 the addition of such metals as zinc, nickel, copper and silver produces a wide range of physical and chemical properties such as color, hardness, corrosion resistance and melting points. These important factors made gold alloys desirable in the optical work and for jewelry. In 14-karat gold alloys, as well as in 10-karat or 12-karat, it is possible to have two golds of the same color, one of which will corrode more than the other, although it may be harder. Some of these alloys have been investigated by F. E. Carter,' E. M. Wise,= and L. Sterner Rainer.4 In this group of alloys the gold content of 58.3 per cent (14-karat) was held constant, while the copper varied from 36 to 24 per cent. The balance of the alloy consisted of one, two, or three of the metals silver, zinc, and nickel. All the alloys were melted in an induction furnace and cast into an ingot that measured 3 by 1/4 by 3/4 in. The method of determining the melting points, color determinations and acid test have been discussed in previous papers by the author.2, 3 It is necessary to use small test bars (Fig. I). The tensile bars were annealed at 1300oF. for 20 min. and then air-cooled. There being a very marked drop when the yield point was reached, "the drop of the beam" method was used in determining the yield point. Alloys Gold-copper.zilzc A~loys.—Gold-copper-zinc alloys melt, cast, and labricate easily. The low melting points, however, limit their use to some extent. The physical properties of these alloys are not entirely satisfactory. When the ultimate strength is satisfactory, the elongation and reduction of area are too low (Table I). Gold-copper-sinr-nickel A lloys.—In this group of alloys, in which zinc and nickel replace copper in approximately equal parts (Table I), the yield point, hardness, and ultimate strength increase with the increase of zinc and nickel content, while the reduction of area and elongation decrease. The physical properties are desirable, particularly of the white gold alloys. The alloys of this group are not difficult to cast and fabricate, and most of these colors could be used commercially. Gold-copper-nickel A lloys.—Gold-copper-nickel alloys are similar to the gold-copper-zinc and the gold-copper-zinc-nickel alloys. They do, however, possess high yield point, ultimate strength and hardness, somewhat higher than those of the other two groups mentioned (Table I). The difficulty with these alloys is that they fire-crack readily and heavy rolling is necessary between annealings. Being hard to fabricate, many

Jan 1, 1941

By Tracy C. Jarrett

In 14-karat gold alloys, as in 10-karat gold alloys,3 the addition of such metals as zinc, nickel, copper and silver produces a wide range of physical and chemical properties such as color, hardness, corrosion resistance and melting points. These important factors made gold alloys desirable in the optical work and for jewelry. In 14-karat gold alloys, as well as in 10-karat or 12-karat, it is possible to have two golds of the same color, one of which will corrode more than the other, although it may be harder. Some of these alloys have been investigated by F. E. Carter,' E. M. Wise,= and L. Sterner Rainer.4 In this group of alloys the gold content of 58.3 per cent (14-karat) was held constant, while the copper varied from 36 to 24 per cent. The balance of the alloy consisted of one, two, or three of the metals silver, zinc, and nickel. All the alloys were melted in an induction furnace and cast into an ingot that measured 3 by 1/4 by 3/4 in. The method of determining the melting points, color determinations and acid test have been discussed in previous papers by the author.2, 3 It is necessary to use small test bars (Fig. I). The tensile bars were annealed at 1300oF. for 20 min. and then air-cooled. There being a very marked drop when the yield point was reached, "the drop of the beam" method was used in determining the yield point. Alloys Gold-copper.zilzc A~loys.—Gold-copper-zinc alloys melt, cast, and labricate easily. The low melting points, however, limit their use to some extent. The physical properties of these alloys are not entirely satisfactory. When the ultimate strength is satisfactory, the elongation and reduction of area are too low (Table I). Gold-copper-sinr-nickel A lloys.—In this group of alloys, in which zinc and nickel replace copper in approximately equal parts (Table I), the yield point, hardness, and ultimate strength increase with the increase of zinc and nickel content, while the reduction of area and elongation decrease. The physical properties are desirable, particularly of the white gold alloys. The alloys of this group are not difficult to cast and fabricate, and most of these colors could be used commercially. Gold-copper-nickel A lloys.—Gold-copper-nickel alloys are similar to the gold-copper-zinc and the gold-copper-zinc-nickel alloys. They do, however, possess high yield point, ultimate strength and hardness, somewhat higher than those of the other two groups mentioned (Table I). The difficulty with these alloys is that they fire-crack readily and heavy rolling is necessary between annealings. Being hard to fabricate, many

