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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 J. J. McKetta, O. L. Culberson

INTRODUCTION The equilibrium constants for methane and for water, and for ethane and water have been calculated from experimental data for the two binary systems.2,3,11,12 These constants are for the two-phase systems for the temperature range of 100" to 340°F and the pressure range of 200 to 10,000 psia. The constants for ethane are greater than those for methane. Equilibrium constants for a natural gas from a natural gas-water system6 are about the same as those for methane. Equilibrium constants for water in all three systems are very nearly the same over the greater part of the range of temperatures and pressures studied. In ideal solutions, the vapor-liquid equilibrium constants for a component should be the same in all such solutions at a given temperature and pressure.5 Few solutions are ideal, and consequently the use of generalized constants often leads to error in situations where they do not actually apply. In decidedly non-ideal systems, it is desirable to have equilibrium constant data for the specific system. Vaporization equilibrium constants may be calculated either by thermodynamic methods or from experimental vapor-liquid equilibrium data. In the thermodynamic calculation. the equilibrium constant K may be shown to be" K = fP,/fl'..........(1) where fPi is the fugacity of the pure component i at the given temperature and at the vapor pressure of the pure component, and fp is the fugacity of pure i in the gaseous state at the temperature and total pressure of the system. At best the thermodynamic calculation results in a K applicable to ideal solutions. Equilibrium constants calculated from Equation (1) have been found to have only limited agreement with experimental values, even though the solutions for which they were calculated approached ideality."'" If the more volatile component is at a temperature above its critical, the accuracy of the equilibrium constant for the component is made more doubtful by the use of the vapor pressure term under such conditions. In order to make the thermodynamic calculation on a component above its critical temperature, one must resort to one of the empirical methods of extrapolation of the vapor pressure to conditions above its critical point.13 Application of the thermodynamic equilibrium constant then to the methane-water or the ethane-water systems would be risky since the systems are non-ideal, and the methane and ethane are above their critical in most petroleum operations. ETHANE-WATER SYSTEM In the temperature range of from 100° to 340°F and for pressures up to 10,000 psia, the vapor-liquid equilibrium data 'References given at end of paper. Manuscript received in the office of the Petroleum Branch March 16, 1951.

Jan 1, 1951

An Appreciation of Dr. Douglas by Dr. ALBERT R. LEDOUX The Bulletins of the American Institute of Mining Engineers and the program of the International Engineering Congress, held last September at San Francisco, called attention to an important feature in the pro¬ceedings of the Congress; viz., the public presentation to Dr. James Douglas of the John Fritz Medal, for notable achievements in mining, metallurgy, education. and industrial welfare. Dr. Douglas' health, unfortunately, did not permit of his taking the journey to California. While he had been willing that the bestowal of the medal should be a public ceremony, his natural modesty made him shrink somewhat from what he considered something of an ordeal, and he begged those who were to take part in it to use restraint in anything which they might have to say as to his work and attainments. It was, therefore, with some considerable satisfaction on his side that he learned that the medal would be given him without a public, ceremony in New York, or elsewhere. . On Dec. 5, 1915, the writer of this had the pleasure of handing him the medal, certificate, and official letters of transmittal, at his home at Spuyten Duyvil, where lie was surrounded by his children and grandchildren, with one or two of his most intimate friends. He begged the writer to return his thanks to the Committee of Award; and again to express the feeling that nothing in his career merited so great an honor. On this point all of the members of the Institute will share the writer's feeling that Dr. Douglas is too modest. James Douglas was born at Quebec, Canada, in November, 1837. His father Was a distinguished physician and surgeon, employing his skill in the field of philanthropy: He established the first retreat for the insane in the Dominion, to which lie. devoted himself up to the time of his departure from Canada, when it was taken over by the Government. The son spent 2 years in study at the University of Edinburgh, which lie entered in 1855. Returning to Canada, he graduated from Queens University, at Kingston, Ontario, with the degree of Bachelor of Arts, having also studied medicine, and later theology. After his graduation he traveled extensively with his father in Europe and in the Orient, visiting Egypt several time's. They returned with important archaelogical collections, which Dr. Douglas subsequently donated to the Metropolitan Museum of Art in this city. He then returned to Edinburgh, where he continued his course in medicine, surgery being perhaps his chief interest at that time. He was subsequently licensed to preach and his contemporaries bore testimony to his broad philanthropy and to the sympathy which dominated his every act. His taste was distinctly literary; he had carried off a prize at Edinburgh in English literature.

Jan 1, 1916

By C. Richard Tinsley

INTRODUCTION Project financing has been defined by various authors in this book. It is founded on reliance upon the project's own future cash flows and secondarily on the collateral value of the asset base developed. It is chiefly provided by the banking community who, after an assessment of the risks involved (See Chapter 9) analyse the company's presentation (See Chapter 10) in order to structure a financing package often at a leverage of up to 80% debt. This paper describes the various support and structuring techniques used to delimit and abate the risk components perceived from the banks' experience on project development especially for the period before cash flow is generated (pre completion). ADVANTAGES The advantages of project financing extend beyond the offloading of risks to banks. Among the advantages are the following: 1. Longer loan maturity than conventional, unsecured financing; 2. Loan disbursement and repayment tailored to specific mine; 3. Ability of a joint venture without a "track record" to raise financing; 4. Obtain financing where further direct borrowing (corporate credit) limited by existing indentures; 5. Possibility of arranging finance off-balance sheets; 6. Leverage return on equity; 7. Obtain tax savings with certain project financing structures; and 8. Obtain flexible loan repayment conditions. It can also be said that from the point of view of the company, project financing has certain disadvantages which can be summarised as follows: 1. Perceived higher cost (risk premium) compared with straight corporate credit; 2. More documentation; and 3. Need to negotiate risk-sharing aspects. The main attraction of project financing is the ability to pass certain risks on to the lenders within a flexibly funded transaction. (For a more detailed description of the specific risks see the author's paper at the beginning of Chapter 9. The same risk system is followed here.) The typical project financing has corporate support prior to completion and will usually carefully control the resultant cashflow after completion to ensure the bank does not unnecessarily assume further risks of an equity nature. WITHIN THE COMPANY'S CONTROL Operating Risk This is broken into three interrelated segments for ease of description. Technical Component: This must be specifically addressed if new technology or unproven adaptations are to be used. The banks will have scrutinized the sampling and bulk testing work, perhaps grilling the geological, mineral processing, metallurgical, and mining engineering staff or consultants directly. A number of supports are available such as: TECHNOLOGY GUARANTEE: Either the company itself or the process developer will guarantee that the technology will work for a period of, say, six months to two years after startup. If not, then financial penalties will apply although these are rarely sufficient to repay the loan. Many process developers are weak financially and may have little substance to back such a guarantee.

