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By B. Fazan, O. D. Sherby, J. E. Dorn

McLean's technique was employed to determine the effect of temperature on the contribution of grain boundary shearing to the total creep strain in pure aluminum over the range of 610° to 747°K. The contribution of grain boundary shearing at the same stress was found to depend upon a temperature-compensated time, where the activation energy AH was practically identical with that for total high temperature creep. SEVERAL outstanding investigations by McLeanl-' have demonstrated that the total creep strain in polycrystalline aluminum at 473°K arises from microscopically detectable slip, subgrain tilting, and grain boundary shearing. Whereas microscopically detectable slip arises from dislocations that move out of the grains, subgrain tilting is due to entrapment of dislocations of like sign in subgrain bound-arles. Consequently, creep in polycrystalline aggregates appears to be the resultant of two mechanisms, namely, migration of dislocations and grain boundary shearing. This suggests that an appropriate law for creep should contain two additive terms ?1 = ?d + ?yb where the total creep strain, ?1, depends on the sums of the creep strains arising from motion of dislocations, ?d, and from grain boundary shearing, ?yb. But extensive investigations5 over wide ranges of alloys, grain sizes, temperatures, and stresses have shown that the total creep strain is quite accurately dependent on the single term functional relationship ?1 = f (?), s = constant where s is the stress (constant),* ? = te-?H/RT, t is the time under stress, AH is the activation energy, R is gas constant, and T is absolute temperature. Since Eq. 2 was found to be valid over those ranges where appreciable grain boundary shearing is observed, it appears probable that the activation energy for grain boundary shearing might be identical with the activation energy for migration of dislocations. Thus, under a given stress, it could be thought that where fd and fgb represent the appropriate functions for each mechanism of creep. The primary objective of this investigation was to obtain a direct check on the accuracy of this hypothesis. Experimental Procedure and Results Rolled aluminum sheet (99.987 pct Al), 0.100 in. thick, was used in this investigation. Creep specimens having a 0.25 in. wide, 3 in. long gage section were so machined that their axes were in the rolling direction. All specimens were annealed for 9 hr at 894°K before testing to produce a mean grain diameter of about 0.1 in. One face of each specimen was polished electrolytically in 10 pct HBF4. In order to permit accurate measurements of grain boundary shearing, the polished surface was lightly scribed with a ruling machine accurate to ±0.0001 in. to give a uniform grid of lines which were 0.01 in. apart. Although it was thought that surface working might modify the creep behavior in the vicinity of the scribed grid lines, this technique nonetheless was employed because such local differences in creep properties should not modify seriously the fractions of the total creep strain due to grain boundary shearing or to migration of dislocations. All creep tests were conducted under constant load with an initial stress of 250 psi. The specimen tem-

Jan 1, 1955

By Kehsin Kuo

DIE steel with 1.47 pct C, 0.42 pct Mn, and 8.22 pct W contains Fe,C and WC in the annealed state and WC embedded in a martensitic matrix in the hardened state (quenched from 800°C). The presence of a large amount of undissolved angular WC carbide particles makes this steel extremely wear-resistant. However, the WC carbide begins to dissolve in the austenite when the heating temperature is raised above 1000°C, but this solution process is still not complete at 1250°C although partial melting has already taken place at the austenite grain boundaries. At 1325 C, this steel contains austenite and liquid metal but no WC carbide, Fig. 1. On quenching into brine, the liquid metal solidifies into a constituent which etches differently from the austenite-martensite matrix. This constituent appears lighter than the matrix at the 1250°C stage when etched with 2 pct nital but darker in Fig. 1 when etched with Murakami's reagent. Such a constituent has also been found in burnt tungsten high speed steels. This constituent has been isolated from the matrix by anodic dissolution in a 5 pct HC1 electrolyte and was found by the X-ray powder method to be iso-morphous with &manganese, Table I. The agreement in line intensity between these two phases indicates that there is no ordering in this new phase. The calculated cube edge of this phase is 6.395A, somewhat larger than that of ß-manganese (6.30A). Besides this phase, the anodic residue also contains free carbon from the matrix and amorphous WO,, although the X-ray powder pattern of the residue shows the presence of only this phase. This makes it impossible to determine directly the composition of this phase from the residue. Attempts to prepare an alloy containing only this phase have hitherto been fruitless. The following experiments serve to show that this phase can only be obtained by drastic quenching from the liquid state and that its tungsten and carbon contents must be lower than those in the Fe,W,C carbide. On air cooling from 1325oC, the liquid metal solidifies into a eutectic consisting of austenite and the Fe3W3C carbide. The nature of this dark-etching Fe3W3C has also been ascertained by X-rays. This eutectic becomes coarser on furnace cooling. The solidification of a specimen cooled for 5 min from 1325" to 1200°C and water quenched is still not complete and the fine eutectic is formed during the quenching. Since this new phase can be replaced by a eutectic of austenite and the Fe,W,C carbide, its composition must lie somewhere between the latter two phases. The special features of this phase are: 1—it can only form directly from the liquid state by drastic quenching and 2—it is a ternary phase of iron, tungsten, and carbon. The ß-manganese structure of this phase is also interesting. In the Periodic Table, iron and tungsten lie on opposite sides of manganese; a certain combination of these two elements, in the presence of carbon, may have average properties similar to those of manganese. It has already been established that the x phase, a ternary one of iron, chromium, and molybdenum, has the a-manganese structure."' A similar phase has also been found in the ternary system Fe-Cr-W and in the following binary systems: Re-Cb, Re-Ta, Re-Mo, and Re-W.6 References 1 G. D. Preston: Philosovhical Magazine 11928) 5. 7th Series, p. 1207. - K. W. Andres: Nature (1949) 164, p. 1015. 35. G. McMullin, S. F. Reiter, and D. G. Eberling: Trans. ASM 11954) 46, p. 799. ' J. S. Kasuer: Acta Metallurgica (19541 2, p. 456. • H. J. Goldschmidt: Trans. ASM (19541 46, p. 807. P. Greenfield and P. A. Beck: Private communication.