Jan 1, 1941

By Warren E. Wilson

The transportation of solids in pipe lines is a matter of deep concern in many fields of engineering. Much experimental and theoretical work has been done in an effort to devise means of designing pipe lines that will satisfactorily transport given solid loads, but there remain many unanswered questions in this field. The present discussion will be confined to a rather narrow portion of this field and will endeavor to point out certain factors that may well be considered when comparing the relative economy of various installations. The data have been presented previously but a new interpretation was prompted by a suggestion in a paper by Professor O'Brien,1 of the University of California, that the friction work per pound of dry material should be considered in determining the relative efficiency of various installations. This method of considering relative economy in various pipe lines leads to some rather unexpected conclusions, especially with reference to the economy of large pipe sizes. A previous suggestion by the writer3 concerning the economy of a rather peculiar type of installation is strengthened. It is not believed that the considerations set forth herein apply directly in the case of dredge lines, where economy is largely a matter of a high rate of pumping in order to reduce the unit overhead charge. However, it is believed that some value may be gained from these considerations in cases involving the disposal of a fixed amount of solids per unit time with a minimum expenditure of energy and at a low cost for replacement of worn pipes. Such situations are not uncommon in the disposal of mill tailings and the disposal of solids deposited from irrigation waters. It was found that data leading to general conclusions for various pipe sizes were not available but certain definite trends are indicated and methods of analyzing available data are presented in the hope that they may be of assistance in preparing engineering estimates on designs of pipe lines of the type described above. Energy Requirements Carrying out the idea contained in ' Professor O'Brien's paper concerning the method of computing energy required to transport solids, the following analysis leads to some rather interesting conclusions. Let us represent: Solids load in term of mass per unit time by W Ratio of mass of suspended solids to total mass of mixture flowing by p Volume rate of flow of mixture by Q Length of pipe by L slope of energy grade line by s Mass per unit volume of solids by m. Mass Per unit volume of liquid by mi Mass per unit volume of mixture by mm We then have as an expression for the solids load: W = pQmm The work done per unit mass, P, on the mixture to move it along the pipe the

Jan 1, 1948

By P. Chiotti, G. R. Kilp

IN the study of zinc-zirconium1 and zinc-uranium2 systems, vapor-pressure measurements were made in order to establish the equilibrium phase diagrams for a pressure of 1 atm. In each of these systems, only zinc has an appreciable vapor pressure over the temperature range investigated. The zinc pressure was measured over a sufficiently wide temperature and composition range to permit calculation of the standard free energy, enthalpy, and entropy of formation for the compounds ZrZn, ZrZn2, ZrZn3, ZrZn6, ZrZn14 , and U2Zn17. In these calculations the compounds were treated as line compounds. Although the exact composition range was not determined, metallographic and thermal data indicate that the solubility range for these compounds is small. It is to be noted that the compound initially reported to correspond to the formula UZn9, 2 has been shown by the crystal structure work of Makarov and vinogradov3 to correspond to the formula U2Zn17,. The crystal structure is similar to that for the compounds Th2M17, investigated by Florio,4 et al; here M represents iron, cobalt, or nickel. Therefore, thermodynamic calculations are based on the formpla U2Zn17 EXPERIMENTAL The dew-point method employed to measure the vapor pressure of zinc over uranium-zinc alloys has been described previously.2 The same procedure and apparatus were used in measuring the zinc pressure over zinc-zirconium alloys. In the case of alloys in the two-phase region consisting of a zirconium and the compound ZrZn, the Knudsen effusion method was employed to obtain a few values in the temperature range 600" to 560°C. In most cases, tantalum crucibles were used to contain the zirconium alloys. THERMODYNAMIC PROPERTIES OFU2Zn17 A least-squares treatment of the vapor-pressure data obtained for 35 and 65 wt pct U alloys in the temperature range 650° to 940°C gave lOg10PAtm = 7,713/T + 6.33 Here, as in following equations, T represents degrees kelvin and P represents the zinc vapor pressure in atmospheres. The probable errors for the two constants were calculated to be 60.68 and 0.0563, respectively. This relation represents the equilibrium dissociation pressure for the reaction U2Zn17 (s) - 2U(s) + 17Zn(v) The solubility of zinc in solid uranium is negligible and the only additional information required to calculate the free energy of formation of U2Zn17 is the free energy of vaporization of pure zinc. K. K. Kelley5 gives the relations, AF°= 30,902 + 6.03Tlog T + 0.275 X 10-3T2 - 45.03T

Jan 1, 1961

By Warren E. Wilson

The transportation of solids in pipe lines is a matter of deep concern in many fields of engineering. Much experimental and theoretical work has been done in an effort to devise means of designing pipe lines that will satisfactorily transport given solid loads, but there remain many unanswered questions in this field. The present discussion will be confined to a rather narrow portion of this field and will endeavor to point out certain factors that may well be considered when comparing the relative economy of various installations. The data have been presented previously but a new interpretation was prompted by a suggestion in a paper by Professor O'Brien,1 of the University of California, that the friction work per pound of dry material should be considered in determining the relative efficiency of various installations. This method of considering relative economy in various pipe lines leads to some rather unexpected conclusions, especially with reference to the economy of large pipe sizes. A previous suggestion by the writer3 concerning the economy of a rather peculiar type of installation is strengthened. It is not believed that the considerations set forth herein apply directly in the case of dredge lines, where economy is largely a matter of a high rate of pumping in order to reduce the unit overhead charge. However, it is believed that some value may be gained from these considerations in cases involving the disposal of a fixed amount of solids per unit time with a minimum expenditure of energy and at a low cost for replacement of worn pipes. Such situations are not uncommon in the disposal of mill tailings and the disposal of solids deposited from irrigation waters. It was found that data leading to general conclusions for various pipe sizes were not available but certain definite trends are indicated and methods of analyzing available data are presented in the hope that they may be of assistance in preparing engineering estimates on designs of pipe lines of the type described above. Energy Requirements Carrying out the idea contained in ' Professor O'Brien's paper concerning the method of computing energy required to transport solids, the following analysis leads to some rather interesting conclusions. Let us represent: Solids load in term of mass per unit time by W Ratio of mass of suspended solids to total mass of mixture flowing by p Volume rate of flow of mixture by Q Length of pipe by L slope of energy grade line by s Mass per unit volume of solids by m. Mass Per unit volume of liquid by mi Mass per unit volume of mixture by mm We then have as an expression for the solids load: W = pQmm The work done per unit mass, P, on the mixture to move it along the pipe the