Jan 1, 1985

By Harmon D. Nine

DISCONTINUITIES in the strain vs cycles to failure (S-N) fatigue curves have been reported for polycrystalline materials by Porter and Levy for copper,&apos; by Benham and Ford for mild steel,&apos; and by Williams and Stevens for 18/5 stainless steel.3 However, the considerable scatter of the points for polycrystalline materials have made a statistical analysis of the data necessary to confirm the discontinuities. By using oriented single crystals of high-purity material and low grown-in dislocation content, the reproducibility has been improved to a degree which makes statistical analysis unnecessary and clearly shows discontinuities in the S-N curves. A recent publication4 reports an abrupt change of slope in the S-N curve for ( 100) axially oriented copper single crystals fatigued in torsion. The reported discontinuities in the S-N curve, along with a different mode of failure in the two branches of the curve, have been interpreted as being due to two different amplitude-dependent mechanisms. Further work on copper single crystals of (111) axial orientation has now been completed which supports the existence of an amplitude-dependent change in the mechanism of fatigue. In the present study torsional-fatigue experiments were performed at room temperature in air on (111) axially oriented single crystals. The crystals were grown and prepared as reported in Ref. 4. Two different methods of growing the crystals also discussed in Ref. 4 produced crystals of two different perfections: Type I with dislocation density of >l06 per sq cm and Type I1 with dislocation density of <l05 per sq cm. In accordance with the accepted hypothesis that crystal flaws are primarily responsible for the scatter of fatigue lifetimes, particularly at low amplitudes, the values for the three lowest amplitudes for Type I crystal are believed to be uncertain. They are marked in braces in Fig. 1. On the other hand, at amplitudes above a surface shear strain (SSS) of *0.003, the data for both types of crystals are in agreement. Most remarkably the S-N curve for torsional fatigue of (111)-oriented single crystals is composed of three segments separated by rather large discontinuities, Fig. 1. Metallographic and X-ray measurements indicate that the lower branch corresponds to the low-amplitude (F) region of the (100) copper single-crystal results as discussed in Ref. 4, and the two upper branches correspond to the high-amplitude (H) region. The lower discontinuity in the (111) S-N curve and metallographic evidence give further support to the hypothesis that different mechanisms of failure operate for high and low strain amplitudes. Reference to the resolved shear stress diagram, Fig. 2, shows that the highest stressed systems in

Jan 1, 1965

By B. N. Bose, M. F. Hawk

SINCE Davenport and Bain&apos; introduced the isothermal transformation technique for the study of austenite decomposition in steels, a new field of investigation has opened up. Extensive research has been carried out on many different steels, but relatively little work has been done on eutectoid transformations in analogous alloy systems. The researches of Smith and Lindlief,² Mack,³ and Klier and Grymko²0 on the beta-phase transformation in copper-aluminum alloys, of Hibbard, Eichelrnan, and Saunders4 and Smith5 on the kappa-phase transformation in copper-silicon alloys, of Chaudron and Forester6 on the decomposition of "FeO," and of Wasserman7 on similarities between the iron-carbon, copper-aluminum, copper-tin, and copper-beryllium systems essentially comprise the field. The iron-nitrogen system, in view of its remarkable similarity to the iron-carbon system, is particularly attractive for the study of eutectoid decomposition. The present investigation is concerned with the study of isothermal transformation, proceeding by the familiar nucleation and growth processes, and of martensitic transformation characteristics of pure iron-nitrogen alloys. The kinetics of transformation and the morphology of the transformation products have been investigated, for these must be the factors determining the properties and behavior of the final product. The Iron-Nitrogen System he binary iron-nitrogen phase diagram has been a matter of considerable disagreement among vari01.1s investigators. However, the phase diagram according to Eisenhut and Kaupp8 and Lehrer10 is now considered essentially correct as reproduced in fig. 1. The important values, 2.35 pct nitrogen and 591°C, for the co-ordinates of the eutectoid point (obtained from this diagram and used in the re- search to be described) were confirmed in a concurrent study of Paranjpe, Cohen, Bever and Floe." The eutectoid decomposition involves the transformation of the ? face-centered cubic interstitial solid solution of nitrogen in iron to the a body-centered cubic interstitial solid solution of nitrogen in iron and the ?&apos; nitride of iron. This nitride is essentially the compound Fe,N; it also possesses a face-centered cubic lattice but a considerably larger one than the ?; the nitrogen atoms in ?&apos; are arranged in an ordered way in the centers of the unit cubes.8,10,11 A martensitic structure has also been reported8,12 in iron-nitrogen alloys and was studied in the research to be described here. Materials and Methods The specimens used in this investigation were prepared by nitriding "pure" iron. This iron was supplied by the Westinghouse Research Laboratories and is the product bearing their trade name "Puron"; it contains about 0.04 wt pct total impurities, the major portion of which is oxygen. Specimens were ribbons several inches long, a tenth of an inch wide, and 0.125 mm thick; this was the