Jan 1, 1957

By P. Marier, T. R. Ingraham

When anhydrous cupric sulfate is heated in a stream of nonreactive gas, cupric oxysulfate is formed. When this reaction is complete, the cupric oxysulfate then decomposes to cupric oxide, which is the normal end product of reaction. The kinetics of each of these reactions has been studied using pellets prepared from finely divided cupric sulfate and from finely divided cupric oxysulfate. In each case, the reactant-product interface within the pellet is well-defined, and by normalizing the decrease in inter facial area with the weight fraction of the pellet decomposed it has been shown that the interface migrates into the pellet at a uniform rate at constant temperature. The activation energy estirnated for the decomposition of cupric sulfate is 57 ± 7 kcal per mole and that for cupric oxysulfate is 67 ± 8 kcal per mole. The rate of interfacial reaction is flow-sensitive, increasing with increasing flow of a sweep gas in the range from 50 to 2000 cu cm per min. The rate of decomposition is retarded by sulphur trioxide in the sweep gas. The relationship between sulfur trioxide Partial pressure and rate is consistent with the Langmuir Adsorption Isotherm governing the retention of sulfur trioxide in the interfacial layer. MOST of the work reported on the thermal decomposition of cupric sulfate and of cupric oxysulfate is related to the thermodynamics of the individual decompositions.'-4 No information is available on the rates of the individual reactions, on their activation energies, or on the effects of gas flow or of partial pressure of sulfur trioxide on the reaction rates. Some dubious conclusions based on relative reaction rates have been drawn from studies on the oxidation of sulfides. For example, on the basis of the products observed in a quenched system, it has been suggested5" that, when copper sulfide is roasted, the cupric oxide which is formed arises from the decomposition of either cupric sulfate or cupric oxysulfate. This is very difficult to reconcile with the thermodynamics of the C-S-O System,3 which support the probability that both cuprous oxide and cupric oxide precede cupric oxysulfate and cupric sulfate in the sequence of products formed during the oxidation of cuprous sulfide. In this paper the individual sulfate decomposition reactions will be examined and suggestions will be advanced for the mechanism of reaction. This will be based on the effects on reaction rate of changes in interfacial area, flow rate, and back-pressure of sulfur trioxide. EXPERIMENTAL Materials. The copper source material used in all experiments was Fisher Certified Reagent Grade anhydrous cupric sulfate, for which the following analysis was supplied by the manufacturer: chloride, 0.002 pct; alkalies and earths, 0.2 pct; insoluble, 0.002 pct; iron, 0.020 pct. Cupric oxysulfate was prepared by roasting cupric sulfate for 48 hr, with frequent rabbling, in an open tray in a muffle furnace maintained at 725°C. At this temperature, cupric sulfate develops about 0.16 atm pressure of combined sulfur trioxide, sulfur dioxide, and oxygen. Cupric oxysulfate develops only about 0.05 atm pressure, and is stable until