Jan 1, 1948

By J. Weertman

The paper of Gifkins and Snowden considers the interesting but difficult problem of determining the stress dependence of secondary (steady-state) creep at low stresses. These authors have concluded that at stresses below 250 psi (2 x 107 dynes per sq cm) the secondary creep rate of lead is proportional to the stress (viscous creep) and is not proportional to the stress raised to about a fifth power. The experimental data considered by them were obtained on tests conducted at room temperature and at 50°C. The lowest stress employed was 50 psi (3.5 X 106 dynes per sq cm). The authors pointed out the main difficulty in determining the stress dependence of creep at low stresses. The creep tests must be run for very long lengths of time. However they made no estimates of when an experimental creep rate determination must be rejected because it does not represent a true steady-state or minimum creep rate. In order to be certain that a creep curve is within the steady-state region, the total creep strain should be of the order of 0.1 to 0.2. For a creep test of a year's duration this requirement implies that a secondary creep rate smaller than about 10-3 per hr cannot be measured reliably. The corresponding creep rate for a 10-year test is 10-6 per hr. The creep rates of the tests that were considered by the authors to prove the existence of viscous creep were of the order of or less than 10-6 per hr. One can conclude reasonably that this data does not prove unambiguously that large strain steady-state creep rate of lead is proportional to the stress in the stress range of 50 to 250 psi (3.5 x 106 to 2 X 107 dynes per sq cm). Another technique can be used to obtain the stress dependence at low stress levels. The creep rate is a very sensitive function of temperature. The creep rate can be increased by very large amounts merely by increasing the temperature. We carried out steady-state creep tests on lead single crystals25 at temperatures up to 320°C. We were able to obtain creep rate data down to stresses as low as 35 psi (2.5 x 10' dynes per sq cm). Our smallest creep rate was 8 x 10-5 per hr. Thus we obtained large strain, steady-state creep rates to even lower stresses than were considered by Gifkins and Snowden. No evidence was seen for viscous creep. The creep rate was proportional to the stress raised to about a 4.5 power down to the lowest stresses. Since there is no reason to believe that changing the temperature should change the stress dependence of steady-state creep, we feel that large strain viscous creep does not occur in the stress range quoted by the authors for lead single crystals or large-grain polycrystalline samples of lead. This conclusion does not imply that viscous creep may nat occur in a lower stress range or in the same stress range for fine grain material or at creep strains very much smaller than 0.1. Support by the U.S. Office of Naval Research is acknowledged. Authors' Reply R. C. Gifkins and K. U. Snowden We thank Dr. Weertman for his discussion and although, as we hope to show, we do not agree with his reservations, we do concur in stressing the importance of ensuring that creep rates are reliably obtained. Dr. Weertman appears to be content to accept n = 1 for low stresses with fine-grained material but not for single crystals. We believe our results show that the former result cannot be accepted without also accepting the latter. We will also show that the probable errors in our minimum creep rates are insufficient to alter our conclusions, that the criterion proposed by Dr. Weertman is arbitrarily restrictive and his alternative experimental approach possibly invalid. 1) A principal result of our Fig. 1(a) is that n = 1 for polycrystalline specimens at room temperature and 50°C for stresses below -250 psi. There was evidence that crystal slip and grain boundary sliding contributed approximately equaily to the overall strain in this low-stress regime. This implies that either a) grain boundary sliding controls slip within the grains or b) both grain boundary sliding and crystal slip independently occur according to mechanisms which give n = 1. Alternative a does not seem acceptable, so we were forced to consider b. This led us to reexamine work on bicrystals by Strutt and Gifkins and plot curves Fig. l(b). Previously Strutt et al. (loc. cit.), had merged these points with others using the Zener-Holloman parameter and thus, we now believe, had been led to overlook the behavior where n = 1. Curves C and D in Fig. l(b) did appear to confirm the hypotheses that n = 1 for crystal slip at these low stresses and the sliding curve F was similarly of the expected form. It was comparatively easy to find a quantitative theory to account for n = 1 for sliding and the similarity of curves C and D to curve F (all obtained from the same set of specimens) led us to feel that the single-crystal curves were valid. 2) We believe the secondary creep rates for both the polycrystalline and single-crystal specimens to be in error by factors c2. In Fig. 6 creep curves for polycrystalline specimens of lead(1) and lead(II) are reproduced as curves a and b, respectively, and curve c is for a single crystal at 100 psi. It is clear that, although the attainment of secondary creep rate takes 2 years for a and 150 days for b, thereafter the curve is linear for periods of 7 and -1 year, respectively. The single crystal has a linear portion commencing after 20 and extending to 90 days. Creep extension was measured directly using a traveling microscope reading to 0.01 mm on gage lengths marked on the specimens; the gage lengths