Jan 1, 1951

SOME days ago a visiting member from Pittsburgh who is an ardent supporter of the Institute remarked: "There are a lot of men who would be members of the Institute if it weren&apos;t so expensive. It is not so much the $15 dues as the $20 initiation fee. This makes quite a hurdle, especially for the younger fellows." A little further conversation developed the fact that the member had never learned of the changes in the By-laws regarding initiation fees and dues made by unanimous vote of the Board of Directors last November. As a great many others doubtless are unaware of these changes, the substance of two of the amendments is here repeated. They provide: (1) That the initiation fee for Junior Members (heretofore ten dollars) he abolished. (2) That the age limit for entrance as a Junior Member be increased from 27 years to 33; provided further, that the period during which the dues of a Junior Member are ten dollars shall be a maximum of six years but in no event shall extend beyond his thirty-third birthday. The Junior Member gets the identical privileges enjoyed by his seniors and he likewise assumes the same obligations with the sole exception of the financial payments. This one exception is justified by the fact that the engineers of more mature years, who are established in the profession, - are able and willing to assume a slightly greater financial burden. In effect, it is a small subsidy for the younger men; but these in turn will later enter the group of those that give instead of receive assistance. The practical result is that an engineer under 27 can obtain every privilege and benefit of membership for six years on the payment of only $10 per year without any initiation fee. A man of thirty can do the same for a period of three years. Incidentally, a candidate applying for membership (either as senior or junior) in the next few months need pay dues for the second half of 1935 only. A Junior Member -can be enrolled with an immediate outlay of only $5. The Institute does not seek-members indiscriminately merely to swell the number. These facts are not presented as a "bargain" offer in any sense. The standards for admission are high and are watched zealously. But it frankly-wants to give qualified men who can benefit from membership every encouragement to apply. Naturally, the Institute does not want lack of accurate information regarding initiation fees and -dues to be a stumbling block to any that are eligible and desirous of enrolling. Members are urged to take it upon themselves to clear up misapprehensions on this point, particularly among younger engineers.-Editorial reprinted from MINING AND METALLURGY, May, 1935.

Jan 1, 1935

By W. D. Robertson, D. A. Koss, A. J. Goldman

THE significance of the hcp (E) structure, which appears when Fe-Cr-Ni alloys (stainless steels) are transformed martensitically, has been the subject of considerable study and speculation.&apos;-7 It has been proposed that the hcp structure is an intermediate phase in the transformation: fcc (austenite) — hcp (E) -bcc (0, martensite). However, recent studies by transmission electron microscopy6,7 have indicated that the hcp structure may be a consequence of the large shear strain (10 deg) associated with the fcc to bcc transformation. That is, the transformation to a bcc structure is accompanied by extensive dissociation of dislocations in the parent austenite, which has a low stacking-fault energy.&apos;-&apos;&apos; X-ray diffraction analysis of the transformed alloy reveals a pattern of lines corresponding to an hcp structure, together with the parent austenite and the bcc product. The fact that the hcp structure is observed only in association with the bcc product in these alloys1&apos;4&apos;6&apos;7 lends support to the conclusion that the hcp structure is a secondary product of the transformation. But, the evidence is circumstantial and more definite resolution of the two possibilities mains to be obtained. If the hcp structure is an intermediate product of the transformation, as in 1) above, then two distinct Ms temperatures should be observed, Ms and To evaluate this possibility, three different techniques that are particularly sensitive to the structural changes accompanying such transformations have been used in an attempt to detect two transformation temperatures in an Fe-15.1 Cr-11.7 Ni alloy: 1) high-sensitivity differential thermal analysis, 2) the temperature dependence of resonant frequency (elastic moduli), and 3) internal friction of cylindrical specimens vibrating in either longitudinal or torsional modes. To obtain the necessary sensitivity, a differential thermal analysis technique was developed for the purpose, Fig. 1. The differential temperature between a nickel standard and the specimen was amplified to produce a sensitivity of 0.02OC (0.7 v) in temperature difference. The specimen and the standard were surrounded by a copper block and the entire assembly was immersed in a solution of methyl and ethyl alcohol, freezing point, - 140OC, which provided the necessary thermal stability to reduce temperature fluctuations to negligible proportions. A cooling rate of about 1.5OC per min was obtained by bubbling liquid nitrogen through the liquid bath. In order to calibrate the experiment with respect to the evolution of heat in the transformation from fcc to hcp structures, differential cooling curves were obtained for an Fe-19.8 Mn alloy, which transforms martensitically to E.&apos;"-&apos; a Ms(e) temperature of 145°C was clearly defined by a temperature