Jan 1, 1965

By B. F. Buie

For over 200 years meerschaum has been a significant item of trade between the Near East and countries to the west. Best-known for its use in making smoking pipes and cigar and cigarette holders, it is also used in making a variety of decorative and ornamental items. It is easily carved, and is given an attractive, lustrous finish by rubbing. No published specifications are known, but compact form, purity, uniform whiteness or light color, and uniform, porous texture appear to be requisites. Fig. I a shows the appearance of a piece of crude meerschaum from Turkey; Fig. lb a carved item; and Fig. lc, d, and e show the fibrous and porous texture as revealed by the scanning electron microscope. Neither a major industrial mineral nor a precious stone, meerschaum nevertheless holds a record of long-and continuing-association with art and personal affairs of man. It is also a mineral to which modem methods of exploration and production probably could be profitably applied. An interesting account of the preparation and use of meerschaum in the early part of this century is given by Sterrett (1907). Geology and Mining Mineralogy Meerschaum is recognized now to be the compact variety of sepiolite, the claylike variety of which is one of the minerals included in the chapter on clays. The word meerschaum, from the German meaning "sea foam," was in earlier times used synonymously with sepiolite, a word of Greek origin suggestive of the resemblance of the compact variety-then the only variety known-to cuttlefish bone. At one time meerschaum was used as the commercial name, and sepiolite for the scientific name. However, to think of meerschaum as the name by which sepiolite is known commercially is no longer valid, in view of the recent emergence of the earthy variety as a competitor of bentonite and other clay materials. Present tendency is to restrict the term meerschaum to the compact variety, and to use the term sepiolite as a more general name to include both the compact and earthy varieties. This is the terminology followed in this publication. Meerschaum typically is white to light gray, has a hardness of 2 to 2 ½ , conchoidal to irregular fracture, and specific gravity varying with porosity from about 2 to less than 1. The composition is somewhat variable,- but is near that determined by Schaller (1936) for sepiolite as 2MgO.3SiO2.4H2O. A more modern for mula based on X-ray determination of the crystal structure is given by Caillére and Henin (1961) as (Site) (Mg9)030(OH)6(0H2)46H20. The reason for the firm, compact nature of meerschaum, in contrast with the earthy variety of sepiolite, is not fully understood. It may be due to the presence of a very minor amount of some bonding material such as silica. Scanning electron microscope (SEM) photographs of a specimen from Turkey (Figs. lc-le) indicate that the meerschaum is composed predominantly, if not entirely, of crystalline fibers which merge into sheetlike forms in a complex, intertwined mass. Detailed X-ray and crystal structure data, as well as some data on thermal stability range, are given by Caillère and Hénin (1961) for the sepiolite family of minerals. Mode of Occurrence and Origin Most authors have attributed the origin of meerschaum to alteration of serpentine or other magnesian minerals. The occurrence in alluvium and other surficial deposits does not necessarily indicate that the alteration was supergene. In fact, hydrothermal origin appears more likely for some deposits, though not for all.

Jan 1, 1983

By Albert S. Trube

Increasing emphasis is being placed on the necessity for obtaining reasonably accurate estimates of the physical properties of reservoir fluids well in advance of more accurate laboratory data. One such factor is the isothermal coefficient of expansion of an undersaturated hydrocarbon liquid which may be contained in a particular reservoir. This coefficient, or liquid "compressibility", has often been assumed to be relatively insensitive and nearly constant. Although this assumption may be nearly correct in the case of high specific gravity liquids, it cannot apply in the case of medium to low specific gravity liquids. Any treatment of the nature of liquid compressibilities must give consideration to the variable nature of the isothermal expansion coefficient and the fact that it can be both pressure sensitive and temperature sensitive. The isothermal coefficient of expansion, or compressibility, of a substance is defined as -c = 1/V (?V/?p)T......(1) The value of Eq. 1 may be approximated for a finite pressure change by using the well-known relation, c = V1 - V1/Ve (p2-p1), ........(2) in which p1 > p1 and V2 > V2 and V1 + V2/2. The instantaneous compressibility may also be estimated from the slope of a curve on which log V is plotted vs pa. In this instance, it has been shown that c = In V1/V2/p2-p1 ...........(3) Eq. 3 may be used for variable compressibilities by plot-ting V vs p on semi-log paper. In this case, the instan-taneous or point compressibility is c = 2.303 m.......... . (4) in which m is the slope of the curve at a point in log cycles per psi. ISOTHERMAL COMPRESSIBILITY OF UNDERSATURATED LIQUID In the case of gases, the compressibility has been defined by Muskat' and others as Co = 1/p - ?z/z?p ..........(5) This was later generalized through application of the theorem of corresponding states' to co = 1/pr - (?z/z?pr) T8 ........(6) in which c, is defined as the pseudo-reduced compres-sibility and is numerically equal to (c.p,) and the sign is arbitrarily changed for mathematical convenience. Eq. 6 is general and applies to gases and liquids. In the case of liquids, c. = c1,pe, but if Eq. 6 is used, values of z and ?z/?p, must be determined for the liquid in question. The difficulty of obtaining accurate values of ?z/?p,, particularly in the region where T, is approaching 1.00, was pointed out in the previous paper'. This method of approach is unreliable for extension into computations of liquid compressibilities. On the other hand, c, can also be defined as follows: - Cr = 1/Vr (?Vr/?pr) Tr ......(7) and from which, Cr = 1/pr (?pr/?pr) Tr .....(8) In accordance with the theorem of corresponding states, Vr = V/Vr, p, = p/pr and pr = p/pr. Ref. 2 pro-vides an excellent source of reduced density, reduced pressure and reduced temperature data for a wide variety of fluids. For the purpose of this investigation, the set of fluids2 having ze = 0.27 was chosen because it in-cludes most of the heavier hydrocarbons usually found in those complex mixtures loosely defined as "reservoir oils". Data on undersaturated liquids in Ref. 2 were rearranged to conform with Eq. 8. To simplify the computation of cr, the isothermal p, data were plotted vs the log of pr, in which case for any straight line or tangent cr = 1/M pr pr .....(9)