Jan 1, 1968

By H. H. Klepfer, M. E. Snyder

UNTIL very recently, the commercial availability of the rare earths as metals has been very limited. Fabrication of mill products from these metals has not been studied in most cases. This note reports the results of the development of fabrication techniques for thulium. Thulium has a melting point of about 1550°C and a hexagonal close-packed crystal structure. It oxidizes in air to give a black oxide (TmzO,). The procedures for producing thin thulium foil were developed on one ingot weighing about 220 g and were subsequently applied in processing about a pound of metal to foil. Several alternates for the various fabrication steps were investigated and will be discussed. The metal fabricated was in the form of commercial chill-cast ingots 1 in. in diam and 2 in. long weighing approximately 220 g. Impurities in the ingots were reported by the vendor to be 4000 ppni tantalum, 2000 ppm calcium, 200 ppm nickel, 100 to 200 ppm iron, 100 ppm europium, and less than 100 ppm copper, lutetium, and ytterbium. In addition to these impurities, several salt-like inclusions as large as l/8 in. in diam were revealed along the center line of the one ingot sectioned. Preliminary tests indicated that small wafers cut from the as-cast ingot would not fabricate readily by rolling. Forging of copper-jacketed wafers was therefore attempted. At 1550"F forging was satisfactory but an apparent reaction of copper with thulium demanded investigation of lower temperatures. Therefore, the remainder of the test ingot was forged at 1450°F—with only minor cracking. All ingots forged were inserted into copper tubes of 1 in. 1D and 0.125-in. wall thickness. The jackets were sealed by flattening the ends of the tubes and welding under helium. Heating time at 1450°F was 30 min. Press forgings of 1/8 in. per pass were used, followed by 10 min reheats. When the ingots had been squared and reduced to 0.250 in. in thickness, the original copper jacket was stripped off and replaced by a new jacket in preparation for hot rolling. Hot rolling at 1450" F without edge cracking was readily accomplished after forging. Excellent results were obtained with 10 pct reductions of thickness followed by 5 to 10 min reheats. After reduction of thickness from 0.250 to 0.100 in. the copper jacket was removed. It was found, in fact, that hot rolling in air was possible. A tenacious black oxide similar to that seen on zirconium was formed during 3 min reheats at 1450°F. Reduction in air to 0.010 in. foil was possible taking 10 pct reductions per pass. The oxide coat formed during hot rolling in air could best be removed by sand blasting and pickling. Common pickling solutions containing polar solvents were found to attack the metal too rapidly and a concentrated nitric-hydrofluoric acid mixture attacked neither the oxide nor the metal. The most satisfactory pickling solution was 52 vol pct concentrated nitric acid-48 vol pct glacial acetic acid. After forging to 0.250 in., vacuum annealing and cold rolling was found to be another satisfactory alternate to hot rolling in copper jackets. After forging. a hardness of Rockwell B76 was found. Annealing in vacuum (2 X l0-5 mm of Hg) for 1 hr at 1200"F did not alter this value. Annealing at 1470"F for 1 hr brought the hardness down to R;]63. With cold rolling (5 pct per pass) the hardness returned to about R,1:76 after 20 pct reduction and edge cracking became noticeable. However, cold rolling to a total of 40 pct reduction in thickness (RI,,83) was possible before edge crack propagation became serious. Good surface finish was obtained, and the metal loss due to oxidation was minimized by cold rolling and vacuum annealing. Using this procedure the yield of 1.25 in. wide by 0.010 in. thick foil from a 1-in. diam ingot was about 40 pct.

Jan 1, 1961

By J. J. Gilman

THEORIES of fracture in metals have been based primarily on the dependence of fracture strength on grain size. This dependence was first observed by Masing and Polanyi.l These workers, as well as 0rowan12 and Davidenkov and Wittman,' thought the grain size could be equated with the crack size in the Griffith condition for crack propagation.4 In this way they could account for the observed proportionality between fracture stress and the reciprocal square root of the grain size. The chief results of recent investigations of the fracture strength of polycrystals are summarized in Fig. 1. Low for iron,5 Petch for iron,' Greenwood and Quarrel for zinc, Petch and Zein for zinc,' and Hauser, Landon, and Dorn for magnesium'' have all found that the fracture stress of a polycrystal is proportional to the reciprocal square root of the grain size. Also, they find that, for large grain sizes, the fracture stress lies near the extrapolation of the yield-stress curve determined at small grain sizes; where measurable plastic strain precedes fracture. Low9 has gone a step further and shown that, in Range 1, the fracture stress in tension is almost identical to the yield stress in compression for a given grain size. Homes and Gouzou, 10 and Low also have shown that, in Range 2 of Fig. 1, microcracks form when the yield stress is reached, but they do not cause failure until the stress reaches a much higher value. The fact that yielding always precedes fracture suggests that fracture is induced by plastic flow. A mechanism by which this might occur was first proposed by Zener.11 He pointed out that blocked dislocations would cause stress concentrations which might cause fracture. The blocking would be caused by grain boundaries. This idea has been developed by Eshelby, Frank, and Nabarro,12 by Koehler,13 and by Stroh.14 By means of etchpits blocked dislocations have been observed in brass by Jacquet,15 in zinc by Gilman,16 and in lithium fluoride by Gilman and johnston. The blocked-dislocation theory and the experiments that bear on it have been summarized by Mott.18 One of the strong points of the blocked-dislocation theory is that it can explain the grain-size dependence of the fracture stress in a natural way. However, Low9 has pointed out that the theory is not satisfying when it is considered quantitatively. Gilman10 also has criticized the theory and presented an alternative interpretation of the relation between fracture stress and grain size. Since the blocked-dislocation theory is not the only theory that can explain in the grain-size effect, it is necessary to find other evidence either to support or deny it. In this investigation the following points were studied: 1) If blocked dislocations normally cause fracture, then the fracture stress ought to be very high in the absence of plastic glide. Is it? 2) If dislocations must be blocked in order for metals to fracture, then certain types of grain