Jan 1, 1964

By G. E. Tardiff, A. A. Hendrickson

THE objectives of this communication are to present the solid-solution strengthening data for silver-base zinc single crystals and to evaluate the importance of strength contributions from several mechanisms through the use of this data combined with that for the silver-base aluminum case.&apos; Some features of the yield point behavior of silver-base zinc crystals were previously reported.&apos; Silver-base zinc alloys were prepared by induction melting 99.99 pct Ag with 99.9 pct Zn in high-purity graphite crucibles contained in argon-filled quartz tubes. After the first melting, the ingots were cut into short lengths, redistributed in the molds, and remelted in order to reduce solute-concentration variations. Alloy single crystals were then grown from the melt through the use of a modified Bridgeman technique which consisted of lowering the graphite crystal mold through a hot zone at a rate of 3/8 in. per hr. As in the melting operation, the molds were contained in argon-filled quartz tubes. Gage lengths 2 cm in length were introduced by both spark machining (circular cross sections) and abrading and acid etching (rectangular cross section) followed by electropolishing (a comparison of the critical resolved shear-stress values prepared by the two techniques showed no differences in strength values). The final cross-sectional areas of the crystals were approximately 5 sq mm. Prior to testing, the crystals were annealed at 600°C for 20 hr in argon atmospheres, furnace-cooled, and lightly electropolished. Crystal orientations were determined using the back-reflection method. The tensile testing was done on a Model FM Instron at a strain rate of 1(T4 per sec. Test temperatures of 77", 200°, and 400°K were attained by immersing the specimens in liquid nitrogen, dry ice-acetone mixtures, and silicone oil, respectively. The critical resolved shear-stress (CRSS) values for silver-base zinc crystals as a function of composition and testing temperature are given in Fig. 1. It will be noted that the CRSS for silver-base zinc solid solutions, as in the silver-base aluminum1 case, depends on temperature in a manner typical of fcc solid solutions: at high temperatures (-300°K and above), the CRSS is relatively temperature-independent but becomes strongly dependent on temperature at lower testing temperatures. A reasonable picture of solid-solution strengthening for silver-rich solutions at room temperature based on "direct" strengthening mechanisms3 is as follows. Since silver alloys have low stacking-fault energies, extended dislocations are expected and it is possible that Suzuki locking4 makes the major contribution to the room-temperature solute strengthening. This provides essentially temperature-independent strengthening since thermal motions of the dislocation line are not large enough to aid the dislocation in escaping the solute atmosphere extending over the fault width. An estimate of the

Jan 1, 1964

By Walter Showak

The published phase diagrams for the copper-zirconium system1,2 indicate that the solid solubility of zirconium in copper is not accurately known. Studies made on relatively impure alloys by Pogodin, Shumova, and Kugucheva3 yielded a maximum solubility value of 1 wt pct Zr at the eutectic temperature. Allibone and sykes5 reported that an as-cast 0.2 wt pct Zr alloy is single phase at room temperature. Limited results obtained by Raub and Enge14 indicated that zirconium solubility in copper is less than 0.13 wt pct Zr at 940°C. Tn 1960, on the basis of a microstructural examination of several copper-rich Cu-Zr alloys, saarivirta6 placed the maximum solubility of zirconium in copper at 0.15 wt pct at the eutectic temperature, 980°C. The present note describes results obtained during a re-investigation of the Cu-Zr system for the purpose of accurately establishing the solidus and solvus curves and the eutectic temperature in copper-rich alloys. High-purity copper (99.99 pet) and zirconium (99.64 pet) consolidated reactor grade sponge were used to prepare several alloys, containing up to 2 wt pct Zr, by induction melting in graphite crucibles in vacuum and chill casting into a split steel mold. The melting procedure consisted of first melting the copper charge and then adding the bulk zirconium wrapped in pure copper foil. Chemical analyses were made of both the cold-rolled alloy ingots after homogenization at 925°C for 450 hr in evacuated quartz capsules and of small specimens which had been used in the phase diagram studies. &apos;The carbon content of each alloy was also determined and was found to be less than 0.001 wt pct in every case. Metallographic and electrical resistivity measurements were used as the primary methods for this investigation, although some thermal analysis studies were also performed. Heat treatments of all the alloys were carried out with the specimens wrapped in molybdenum or alloy foil (of the same composition as the specimen) and sealed in quartz tubes either in vacuum or under a purified helium atmosphere. Following high-temperature anneals for long periods of time, slight depletion of zirconium from the specimen surface was observed. Therefore, careful preparation of samples for microscopic examination and chemical analysis of the samples themselves was necessary to check the composition of samples used in determining phase boundaries. Points on the solvus curve were determined on quenched specimens by both isothermal reaction after solution heat treatment at 950°C for 8 hr and by isothermal annealing of alloy specimens at successively higher temperatures for times ranging from 24 to 500 hr. Liquation studies for positioning of the solidus and eutectic temperatures were performed by holding a pre-

Jan 1, 1962

By P. W. Bakarian

PREVIOUS determinations1,2,3 of the texture of magnesium and its alloys have shown only slight variations in the principal features of the structure. This investigation presents pole figures for magnesium and two of its alloys, in which differences of some magnitude will be shown. Schmid and Wassermann have considered the texture of magnesium in analogy with that of zinc-also a hexagonal lattice. Whereas the zinc texture is said to be derived primarily through basal slip and secondarily through {102}† twinning, the {102} twinning is considered impossible at the later stages of the rolling in magnesium because of its smaller axial ratio. This state of affairs appears reasonable for pure magnesium, but for alloy textures the situation is more complex. A double orientation similar to that found in zinc has been reported by J. D. Hanawalt,4 and the addition of small amounts of calcium to magnesium and its alloys to produce a double texture was noted by J. C. McDonald.5 The pole figures of this investigation, using an improved X-ray technique, show these various textures. The dependence of directional properties of rolled sheet on modifications of texture is well recognized. Correlation of physical properties with existing texture should be even more significant if quantitative valuations are attached to the various areas on the pole figures. Such a quantitative technique is developed herein. EXPERIMENTAL METHOD Two alloys were used, besides high-purity magnesium. In each case, the metal was extruded to bars 32 in. thick and hot-rolled to a thickness of about 0.075 in. It had been established previously that such a reduction was more than sufficient to eliminate the extruded structure. The rolling proceeded in the same direction as that of the extrusion, without any cross rolling. The temperatures corresponded to normal commercial practice, averaging around 600°F. A unique method of preparing the sample was developed in this work. Instead of using a flat specimen, a stem of the metal was cut out of the rolled sheet in the desired direction (rolling direction) as shown in Fig. 2. From a sheet of 0.075 to 0.065-in. gauge, the stem was cut to a square cross section with a jeweler&apos;s saw, rounded with a file and polishing paper to a diameter of 0.060 in, and evenly etched in dilute hydrochloric acid to a diameter of 0.038 ± 0.001 in. In this way, a cylinder of the original sheet with its axis in the desired direction was produced. By using this type of specimen for the pin-point pictures, any variance in the absorption of the diffracted beam at the various angular settings of the specimen, was completely eliminated.*