Jan 1, 1958

By Michael Shaughnessy, O&apos

The outstanding features of the Coloinbian situation for the year 1929 were legal and political. The passage of Law 84 and the promulgation of the Regulatory Decree 150 were recounted in the review for 1928, as was also the Presidential proclamation suspending this law and its accompanying decree until decision could be reached in the suits filed against them before the Supreme Court and the Council of State. Early this year the Minister of Industries, Jose Antonio Montalvo, announced the appointment of a commission of foreign experts to aid in drafting a new petroleum law. He requested all of the foreign experts employed not to consult with the oil company representatives in Bogota, and these experts were therefore shut off from receiving any suggestions from those who had actually operated in the country and knew the conditions under which operations would take place. It was to be expected that the provisions of a law suggested under such circumstances would not meet operating conditions satisfactorily. The specific objections are stated in O'Shaughnessy's South American Oil Reports (April, 1929). An especially qualified commentator observes that one of the curious provisions of the proposed law was the high royalty on gas—5c. per 1000 cu. ft. of gas produced. There was also a provision requiring 20 per cent. of the stock of the company operating in Colombia to be offered for sale to Colombians. The bill failed to pass Congress in the closing hours of the session. The Supreme Court, in the meantime, handed down its decision on Law 84 of the previous year and Regulation 150 covering the enforcement of that law. Contrary to expectation, the majority opinion of the Court practically affirmed the constitutionality of both the law and the regulatory decree, with the exception of Article 20 and parts of Article 21 of the decree which referred specifically to the registration of private properties. At the time the suit was filed against Law 84 and Decree 150 the operation of these measures was suspended by the Executive. Law 84 and its Regulatory Decree 150 still remain suspended as the Council of State has not yet brought in a decision upon the questions raised in the suits instituted by the various companies against the law and decree, and at the moment of this writing it appears unlikely that such a decision will be reached by that body.

Jan 1, 1930

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,' liquid mercury upon brass,4 and liquid mercury upon nickel.' 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.' 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 L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall' support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall' support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By Carlton Beal

This paper presents useful charts for conversion of various viscosimeter units into centipoises and graphically summarizes published investigations of the viscosity of air, water and natural gas at high temperatures and pressures. Where possible, charts and correlations were constructed to cover a range of temperature (60°F. to 300°F.) and pressure (14.7 lb. per sq. in. abs. to 8000 lb. per sq. in. gauge) encountered in oil fields. Correlation charts, for the purpose of predicting crude oil viscosity and solubility behavior at oil field temperatures and pressures, were constructed from an analysis and correlation of 1332 viscosity and solubility observations from 953 crude oil samples taken from 747 oil fields. Of these fields, 501 are in the United States, including 75 in California. Of the 1332 observations, 1215 were viscosity values, including 786 of gas-free crude oil, 351 of oil saturated with gas, and 78 under-saturated with gas at pressures above the bubble point. Results show that crude oil viscosity at various reservoir conditions can be predicted with average deviations varying from 24.2 per cent for gas-free crude oil to as little as 2.7 per cent for undersaturated crude oil "above the bubble point." The solubility of crude oil may be predicted from oil gravity and saturation pressure with an average deviation of 22.0 per cent from observed values. In conclusion, it is shown that the viscosity of a gas and gas-saturated crude oil may be predicted within the accuracy of most reservoir computations. Viscosity is a measure of flow resistance; common units are in centipoises (cp.). The object of this report is to present conversion charts and simplified 'correlation charts showing the viscosity behavior of air, water, gas and crude oil and gas-saturated crude oil under oil field temperatures and pressures, which have been known to be as high as 300°F. and 8000 Ib. per sq. in. gauge under subsurface conditions. The viscosity of a liquid or gas is important because it is a measure of its fluidity, or its ability to flow through pipe lines or oil sands. Viscosity of air has become important because it is being used in secondaryl,2 recovery projects. The viscosity of natural gas and water at reservoir conditions is useful because they are almost universally associated and produced with crude oil. The viscosity of gas-saturated crude oil at reservoir pressures and tem peratures is of particular value in making estimates of oil reserves3 and rate of oil recovery from flush pools when production decline data are limited. Instruments Used to MeasuRe Viscosity There are many types of viscosimeters,4 and the instruments most commonly used to measure the atmospheric viscosity of liquids at moderate temperatures and their practical working ranges have been deScribed5,6 in detail. Fig. I and Fig. 2 are viscosity conversion charts which have