Jan 1, 1959

By E. Brunner, G. L. Hassler, T. J. Deahl

The capillary effects in reservoir rock are discussed in terms of the pressures they cause in sandstones and dolomites. Data for the two-phase case (oil-gas or water-gas) and for the three-phase case (oil, water and gas in rock) are used to demonstrate that in one sense the wetting preference of a rock depends on its saturation. The nature of capillary hysteresis is described for partially stable conditions, and the concept is enlarged. Reproducibly measurable pressures include the "capillary pressure," which is the pressure difference between any two phases that are each interconnected; the "threshold pressure," necessary to force a nonwetting phase through partially saturated rock; the "displacement pressure," which is that special case of the threshold pressure in which both phases fully saturate separate portions of the rock. Displacement pressure is equal to the minimum value of the "capillary pressure." The theory of flow including capillary forces is developed at the producing surface of a well to reveal the presence there of a pressure discontinuity in the gas (or other nonwetting) phase that can be controlled to the end that more oil may be poduced from an oil field. Experiments with packed sand-flow tubes having artificial producing surfaces support the theory. Introduction The basic surface quantities acting in an oil field are two: namely, surface tensions and contact angles. These are the quantities, variously expressed, and particularized as spreading forces, adhesion tensions, heats of wetting, etc., which are measured in the laboratory by techniques mostly confined to flat or circularly cylindrical surfaces. Such measurements have not had the extensive engineering application they seem to deserve because in most practical cases they are unavoidably compounded with the complex and unapproached subject of the internal shape of the interstices of rock. In this paper it is intended that the pressure differences developed in rock by capillarity be examined, defined, and given some engineering use in terms of some new measurements that have been made. Such pressure differences—namely, the capillary pressure, the displacement pressure and the threshold pressure—seem to provide a proper contact between the basic molecular quantities and the oil field. While certain modifications of usage will be undertaken, the present effort rests upon the background of work by the U. S. Geological Survey,l by Versluys, and especially by W. 0. Smith, 3,4,5 which has been reviewed recently in papers by Leverett.=s7 The most important concept of pressure difference is the capillary pressure, a function of saturation that expresses the pressure difference between the interconnected phases in a rock. It is often measured when water and air are the fluids present, but it can be measured with other fluids. A number of curves of capillary pressure have recently been measured by a method which it is intended shall be published in a later paper. Since heretofore capillary-pressure measurements upon rock have not been

Jan 1, 1944

By G. L. Hassler, E. Brunner, T. J. Deahl

The capillary effects in reservoir rock are discussed in terms of the pressures they cause in sandstones and dolomites. Data for the two-phase case (oil-gas or water-gas) and for the three-phase case (oil, water and gas in rock) are used to demonstrate that in one sense the wetting preference of a rock depends on its saturation. The nature of capillary hysteresis is described for partially stable conditions, and the concept is enlarged. Reproducibly measurable pressures include the "capillary pressure," which is the pressure difference between any two phases that are each interconnected; the "threshold pressure," necessary to force a nonwetting phase through partially saturated rock; the "displacement pressure," which is that special case of the threshold pressure in which both phases fully saturate separate portions of the rock. Displacement pressure is equal to the minimum value of the "capillary pressure." The theory of flow including capillary forces is developed at the producing surface of a well to reveal the presence there of a pressure discontinuity in the gas (or other nonwetting) phase that can be controlled to the end that more oil may be poduced from an oil field. Experiments with packed sand-flow tubes having artificial producing surfaces support the theory. Introduction The basic surface quantities acting in an oil field are two: namely, surface tensions and contact angles. These are the quantities, variously expressed, and particularized as spreading forces, adhesion tensions, heats of wetting, etc., which are measured in the laboratory by techniques mostly confined to flat or circularly cylindrical surfaces. Such measurements have not had the extensive engineering application they seem to deserve because in most practical cases they are unavoidably compounded with the complex and unapproached subject of the internal shape of the interstices of rock. In this paper it is intended that the pressure differences developed in rock by capillarity be examined, defined, and given some engineering use in terms of some new measurements that have been made. Such pressure differences—namely, the capillary pressure, the displacement pressure and the threshold pressure—seem to provide a proper contact between the basic molecular quantities and the oil field. While certain modifications of usage will be undertaken, the present effort rests upon the background of work by the U. S. Geological Survey,l by Versluys, and especially by W. 0. Smith, 3,4,5 which has been reviewed recently in papers by Leverett.=s7 The most important concept of pressure difference is the capillary pressure, a function of saturation that expresses the pressure difference between the interconnected phases in a rock. It is often measured when water and air are the fluids present, but it can be measured with other fluids. A number of curves of capillary pressure have recently been measured by a method which it is intended shall be published in a later paper. Since heretofore capillary-pressure measurements upon rock have not been