Jan 1, 1941

By Herbert Hoover, Harlod Washburn

This paper is in the nature of a rough preliminary report on the progress that has been made in the application of the mass spectrometer to various problems arising in the petroleum industry. A few years ago the authors considered a number of the problems that were arising in the qualitative and quantitative measurement of small amounts of hydrocarbons. The methods available of making analyses by chemical techniques appeared to leave much room for improvement. Without going into the reasons at this point, attention was turned to the possibility of employing physical instead of chemical methods of accomplishing the desired results. A preliminary investigation disclosed that the mass spectrometer presented a possibility of solving many problems which could not easily be accomplished by other methods. Work was begun in developing the necessary apparatus and technique. A great deal of encouragement and many valuable suggestions were received from Dr. Robert A. Millikan, Dr. W. R. Smythe, and Dr. W. N. Lacey, of the California Institute of Technology, and from Dr. E. 0. Lawrence, who recently received the Nobel Prize, of the University of California. The authors particularly wish to acknowledge the very great willingness of these outstanding scientists to be helpful in solving many of the problems that were involved. So far as the authors are aware, this was the first application of the mass spectrometer to commercial work. The results were considerably better than had at first been anticipated. Briefly, it is possible to run a qualitative and quantitative analysis of an unknown mixture of hydrocarbon gases, with an accuracy of better than plus or minus 5 per cent of each of the various constituents. An exceedingly high degree of sensitivity has been obtained, and a relatively short time is required to complete an analysis. Furthermore, it is unnecessary to separate a mixture of gases into its various components in order to complete the analysis. The Mass Spectrometer The mass spectrometer should not be confused in any way with the optical 01 grating type of spectrograph now in general use. The operation of the mass spectrometer is entirely different in principle and bears practically no resemblance to the optical or grating instruments. The original conception and development of the mass spectrometer dates from and is generally credited to Aston, of Cambridge, England. An early accomplishment of his research, about 20 years ago, was the discovery that the inert gas neon was actually a mixture of two kinds of atoms, one of the atomic weight 20 and the other of atomic weight 22. These two components occurred mixed in such proportion as to yield the usual atomic weight of 20.2. The study was continued and most of the elements were shown to be mixtures of components whose atomic weights can, to in

Jan 1, 1941

By P. W. Bakarian

Previous determinationl,2,3 of the texture of magnesium and its alloys have shown only slight variations in the principal features of the structure. This investigation presents pole figures for magnesium and two of its alloys, in which differences of some magnitude will be shown. Schmid and Wassermann have considered the texture of magnesium in analogy with that of zinc—also a hexagonal lattice. Whereas the zinc texture is said to be derived primarily through basal slip and secondarily through {IO2}† twinning, the {102} twinning is considered impossible at the later stages of the rolling in magnesium because of its smaller axial ratio. This state of affairs appears reasonable for pure magnesium, but for alloy textures the situation is more complex. A double orientation similar to that found in zinc has been reported by J. D. Hanawalt,4 and the addition of small amounts of calcium to magnesium and its alloys to produce a double texture was noted by J. C. McDonald.5 The pole figures of this investigation, using an improved X-ray technique, show these various textures. The dependence of directional properties of rolled sheet on modifications of texture is well recognized. Correlation of physical properties with existing texture should be even more significant if quantitative valuations are attached to the various areas on the pole figures. Such a quantitative technique is developed herein. Experimental Method Two alloys were used, besides high-purity magnesium. In each case, the metal was extruded to bars 1/2 in. thick and hot-rolled to a thickness of about 0.075 in. It had been established previously that such a reduction was more than sufficient to eliminate the extruded structure. The rolling proceeded in the same direction as that of the extrusion, without any cross rolling. The temperatures corresponded to normal commercial practice, averaging around 600°F. A unique method of preparing the sample was developed in this work. Instead of using a flat specimen, a stem of the metal was cut out of the rolled sheet in the desired direction (rolling direction) as shown in Fig. I. From a sheet of 0.075 to 0.065-in. gauge, the stem was cut to a square cross section with a jeweler&apos;s saw, rounded with a file and polishing paper to a diameter of 0.060 in. and evenly etched in dilute hydrochloric acid to a diameter of 0.038 + 0.001 in. In this way, a cylinder of the original sheet with its axis in the desired direction was produced. By using this type of specimen for the pin-point pictures, any variance in the absorption of the diffracted beam at the various angular settings of the specimen, was completely eliminated.*