Jan 1, 1946

By Carlton Beal

This paper presents useful charts for conversion of various viscosimeter units into centipoises and graphically summarizes published investigations of the viscosity of air, water and natural gas at high temperatures and pressures. Where possible, charts and correlations were constructed to cover a range of temperature (60°F. to 300°F.) and pressure (14.7 lb. per sq. in. abs. to 8000 lb. per sq. in. gauge) encountered in oil fields. Correlation charts, for the purpose of predicting crude oil viscosity and solubility behavior at oil field temperatures and pressures, were constructed from an analysis and correlation of 1332 viscosity and solubility observations from 953 crude oil samples taken from 747 oil fields. Of these fields, 501 are in the United States, including 75 in California. Of the 1332 observations, 1215 were viscosity values, including 786 of gas-free crude oil, 351 of oil saturated with gas, and 78 under-saturated with gas at pressures above the bubble point. Results show that crude oil viscosity at various reservoir conditions can be predicted with average deviations varying from 24.2 per cent for gas-free crude oil to as little as 2.7 per cent for undersaturated crude oil "above the bubble point." The solubility of crude oil may be predicted from oil gravity and saturation pressure with an average deviation of 22.0 per cent from observed values. In conclusion, it is shown that the viscosity of a gas and gas-saturated crude oil may be predicted within the accuracy of most reservoir computations. Viscosity is a measure of flow resistance; common units are in centipoises (cp.). The object of this report is to present conversion charts and simplified 'correlation charts showing the viscosity behavior of air, water, gas and crude oil and gas-saturated crude oil under oil field temperatures and pressures, which have been known to be as high as 300°F. and 8000 Ib. per sq. in. gauge under subsurface conditions. The viscosity of a liquid or gas is important because it is a measure of its fluidity, or its ability to flow through pipe lines or oil sands. Viscosity of air has become important because it is being used in secondaryl,2 recovery projects. The viscosity of natural gas and water at reservoir conditions is useful because they are almost universally associated and produced with crude oil. The viscosity of gas-saturated crude oil at reservoir pressures and tem peratures is of particular value in making estimates of oil reserves3 and rate of oil recovery from flush pools when production decline data are limited. Instruments Used to MeasuRe Viscosity There are many types of viscosimeters,4 and the instruments most commonly used to measure the atmospheric viscosity of liquids at moderate temperatures and their practical working ranges have been deScribed5,6 in detail. Fig. I and Fig. 2 are viscosity conversion charts which have

Jan 1, 1946

By S. F. Ravitz

In his excellent book on the Principles of Flotation, Warkl makes the following significant statement concerning the theory of flotation: Two questions of first-rate importance must be considered . . . First, it must be decided whether the sulfide minerals require a collector in order that they may float, or whether as has been claimed, they possess an inherent float-ability and need no collector. Second, it must be decided whether the xanthate type of collector can react with or be adsorbed by the unchanged sulfide minerals themselves, or whether, as many claim, reaction with the collector is dependent upon initial oxidation of the mineral surface. In the theory of flotation there are no two questions of greater importance than these. Ravitz and Porter2 presented evidence that galena can be floated without a collector, and even without any reagent, provided oxidation products are thoroughly removed from its surface. They found also that thoroughly cleaned galena floated faster when xanthate was used than when a frother alone or no reagent was used, and that, without a collector, the recovery decreased gradually upon exposure of the mineral to air. Their work, however, has met with considerable criticism.l(127).3-6 This paper is presented to answer the objections that have been raised, and to present additional data that confirin their results. The apparatus used to provide oxygen-free conditions for flotation has been described in detail by Ravitz and Porter. An atmosphere of purified nitrogen was maintained within the apparatus; all water and solutions used were freed of dissolved air, and could be transferred where desired by the use of nitrogen Pressure; nitrogen was used as the gaseous medium for flotation. The flotation cell was essentially a glass cylinder 15 cm. long and 4.6 cm. in diameter. Near the bottom was sealed a fritted glass filter, which broke up the gas into small bubbles, and 6 cm. above this filter was a side arm through which the froth overflowed. The pulp was agitated by a glass impeller, which entered the cell through a mercury seal. For each test 17 grams of galena and 75 ml. of water were placed in the cell, after which the speed of the impeller and the rate of gas flow were adjusted. Water was added gradually during the test to keep the froth level at the proper height. The mineral was prepared and cleaned in the following manner. Exceptionally Pure galena was crushed by hand on a clean bucking board, screened to —I50+ 200 mesh, and deslimed on a 200-mesh sieve with a fine spray of water. It was then boiled on a hot plate for a number of hours with several changes of the desired cleaning solution, after which both the solution and the mineral were placed in the "mineral flask" of the apparatus. The cleaning solution was drained off, and the mineral was boiled with oxygen-free water