Jan 1, 1944

By Morris Muskat, J. M. McDowell

In both production and refining operations of the oil industry many processes are controlled by the gas-liquid phase relationships of the hydrocarbon mixtures of interest. The quantitative behavior of fractionating or distillation columns and stills depends on the changes in the equilibrium distributions of the hydrocarbon components between the gas and liquid phases as the pressure or temperature conditions may vary along the length of the column or as the gross operating parameters and compositions are varied. In oil producing operations the nature and amount of gas phase developed within an underground reservoir as it is being depleted and its pressure declines also involve the basic equilibrium gas-liquid phase interactions. The influence of surface conditions of temperature and pressure and various separation procedures on the nature and amount of stock tank oil and natural gas recovered from a given well stream is likewise determined by the same basic phase equilibrium characteristics of the hydrocarbon systems. Such equilibrium separation of the gas and liquid phases in a well stream is of importance both in establishing optimum separator conditions for obtaining maximum stock tank oil yields and in the general problem of crude stabilization. The phenomena involved in these problems and their quantitative aspects can, of course, be established in each individual instance by appropriate laboratory experimentation. It has been found, however, that by associating with the individual hydrocarbon components functional characteristics de- scribing their individual gas - liquid phase equilibrium behavior, the phase properties of the composite mixtures can be predicted by mathematical computation. These characteristics have been termed "equilibrium constants", or "equilibrium ratios"," and are defined by the general equation: where K, is the equilibrium ratio for the jth component, y, is the rnol fraction of that component in the gas phase, and xj is the corresponding mol fraction in the coexisting liquid phase. Considering the Kj as representing available and measurable properties of the individual components of a mixture, and as defined by Eq. (l), it is readily shown that in a coexisting gas-liquid system the rnol fraction concentrations of the individual components in the gas phase, y,, and those in the liquid phase, x,, are given by the expressions: where the nj are the corresponding rnol fraction concentrations in the composite system, and ng is the mol fraction of the whole which is in the gas phase. The basic unknown in Eq. (2) is n,: which gives the gross separation between the gas and liquid phases. This may be determined in principle by imposing the requirement that the sums of the mol fractions in both the gas and liquid phases are unity, i.e. by the equations: The solution of the equivalent Eqs. (3) lying between 0 and 1, when inserted into Eqs. (2), provides a complete description of the compositions of the coexisting gas and liquid phases. While the Eqs. (3) are essentially equivalent to polynomial equations, such transformations are of little value when dealing with multicomponent sys-

Jan 1, 1949

By J. M. McDowell, Morris Muskat

In both production and refining operations of the oil industry many processes are controlled by the gas-liquid phase relationships of the hydrocarbon mixtures of interest. The quantitative behavior of fractionating or distillation columns and stills depends on the changes in the equilibrium distributions of the hydrocarbon components between the gas and liquid phases as the pressure or temperature conditions may vary along the length of the column or as the gross operating parameters and compositions are varied. In oil producing operations the nature and amount of gas phase developed within an underground reservoir as it is being depleted and its pressure declines also involve the basic equilibrium gas-liquid phase interactions. The influence of surface conditions of temperature and pressure and various separation procedures on the nature and amount of stock tank oil and natural gas recovered from a given well stream is likewise determined by the same basic phase equilibrium characteristics of the hydrocarbon systems. Such equilibrium separation of the gas and liquid phases in a well stream is of importance both in establishing optimum separator conditions for obtaining maximum stock tank oil yields and in the general problem of crude stabilization. The phenomena involved in these problems and their quantitative aspects can, of course, be established in each individual instance by appropriate laboratory experimentation. It has been found, however, that by associating with the individual hydrocarbon components functional characteristics de- scribing their individual gas - liquid phase equilibrium behavior, the phase properties of the composite mixtures can be predicted by mathematical computation. These characteristics have been termed "equilibrium constants", or "equilibrium ratios"," and are defined by the general equation: where K, is the equilibrium ratio for the jth component, y, is the rnol fraction of that component in the gas phase, and xj is the corresponding mol fraction in the coexisting liquid phase. Considering the Kj as representing available and measurable properties of the individual components of a mixture, and as defined by Eq. (l), it is readily shown that in a coexisting gas-liquid system the rnol fraction concentrations of the individual components in the gas phase, y,, and those in the liquid phase, x,, are given by the expressions: where the nj are the corresponding rnol fraction concentrations in the composite system, and ng is the mol fraction of the whole which is in the gas phase. The basic unknown in Eq. (2) is n,: which gives the gross separation between the gas and liquid phases. This may be determined in principle by imposing the requirement that the sums of the mol fractions in both the gas and liquid phases are unity, i.e. by the equations: The solution of the equivalent Eqs. (3) lying between 0 and 1, when inserted into Eqs. (2), provides a complete description of the compositions of the coexisting gas and liquid phases. While the Eqs. (3) are essentially equivalent to polynomial equations, such transformations are of little value when dealing with multicomponent sys-