Jan 1, 1942

By W. T. Bishop

For many years pine oil has been used extensively as a frother for the flotation of minerals, particularly sulphides, yet the published information available to the average user on its composition, chemical and physical properties, has been rather meager. It is the purpose of this paper to discuss these points and their relationship to the frothing properties of pine oil used in flotation processes. Pine oil, as the name implies, is a liquid obtained from the processing of wood of the longleaf and other southern pines. It is a complex mixture of naturally occurring terpene derivatives, primarily alcohols, and a smaller amount of terpenes, which has found many uses in various industries. Its use as a frother in flotation processes was the first large-scale application in industry and today the mining industry still consumes large quantities of pine oil but the textile and disinfectant industries consume comparable volumes. Much is used in soap manufacture and laundry operations. The surface-active properties of pine oil are in a large degree responsible for this versatility. History The name "Naval Stores" goes back to the days when pine tar and pitch were used to caulk leaky ships and &apos;Oat their ropes and rigging. Today this term is still used to include not only the oleoresinous products of the pine tree—rosin and turpentine— but other products such as pine oil, pine tar, and the many terpene and resinous compounds obtained by extracting the pine wood or tapping the tree. That part of the industry known as "wood naval stores" dates from about the beginning of this century and today produces a large part of the country&apos;s rosin and turpentine by processing pine wood. In addition, all of our natural pine oil is supplied by the wood naval stores industry, as tapping of the live tree gives only rosin and turpentine. This latter phase is known as the "gum naval stores " industry. The first successful commercial operation of the steam and solvent process of the wood naval stores in industry was carried out by Yaryan at Cadillac, Mich., in 1909.1 This operation did not prove profitable, so Yaryan went south to utilize the longleaf pine, and built a plant at Gulfport, Miss.2 Soon after, another plant was built at Brunswick, Ga., which is still in operation, and in 1914 was reported to have processed about 500 tons of wood per day.&apos; In 1921 Hercules Powder Co. acquired the Yaryan interests, at which time the production of pine oil was only 3 to 5 million pounds per year and flotation was the largest customer. As time went on, technological advances were made, other companies entered the field, and the production of pine oil increased many fold. The growth of the industry was especially marked during the past 10 years, and in

Jan 1, 1947

By Harlod Washburn, Herbert Hoover

This paper is in the nature of a rough preliminary report on the progress that has been made in the application of the mass spectrometer to various problems arising in the petroleum industry. A few years ago the authors considered a number of the problems that were arising in the qualitative and quantitative measurement of small amounts of hydrocarbons. The methods available of making analyses by chemical techniques appeared to leave much room for improvement. Without going into the reasons at this point, attention was turned to the possibility of employing physical instead of chemical methods of accomplishing the desired results. A preliminary investigation disclosed that the mass spectrometer presented a possibility of solving many problems which could not easily be accomplished by other methods. Work was begun in developing the necessary apparatus and technique. A great deal of encouragement and many valuable suggestions were received from Dr. Robert A. Millikan, Dr. W. R. Smythe, and Dr. W. N. Lacey, of the California Institute of Technology, and from Dr. E. 0. Lawrence, who recently received the Nobel Prize, of the University of California. The authors particularly wish to acknowledge the very great willingness of these outstanding scientists to be helpful in solving many of the problems that were involved. So far as the authors are aware, this was the first application of the mass spectrometer to commercial work. The results were considerably better than had at first been anticipated. Briefly, it is possible to run a qualitative and quantitative analysis of an unknown mixture of hydrocarbon gases, with an accuracy of better than plus or minus 5 per cent of each of the various constituents. An exceedingly high degree of sensitivity has been obtained, and a relatively short time is required to complete an analysis. Furthermore, it is unnecessary to separate a mixture of gases into its various components in order to complete the analysis. The Mass Spectrometer The mass spectrometer should not be confused in any way with the optical 01 grating type of spectrograph now in general use. The operation of the mass spectrometer is entirely different in principle and bears practically no resemblance to the optical or grating instruments. The original conception and development of the mass spectrometer dates from and is generally credited to Aston, of Cambridge, England. An early accomplishment of his research, about 20 years ago, was the discovery that the inert gas neon was actually a mixture of two kinds of atoms, one of the atomic weight 20 and the other of atomic weight 22. These two components occurred mixed in such proportion as to yield the usual atomic weight of 20.2. The study was continued and most of the elements were shown to be mixtures of components whose atomic weights can, to in

Jan 1, 1941

By P. W. Bakarian

Previous determinationl,2,3 of the texture of magnesium and its alloys have shown only slight variations in the principal features of the structure. This investigation presents pole figures for magnesium and two of its alloys, in which differences of some magnitude will be shown. Schmid and Wassermann have considered the texture of magnesium in analogy with that of zinc—also a hexagonal lattice. Whereas the zinc texture is said to be derived primarily through basal slip and secondarily through {IO2}† twinning, the {102} twinning is considered impossible at the later stages of the rolling in magnesium because of its smaller axial ratio. This state of affairs appears reasonable for pure magnesium, but for alloy textures the situation is more complex. A double orientation similar to that found in zinc has been reported by J. D. Hanawalt,4 and the addition of small amounts of calcium to magnesium and its alloys to produce a double texture was noted by J. C. McDonald.5 The pole figures of this investigation, using an improved X-ray technique, show these various textures. The dependence of directional properties of rolled sheet on modifications of texture is well recognized. Correlation of physical properties with existing texture should be even more significant if quantitative valuations are attached to the various areas on the pole figures. Such a quantitative technique is developed herein. Experimental Method Two alloys were used, besides high-purity magnesium. In each case, the metal was extruded to bars 1/2 in. thick and hot-rolled to a thickness of about 0.075 in. It had been established previously that such a reduction was more than sufficient to eliminate the extruded structure. The rolling proceeded in the same direction as that of the extrusion, without any cross rolling. The temperatures corresponded to normal commercial practice, averaging around 600°F. A unique method of preparing the sample was developed in this work. Instead of using a flat specimen, a stem of the metal was cut out of the rolled sheet in the desired direction (rolling direction) as shown in Fig. I. From a sheet of 0.075 to 0.065-in. gauge, the stem was cut to a square cross section with a jeweler&apos;s saw, rounded with a file and polishing paper to a diameter of 0.060 in. and evenly etched in dilute hydrochloric acid to a diameter of 0.038 + 0.001 in. In this way, a cylinder of the original sheet with its axis in the desired direction was produced. By using this type of specimen for the pin-point pictures, any variance in the absorption of the diffracted beam at the various angular settings of the specimen, was completely eliminated.*