Jan 1, 1943

By S. F. Ravitz

In his excellent book on the Principles of Flotation, Warkl makes the following significant statement concerning the theory of flotation: Two questions of first-rate importance must be considered . . . First, it must be decided whether the sulfide minerals require a collector in order that they may float, or whether as has been claimed, they possess an inherent float-ability and need no collector. Second, it must be decided whether the xanthate type of collector can react with or be adsorbed by the unchanged sulfide minerals themselves, or whether, as many claim, reaction with the collector is dependent upon initial oxidation of the mineral surface. In the theory of flotation there are no two questions of greater importance than these. Ravitz and Porter2 presented evidence that galena can be floated without a collector, and even without any reagent, provided oxidation products are thoroughly removed from its surface. They found also that thoroughly cleaned galena floated faster when xanthate was used than when a frother alone or no reagent was used, and that, without a collector, the recovery decreased gradually upon exposure of the mineral to air. Their work, however, has met with considerable criticism.l(127).3-6 This paper is presented to answer the objections that have been raised, and to present additional data that confirin their results. The apparatus used to provide oxygen-free conditions for flotation has been described in detail by Ravitz and Porter. An atmosphere of purified nitrogen was maintained within the apparatus; all water and solutions used were freed of dissolved air, and could be transferred where desired by the use of nitrogen Pressure; nitrogen was used as the gaseous medium for flotation. The flotation cell was essentially a glass cylinder 15 cm. long and 4.6 cm. in diameter. Near the bottom was sealed a fritted glass filter, which broke up the gas into small bubbles, and 6 cm. above this filter was a side arm through which the froth overflowed. The pulp was agitated by a glass impeller, which entered the cell through a mercury seal. For each test 17 grams of galena and 75 ml. of water were placed in the cell, after which the speed of the impeller and the rate of gas flow were adjusted. Water was added gradually during the test to keep the froth level at the proper height. The mineral was prepared and cleaned in the following manner. Exceptionally Pure galena was crushed by hand on a clean bucking board, screened to —I50+ 200 mesh, and deslimed on a 200-mesh sieve with a fine spray of water. It was then boiled on a hot plate for a number of hours with several changes of the desired cleaning solution, after which both the solution and the mineral were placed in the "mineral flask" of the apparatus. The cleaning solution was drained off, and the mineral was boiled with oxygen-free water

Jan 1, 1943

By Charles P. Williams

The determinations of the specific gravities of a number of samples of lead produced in Missouri, which form the subject of this note, were undertaken with the view of ascertaining if any approximation to the purity of such leads could be reached in this manner. The results would seem to indicate that, whatever value the method may have in the case of the crude and more impure

By J. E. Ostberg, G. Phragmen, A. Hultgren, S. Wohlfahrt

Detailed study was made of a number of rimming ingots, both low and high carbon, and especially upon effects of superimposed air pressure. Requirement to suppress core bubbles is between 10 and 15 atm; at 6.5 atm freezing was in semikilled manner and at 3 atm, steel was of rising type. Probable mechanism of freezing under various conditions is discussed. AN earlier paper' reported an investigation made by a committee for studying rimming steel ingots appointed by Jernkontorets in Stockholm. The present paper is the outcome of some further work done by the same committee. Since the characteristics of ordinary rimming steel are connected closely .with the amount of gas liberated during freezing and since this amount of gas is governed by the pressure, it was considered of interest to ascertain in what manner and to what extent definite pressures applied to the top of the liquid steel in the mold would affect the solidification process and the consequent structure of a rimming steel of ordinary composition. The experiments were made at the Domnarfvets Steel Works. The steel was made according to normal practice in a 4-ton Rennerfelt electric furnace. Ferromanganese was added in the furnace; no aluminum was added, with one exception. Analyses of the four heats are given in Table I. The top-poured ingots measured about 12 in. sq x 48 in. and weighed about 1300 lb. One or two ingots of each heat were allowed to solidify under pressure, using a special device for admitting compressed air to the upper closed part of the mold, as shown in Fig. 1. A heavy plate sealed with asbestos was bolted to the top of the mold. The plate had a tapered aperture for pouring. Immediately after pouring the hole was closed by a wedged plug, and compressed air was admitted through a hole in the plug. Because of some delay in applying the plug, full pressure was not reached immediately. The pressure was adjusted to the desired value as indicated by a manometer. In order that the interior of the ingot might have the benefit of the pressure, the freezing of the top crust was delayed by a refractory lining applied to the top part of the mold, Fig. 1. Ingots were also cast from each heat without applied pressure, and with and without refractory lining at the top. Axial sections of ingots were cut either of the whole ingot or of some part of it of special interest; sections were polished and usually etched.' To facilitate description of structures the following terms may be used for different types of ingots solidified under gas evolution: 1. Box-hat or boot-leg ingot: Abundant gas evolution during casting and during rimming; no rim holes. 2. Normal rimming ingot: Lively gas evolution during rimming; usually rim holes in lowest part of