Jan 1, 1949

By F. H. Wilson, E. W. Palmer

G. L. Bailey (British Non-Ferrous Metals Research Association, London, England)—I was glad to see this further work on the structure and properties of the Cu-Ni-Fe alloys of low nickel content in which we have been so interested in the United Kingdom since before the war." The authors' data on the variation in solubility of iron in both 5 and 10 pct Ni alloys with temperature is based on more detailed observations than we have made but is generally in line with our own work. The difficulty in these matters is in the identification of the structures obtained. The precipitation of the second phase which we presume to be the a' solid solution, richer in nickel and iron, from the a solution with which it is in equilibrium occurs in such a fine state of division that its resolution by ordinary micro-graphic methods is impossible in the early stages. We have published some electron micrographs which illustrate the effects observed more clearly but we agree with the authors when they say that dark staining characteristics when the alloys are subjected to sea-water corrosion are more sensitive in detecting the presence of the a' phase than is the microscope. After taking this point into consideration, however, I confess to some difficulty in understanding Fig. 4. I can only assume that the precipitates visible at such a low magnification as 150 diam in these relatively coarse forms are produced from iron-rich areas of the initial solid solution due to inadequate homogenization. If this is so I find it difficult to accept the authors' contention that such local variations in iron concentration as are capable of giving the heavy precipitates shown in Fig. 4 do not in fact materially affect the solvus surfaces of their equilibrium diagrams. I share the authors' enthusiasm about the resistance to corrosion of these alloys by seawater but I am not fully in agreement with them on the vexing question of the best iron content for these alloys. In Fig. 3 of ref. 8, we give many results showing that the resistance of these alloys to impingement attack in the Jet Test increases as the iron content rises to 2 pct. With higher iron contents pitting at shielded areas is likely to occur. Admittedly the addition of 0.75 pct Fe produces a large improvement in corrosion resistance compared with a pure 90/10 Cu-Ni alloy, but the further improvement on raising the iron to 2 pct is substantial. We recommend from 1.5 to 2 pct Fe as the desirable range from the point of view of corrosion resistance. While it is true that British practice generally uses a hard tube, the corrosion resistance of the 10 pct Ni alloys has in our work been little affected by the structural condition. Although the annealed alloys blacken in seawater, this effect seems to be superficial and not to be accompanied by any real decrease in

Jan 1, 1953

By M. B. Willey

The Louisiana Continental Shelf is a submarine area extending offshore as much as one hundred miles. The Gulf bottom in this region varies considerably in extent, profile and composition and consists largely of sedimentary deposits, predominantly those of the Mississippi River. It is very young in a geological sense. Up to the present time few major structures have been erected offshore in the Gulf and no comprehensive preliminary tests have been carried out. Results of pile driving tests are of little value as actual bearing capacities far exceed the dynamic resistance to driving as measured by conventional formulas. Soils encountered are, with few exceptions, cohesive and piling consequently develop their supporting power through surface friction. Because of the time required and relatively high costs, no complete load tests have been made. The results of those tests which have been made, and information obtained from pulling piling in one structure, indicate that design loadings could be considerably increased, and it is contended that comprehensive preliminary investigations including an actual load test, combined with borings and examination of materials encountered by competent soil experts, would effect economies in design far in excess of their cost. The Louisiana Continental Shelf—General The Louisiana . . . continental shelf is a submarine area which extends seaward for as great a distance as one hundred miles off the present shoreline. The Gulf bottom in this region is characterized by low slopes and its outer margin is outlined by the fifty fathom (300 ft.) contour. South of the margin of the shelf the slopes steepen abruptly in the continental slope zone and plunge into the deeps of the Gulf of Mexico.l The engineer who is called upon to design a structure on this shelf is concerned only with the uppermost portion to a depth generally not to exceed Ioo to 150 ft. This layer is very young in a geological sense, and it has the characteristics usually associated with infancy. A few of these are lack of strength, lack of uniformity, and high water content. It consists of the sedimentary deposits of the various rivers and streams entering the Gulf. These streams are all heavily burdened in quantities sufficient to fill the areas at their mouths, were it not for the fact that continual subsidence, equal or greater in amount and acting directly opposite, prevail over the sedimentary workings of the streams. This subsidence has been estimated by geologists to be at the rate of at least one foot per century. Influence of Mississippi River The Mississippi River, which has been the predominant factor in the formation of practically all the Louisiana continental shelf, is one of two rivers flowing into the Gulf that have been able to build protruding deltas. The Mississippi has done so because of its enormous size and load. It deposits sediments in amounts sufficient to replace and actually gain on the amount of subsidence.