Jan 1, 1942

By W. T. Bishop

For many years pine oil has been used extensively as a frother for the flotation of minerals, particularly sulphides, yet the published information available to the average user on its composition, chemical and physical properties, has been rather meager. It is the purpose of this paper to discuss these points and their relationship to the frothing properties of pine oil used in flotation processes. Pine oil, as the name implies, is a liquid obtained from the processing of wood of the longleaf and other southern pines. It is a complex mixture of naturally occurring terpene derivatives, primarily alcohols, and a smaller amount of terpenes, which has found many uses in various industries. Its use as a frother in flotation processes was the first large-scale application in industry and today the mining industry still consumes large quantities of pine oil but the textile and disinfectant industries consume comparable volumes. Much is used in soap manufacture and laundry operations. The surface-active properties of pine oil are in a large degree responsible for this versatility. History The name "Naval Stores" goes back to the days when pine tar and pitch were used to caulk leaky ships and &apos;Oat their ropes and rigging. Today this term is still used to include not only the oleoresinous products of the pine tree—rosin and turpentine— but other products such as pine oil, pine tar, and the many terpene and resinous compounds obtained by extracting the pine wood or tapping the tree. That part of the industry known as "wood naval stores" dates from about the beginning of this century and today produces a large part of the country&apos;s rosin and turpentine by processing pine wood. In addition, all of our natural pine oil is supplied by the wood naval stores industry, as tapping of the live tree gives only rosin and turpentine. This latter phase is known as the "gum naval stores " industry. The first successful commercial operation of the steam and solvent process of the wood naval stores in industry was carried out by Yaryan at Cadillac, Mich., in 1909.1 This operation did not prove profitable, so Yaryan went south to utilize the longleaf pine, and built a plant at Gulfport, Miss.2 Soon after, another plant was built at Brunswick, Ga., which is still in operation, and in 1914 was reported to have processed about 500 tons of wood per day.&apos; In 1921 Hercules Powder Co. acquired the Yaryan interests, at which time the production of pine oil was only 3 to 5 million pounds per year and flotation was the largest customer. As time went on, technological advances were made, other companies entered the field, and the production of pine oil increased many fold. The growth of the industry was especially marked during the past 10 years, and in

Jan 1, 1947

By R. P. Carreker, J. G. Leschen, J. H. Hollomon

THE external appearance of a crystal which has undergone plastic flow suggests that adjacent blocks of the crystal have glided bodily past one another along the slip planes. However, the great discrepancy between the shear stresses calculated to effect such a movement and those actually observed has for many years stimulated searches for more satisfactory interpretations of the slip process. Appreciable success in these efforts has been realized by assuming the presence in the crystal of various sorts of imperfections and by considering the consequences of the presence of these flaws when stress is externally applied, The theory that has received the most attention recently-that of dislocations-postulates the occurrence of small, mobile imperfections or dislocations which move through the crystal along the slip direction, each dislocation being attended by a local shear displacement of one interatomic distance. Thus only that portion of the crystal through which the dislocation has passed may be said to have slipped, Since each dislocation produces a displacement of only one interatomic distance, an avalanche or train of many dislocations would be necessary to account for the observed displacements of several hundred or thousand interatomic distances. The salient point of the theory of dislocations is the concept that a slip band does not suddenly appear in its entirety. On the contrary, it grows progressively across the slip plane as the individual dislocations successively appear and advance in a train through the crystal. However, the concept of growth is not intrinsic only to the theory of dislocations, since atomistic mechanisms other than that postulated by the dislocation theory can quite probably also describe the growth of a slip band. For instance, a slip band might resemble a disc-like interface that appeared and then grew continuously from a small size, producing a displacement that increased with the size of the disc, Whatever the precise mechanism, the concept of growth is in itself consistent both with -the observed low values of critical shear stress and with the experimental observation that slip bands. frequently do not traverse the entire crystal. The likelihood that slip bands grow implies that they must first be nucleated and that the initiation of slip can therefore be analyzed in terms of the general concepts of nucleation. Indeed, this suggestion was advanced1 several years ago, but the matter does not appear to have been further pursued. Recent advances in the theory of nucleations2,3,4 have encouraged such a treatment of the slip process. As will presently be demonstrated, this approach to the problem not only accounts successfully for the incubation periods that have been observed5,6 to precede slip but also predicts certain transient effects in the deformation process, The existence of these transients apparently has not hitherto