Jan 1, 1952

By J. W. Marx

A method is given for predicting the complete gravity drainage characteristics of arbitrarily long columns from centrifuge drainage measurements on reconstituted core samples. Oil residuals corresponding to hundreds of years of normal gravity depletion can be obtained in a few hours on the centrifuge. The gravity flow rate at any stage of the depletion process may be determined from the time correlation derived, and experimentally checked, in this study. INTRODUCTION Apart from the original observations of Muskat et al1, research publications2,3,4 on the subject of gravity drainage have been largely concerned with establishing in detail the saturation, S as a function of the height, z, in a draining column at any given time, t. Some form of numerical integration must be employed to obtain production rates and cumulative production even when S(z, t) is known. Furthermore, the relevant experimental work has been concentrated on drainage of a single wetting liquid from unconsolidated media. Since oil production usually concerns the drainage of a partially wetting liquid from consolidated media, in the presence of connate water, and since it is unlikely that sufficient information exists to establish S(z, t) in detail for any natural reservoir, the published research work appears to be, at best, only qualitatively applicable to production problems. With this in mind, the present study was undertaken by the writer. Experiments were planned whose results would have two advantages over existing measurements: 1. Observations were to be made on specific reservoir rock, reconstituted with formation water and formation oil. This would reduce their generality, from the research viewpoint, but increase their utility for production purposes. 2. The measurements were to be self-integrating, i.e., the phenomena were to be described and interpreted in terms of cumulative results. THEORETICAL DEVELOPMENT It was commonly known that centrifuging a liquid bearing porous medium increases the drainage rates and minimizes capillary end effects. The specific problem lay in selecting an acceleration, a, such that the mean residual saturation of a model cylinder was equal to the residual saturation of an arbitrarily long prototype column when the latter was drained by earth gravity alone. The physical conditions required to permit a valid scaling of model drainage time, tm with prototype drainage time, t, may be stated as follows: (a) At t = tm = O, So = Smo; (b) At t = tm? 8 Sr. = Smr.; (c) For all intermediate values of t and dS/dt=dsm/dtm whenever S = Sm; (d) S(z) = Sm(z) = a constant when t = tm = 0. 1 Here S = T I S(z)dz, where h is the length of the « Jo cylindrical column being drained and the subscripts S,Sm, and refer to model, initial, and residual systems, respectively. The first three conditions mean, simply, that an 3 vs t plot will be numerically identical with an S, vs t, plot,

Jan 1, 1957

By Ronald J. Roman

Research pertaining to flow of solutions in leach dumps has generally been neglected. This technical note proposes a method for evaluating the flow patterns and incorporating the results into dump-leaching models. Three dump-leaching models1-3 have been proposed to scale up laboratory test data to expected field results. These models are based on the same physical picture in a dump and differ only in the importance of diffusion or surface chemical reaction rate. Selection of this rate-controlling phenomemon is based on type of ore (sulfide or oxide), physical dimensions of the particles being leached, and the leach heap itself. All three models are applicable to specific types of operations. The models are similar in the use of a size distribution analysis for the dump material and the assumption that the leach solution flows around each particle. Transport of the leaching agent to the interior of the particle takes place by diffusion [(Fig. 1)]. However, normal dumps are of a higher bulk density than the material in a laboratory column used to generate the scale up data. How does this difference in bulk density affect the scale up equations? Increasing the bulk density can be expected to give more particle-to-particle contact; therefore, individual particles will be blinded by each other. As blinding increases with bulk density increase, the particles will behave like larger particles with a coarser apparent size distribution. The extreme will occur when the bulk density reaches that of the undisturbed rock, the entire dump behaving as a single particle with the dimensions of the heap itself. Harris4 alluded to this phenomenon in his paper. An alternative method of describing the same phenomemon is to consider the flow paths of the solution. At high bulk densities leach solution no longer surrounds each particle, but flow paths are separated by several particles and channeling is said to take place. Instead of the particle radius being the maximum distance through which the leaching agent must diffuse, the maximum distance is half the separation distance of the solution flow path. Particle size distribution must then be replaced in the models by the concept of channel separation distribution. Like size distribution, channel separation distribution specifies the cumulative percentage of the rock in the dump situated less than a specified distance from a solution channel. Thus, [ ] Distribution of the solution channels is a function of how the dump was built (among other things), and therefore it cannot be determined in the laboratory. Accordingly, it becomes necessary to determine a range for d and a in existing operations or measuring these parameters before leaching starts. Howard5 gives a clue to one possible technique of measuring solution channel distributions. When his paper was published little was known about the phenomemon of leaching; the importance of this type of data was not recognized. [Fig. 2] is a Y-Y log for one hole drilled

Jan 1, 1978

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 1-3 It is doubtful that this mechanism can ever he 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-commonly 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 atone down its chemical concentration gradient The first measurements of self-diffusion ii ere 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