Jan 1, 1949

By James Terry Duce

In order to facilitate interpretation of the data in this chapter, we print the following excerpts from circulars to authors, compiled by Mr. Frank A. Herald when he was Vice-chairman for Production of the Petroleum Division: Generally in Table 1 the unit for presentation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions-—several units of continuous productive reservoirs of distinctly different structure and of distinctly dzerent stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and/or commercial value. As to each space in the tabulation, it is either (1) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert x; in spaces where the proper entries are determinable but not determinable from data available to the author, the author will please insert y; in spaces where the proper entries are determinable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use 2. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report l,8x,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations

Jan 1, 1937

By William A. Johnson

The fundamental role of diffusion in many reactions occurring in solid metals has long been recognized, and there have been careful measurements of rates of diffusion in numerous alloy systems; but our understanding of the atomic mechanism by which diffusion occurs is scarcely in an advanced state.l-3 It is doubtful that this mechanism can ever be directly ascertained; rather, all imaginable mechanisms must be examined and the one that is in best accord with such data as can be obtained from suitably chosen experiments should be selected. Because of its relative simplicity, diffusion in a system containing only one kind of atomic species—commody called self-diffusion—is of considerable theoretical interest. It may be expected that diffusion theory will not be advanced appreciably until a wide variety of diffusion experiments—of which diffusion in a chemical concentration gradient and self-diffusion are two important types—are carefully performed and inter-compared. Aside from the purely theoretical interest in self-diffusion measurements, such studies will be of considerable engineering importance. The rate of any process in a pure metal requiring the movement of atoms, of which recrystallization and creep are two familiar examples, will be understood more readily with the aid of self-diffusion data.† Self-diffusion implies the diffusion of something into its exact counterpart; the detection of such a process is patently impossible, and it is necessary to substitute for it the diffusion of one isotope (in this case radioactive) into another isotope (in this case stable) of the same chemical element. There is, however, no reason to suppose that a radioactive atom will not diffuse at the same rate as its stable isotope, for all of the isotopes of the same element have exactly the same chemical properties; neither the difference in nuclear energy nor the difference in mass would be expected to exercise an important influence in this phenomenon. In this sense, self-diffusion may be thought of as the diffusion of radioactive atoms down a radioactivity concentration gradient, just as usual diffusion is the diffusion of one kind of atom down its chemical concentration gradient. The first measurements of self-difiusion were made by von Hevesy4-6 using the radioactive lead isotope thorium B in ordinary lead. The recent development of means for producing artificial radioactive elements has made possible similar measurements on gold,7, 8 copper,2, 9 and zinc.10, 11 Many of the data that have been obtained are rather poor, and no adequate reason has been given for their poorness; it appears, however, that the unsatisfactory results are characteristic of the particular experimental procedure employed, and not of self-diffusion measurements in themselves. The experimental technique that has yielded the poorer results is the deposition of a thin layer of radioactive atoms on the surface of a specimen and the determination of the rate of inward diffusion

Jan 1, 1941

By William A. Johnson

The fundamental role of diffusion in many reactions occurring in solid metals has long been recognized, and there have been careful measurements of rates of diffusion in numerous alloy systems; but our understanding of the atomic mechanism by which diffusion occurs is scarcely in an advanced state.l-3 It is doubtful that this mechanism can ever be directly ascertained; rather, all imaginable mechanisms must be examined and the one that is in best accord with such data as can be obtained from suitably chosen experiments should be selected. Because of its relative simplicity, diffusion in a system containing only one kind of atomic species—commody called self-diffusion—is of considerable theoretical interest. It may be expected that diffusion theory will not be advanced appreciably until a wide variety of diffusion experiments—of which diffusion in a chemical concentration gradient and self-diffusion are two important types—are carefully performed and inter-compared. Aside from the purely theoretical interest in self-diffusion measurements, such studies will be of considerable engineering importance. The rate of any process in a pure metal requiring the movement of atoms, of which recrystallization and creep are two familiar examples, will be understood more readily with the aid of self-diffusion data.† Self-diffusion implies the diffusion of something into its exact counterpart; the detection of such a process is patently impossible, and it is necessary to substitute for it the diffusion of one isotope (in this case radioactive) into another isotope (in this case stable) of the same chemical element. There is, however, no reason to suppose that a radioactive atom will not diffuse at the same rate as its stable isotope, for all of the isotopes of the same element have exactly the same chemical properties; neither the difference in nuclear energy nor the difference in mass would be expected to exercise an important influence in this phenomenon. In this sense, self-diffusion may be thought of as the diffusion of radioactive atoms down a radioactivity concentration gradient, just as usual diffusion is the diffusion of one kind of atom down its chemical concentration gradient. The first measurements of self-difiusion were made by von Hevesy4-6 using the radioactive lead isotope thorium B in ordinary lead. The recent development of means for producing artificial radioactive elements has made possible similar measurements on gold,7, 8 copper,2, 9 and zinc.10, 11 Many of the data that have been obtained are rather poor, and no adequate reason has been given for their poorness; it appears, however, that the unsatisfactory results are characteristic of the particular experimental procedure employed, and not of self-diffusion measurements in themselves. The experimental technique that has yielded the poorer results is the deposition of a thin layer of radioactive atoms on the surface of a specimen and the determination of the rate of inward diffusion

Jan 1, 1941