Jan 1, 1948

By E. F. Johnson, F. H. Brinkman, H. J. Welge, S. P. Ewing

This paper presents a method for predicting the manrler in which oil will be displaced from a porous body by enriched gas. The calculations apply to a gas rich enough to give a partially, but not a completely, misci-ble displacement. The method — a three-component, two-phase analysis — takes into account condensation of some of the intermediate hydrocarbons from the injected gas into the oil, as well as enhanced volatility of heavier hydrocarbons at elevated pressures and temperatures. The condensation swells the oil and decreases its viscosity, thus aiding in its recovery. The calculations have been extended to apply to actual crude oil-natural gas systems by arranging the components into three groups according to their volatility. As an approximation, each group is then treated as a single component in the analysis. The influence of an angle of dip for an inclined displacement is also taken into account. The recovery predictions are corroborated by experiments which used both consolidated sand cores and un-consolidated glass beads. In some of these tests, actual live crude oil was displaced by a multicomponent gas typical of enriched gases used in oil fields. INTRODUCTION This paper presents a method for predicting the amount of oil that can be displaced from a homogeneous, linear, porous body at various stages during the injection of enriched, or "wet", gas. The porous body can be in either a horizontal or an inclined position. &apos;This type of displacement is sometimes known as condensing gas drive The method is developed especially for the case in which the injected gas is enriched enough to be partially, but not completely, miscible with the reservoir oil. The need for a calcula-tive procedure for this type of operation is emphasized by the number of field projects where completely miscible drives are not practical, but where near-miscible conditions are feasible. The factors taken into account in the predictive calculations include: (1) the condensation of gas components into the oil, with a resulting increase in oil volume; (2) the lowering of oil viscosity by the addition of lighter ends from the gas; (3) the increase in oil volatility at high temperatures and pressures; and (4) the physical displacement of the oil by the gas. The techniques developed in the paper can be extended to other nonequilibrium displacement processes. Other such processes that we have analyzed include a displacement by lean gas which stripped intermediates from the oil, and a water flood in which the water con. tained in solution a substance somewhat soluble in the oil. ANALYSIS OF ENRICHED-GAS DRIVE GENERAL PRINCIPLES Our method for predicting the amount of oil that can be displaced by an enriched gas uses an analogy between a three-component and a multicomponent system.&apos; The predictive method is based on these assumptions: (1) constant, or nearly constant, pressure; (2) complete equilibrium by diffusion perpendicular to the main direction of flow, but no significant mixing along the direction of flow; (3) constant injection velocity; and (4) flow in a linear porous body. The composition of a liquid or a vapor with respect to three components can be plotted on a three-component, or ternary, diagram like that in Fig. 1. Let Point A represent the composition of the oil originally in place. In this case, Oil A is undersaturated with gas. If Point A lay on the equilibrium Curve BF, the oil would be saturated. In the extreme case where the original oil contained no intermediates or dissolved gas, Point A would lie at the lower left-hand corner of the ternary diagram. In a displacement of Oil A by Gas D, there will be a progressive change in the composition of the oil phase as more and more gas is brought into equilibrium with the oil. The end result of this progressive change is an oil having the composition represented by Point F. This oil is richer in intermediate hydrocarbon and methane than the original oil and, therefore, has a greater forma-

By J. N. Breston, R. V. Hughes

Conclusions drawn by previous research workers with reSPect to the relation between Pressure gradients and/or velocity and oil recovery obtained by laboratory water flood tests have been in disagreement probably due to variable procedures and unnatural conditions and materials. The Bradford Laboratory of the Pennsylvania Grade Crude Oil Association as part of its secondary recovery research program has conducted nineteen water floods on two long cores of widely differing characteristics in an attempt to clarify this relationship and make it an aid in predicting flooding pressures in the field. Unlike previous research procedures the present experiments were conducted with the aim of duplicating field conditions as closely as possible by using long unextracted consolidated cores, a live crude, and natural brines for both flooding and, connate water content. Also, the pressure gradients and flooding velocities were representative of field conditions where similar sands were being flooded. Eleven floods on one core and eight floods on the other core showed increased recoveries and lower residual oil saturation with increased flood pressure gradients and flood velocities. A marked decrease in recovery was obtained from both cores at very low flood velocities. This pressure versus recovery relationship is shown to hold up to the point of water breakthrough and also up to the 100 and 1 produced water to oil ratio point. INTRODUCTION The possibility of water flooding oil sands was suggested by Carl1 of the Pennsylvania Geological Survey in 1880. It is not known when the practice was tried intentionally for the first time, but its beneficial effects were noted in the annual production rate of the Bradford field as early as 1907. The practice was illegal in Pennsylvania until 1921. Early water floods in the Bradford field usually consisted of shooting or splitting the casing secretly to permit subsurface waters to enter the producing sands under hydrostatic head. As it was noted that the benefits of water flooding seemed to be proportional to the quantity of water dumped into the well many also began to utilize surface sources after the practice became legal. It was probably during the middle 20&apos;s before many producers realized that the pressurehead of the water upon the producing sand determined the rate and quantity of water that would enter the sand. Hence, rate and quantity of production appeared to be a direct function of input pressures. By 1927 a few producers had ventured the installation of pressure pumps in order to increase water-input rates and production through the combination of hydrostatic and hydraulic pressures. The adoption of pressure flooding and the "five-spot" drilling pattern in the Bradford field were essentially simultaneous. Water-input pressures in 1930 seldom exceeded 300 p.s.i. at the well head or 1100 p.s.i. at the sand face. Since that time, water-flood producers in the Bradford-Allegany fields have gone to higher and higher pressure until today 600 p.s.i. at the well heads is called a low pressure flood. Many high pressure floods now operate at 1300-1400 p.s.i. at the well head. The limiting and advisable pressure at the sand face has been pronounced as that pressure just under what is required to lift the overburden or to cause formation parting: According to this rule any water flood operation utilizing well-head pressures nearly equal in pounds per sq. in. to 1.1 times the average depth in feet to the top of the producing sand would be considered as a high-pressure flood. Despite the higher pressure trends in the Bradford-Allegany field operations and the results of early laboratory water flooding research, the desirability and benefits of high input pressures are still questioned by many operators, particularly in midwestern water flood operations. The present paper recounts a series of 19 laboratory water floods using two long, consolidated cores of widely differing characteristics saturated with live crude and flooded with oil field brines in an effort to simulate field conditions under • various pressure gradients and flooding velocities. For both cores, higher recoveries and lower residual oil saturations were obtained at higher pressure gradients and flood velocities. This relationship is shown to hold up to the water breakthrough point and also up to the 100 to 1 produced water to oil ratio point.

Jan 1, 1949