Sec. 1. This Division shall be known as the Institute of Metals Division of the American Institute of Mining and Metallurgical Engineers. Sec. 2. The object of the Division shall be to furnish a medium of cooperation between those interested in the metallurgy, fabrication and uses of the nonferrous metals and their alloys; to represent the A. I. M. E. in so far as nonferrous metallurgy is concerned, within the rights given in A. I. M. E. By-law XI., Sec. 1, and not inconsistent with the Constitution and By-laws of the A. I. M. E.; to hold meetings for social intercourse and the discussion of nonferrous metallurgy; to stimulate the writing, presentation and discussion of papers of high quality on nonferrous metallurgy; to reject or accept such papers for presentation before meetings of the Division. Article II—MembeRs Sec. 1. Any Member, Associate, or Junior Associate of the A. I. M. E. in good standing may become a Member, Associate or Junior Associate of this Division upon registering in writing a desire so to do, but without additional dues. Sec. 2. But no one who has been continuously indebted to the A. I. M. E. or to this Division for more than three months shall be entitled to vote or to receive publications to which, as a member of the Division, he would be entitled. Article III—Funds Sec. 1. The expenditure of the funds reccived by the Division shall be authorized by the Executive Committee of the Division. Article IV—Meetings Sec. 1. The Division shall meet at the same time and place as the annual meeting of the A. I. M. E., and at such other times and places as may be determined by the Executive Committee subject to the approval of the Board of Directors of the A. I. M. E. Sec. 2. The annual business meeting for election of officers shall be held within a few days before or after the annual business meeting of the A. I. M. E. Sec. 3. At any meeting of the Division for which notice has been sent to the members of the Division through the regular mail at least one month in advance, a business meeting may be convened by order of the Executive Committee, and any routine business transacted not inconsistent with these By-laws or with the Constitution or By-laws of the A. I. M. E. Sec. 4. For the transaction of business, the presence of a quorum of not less than 25 members of the Division shall be necessary. Article V—Officers and Government Sec. 1. The officers of the Division shall consist of a Chairman, two Vice-chairInen, Secretary and Treasurer. The office of Secretary and Treasurer may be combined in one person, if desired by the Executive Committee. Sec. 2. The government of the affairs of the Division shall rest in an Executive Committee, in so far as is consistent with the By-laws of the Division and the Constitution and By-laws of the A. I. M. E. Institute of Metals Divisiori

Jan 1, 1931

By D. B. Jugle, J. B. Darby

The equilibrium solubility limits of the transition elements Ti, V, Cr, Fe, and Co in liquid tin were determined in the temperature range from 827" to 1211°K. Since the equilibrium concentration of Ti, V, or Cr in liquid tin is moderately dilute in the temperature range investigated, the solubility data were employed to estimate the partial molar enthalpy and the partial molar excess entropy of solution for the three solutes in liquid tin. The reference state s for titanium or vanadium were selected relative to the solute in an intermetallic compound. The thermodynamic quantities for chromium were calculated relative to pure chromium. RECENT experiments1 have shown that the rate of solution of several transition elements in liquid aluminum can be qualitatively predicted from a knowledge of the temperature dependence of the solvent-rich liquidus. In order to extend the analysis to binary tin systems,' it was necessary to know the equilibrium solubility of several of the first-long-period transition elements in liquid tin. Since solubility data for the tin-rich portion of binary systems are meager, the present investigation was undertaken to determine the equilibrium solubility limit of Ti, V, Cr, Fe, and Co in liquid tin in the temperature range from 850" to 1200°K. EXPERIMENTAL PROCEDURE A useful technique3 to determine the equilibrium solubility of a solute in a liquid-metal solvent consists essentially of placing a pure solute in contact with a pure solvent and allowing sufficient time for equilibrium to be attained at the temperature of interest. Subsequently, the solvent is removed and the equilibrium solute concentration in the solvent is determined by an appropriate analytical procedure. The technique can be applied very successfully to relatively simple systems such as the copper-germanium system.3 However, in many binary systems of transition elements with tin, several intermediate phases are known to exist and precipitation of the phases from solution, in solubility experiments, can lead to an erroneously large solubility. The difficulty was avoided in the present work by equilibration of the most solvent-rich intermediate phase with the pure solvent over a range of temperatures. The compounds employed in this investigation, and the temperature range over which each compound is in equilibrium with liquid tin are listed in Table I. No stable intermediate phases are reported in the chromium-tin system4 and, therefore, pure chromium was utilized as the solute. The stoichiometric compounds were prepared by arc-melting on a water-cooled copper hearth in a helium-argon atmosphere. The elemental tin employed in.this investigation was 99.998 pct pure, and typical lot analyses of the transition elements were reported elsewhere.' A sample of an appropriate solute, in the form of a button and in sufficient quantity to exceed the equilibrium solubility, and the pure tin solvent were placed in a high-purity recrystallized-alumina crucible. The crucible and contents were placed in a horizontal furnace under a high vacuum (10-6 torr) and held at temperature for periods varying between 24 and 72 hr. A water-cooled quench tank, partially filled with diffusion-pump oil, was attached close to one end of the

Jan 1, 1970