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By A. B. Cook, C. J. Walker, G. B. Spencer

Although water will displace oil from a petroleum reservoir to a greater extent than gas will, there are some reservoirs in which gas rather than water should be used for pressure maintenance. This is indicated by the high-percentage oil recovery in the case history reports on the Pickton field1 in East Texas and the Raleigh field2 in Mississippi. In gas cycling, total oil recovery includes vaporized products from the immobile oil in addition to oil produced by displacement. If a large part of the immobile oil is vaporized, total oil recovery may be higher than that obtainable from pressure maintenance by water injection. However, the amount of immobile oil vaporized may range from almost 0 to 100 percent, and no simple and reliable method has been presented in the literature for calculating oil vaporization. Development of such a method was the purpose of this study. Several papers concerning the calculation of oil vaporization have been published,3 6 and each is based on the concept dealing with K values — equilibrium constants for the various components in reservoir oils. (K for a component in a system of vapor and liquid in equilibrium is the mole fraction in the vapor phase divided by the mole fraction in the liquid phase.) This appears to be the most logical approach. Yet, the problem is too great for a perfect solution, even with modem laboratories to analyze oils and high-speed digital computers to perform calculations; the number of components in reservoir oils is too large. Because of their complexity no two reservoir oils are exactly alike. Also, K values change not only with variations in pressure and temperature but also with composition of the reservoir oil. In addition, during gas cycling, the lighter hydrocarbons tend to vaporize first. Thus, the reservoir oil becomes more dense and less volatile as gas cycling continues. Furthermore, the greatest amount of oil vaporization occurs near the injection well. Therefore, a simplified method is required for calculating oil vaporization because a rigorous method is not practical. The present methods of calculating vaporization generally require knowledge of the reservoir oil composition in which the mole fractions of the lighter components through hexanes are given; the remaining oil is described as C, + (heptanes and others of greater molecular weights). Assigning one K value for the C,+ system provides the simplest solution, but this incorrectly assumes that K for C, + does not change as gas cycling continues. This assumption can cause large errors because the K value may become less than a thousandth of the original after a large amount of oil vaporization. Another way to solve the problem is to determine changing K values for C, + according to how much of the C, + has been vaporized. To determine these values a sample of the reservoir oil is injected into a pressure-volume cell, and dry gas is batched in and out of the cell. Appropriate measurements and tests are made to determine K

Jan 1, 1970

By D. M. Boulin, E. S. Greiner

Single crystals of vanadium were bent at 293" and 77°K to a maximum fiber strain of about 1 pct. Analysis of slip line and etch markings of- crystals deformed at either temperature show the slip planes are {112}. The slip directions at 298° and 77°K, deterwined from the asterism axes of rotation of crystals compressed in a {110} direclion, were (111). Etch pits, associated with dislocations, were observed in the plastically deformed vanadium. There was no evidence of mechanical twinning. THIS paper presents results on single crystals of vanadium plastically deformed by bending and compressing at 298° and 77°K. Bcc metals have been observed to slip on {110}, (1121, and (123) planes while the slip direction has invariably been found to be ( 111) 1 Lindley and smallman2 have studied the deformation intension of polycrystalline vanadium between 298° and 20°K and reported that at and above 77°K the deformation is predominantly by slip, but at 20°K the deformation is associated with twinning. Later, Edington and smallman3 found that single crystals of vanadium compressed in a (111) direction at 77°K deformed by twinning on { 112}( 111) systems. Clough and pavlovic4 have reported that mechanical twins were observed in vanadium loaded by impact at 77°, 173°, and 195°K, respectively. PREPARATION OF SINGLE CRYSTALS The vanadium single crystals were made from commercial vanadium reported to contain 0.03 pct C, 0.03 pct 0, 0.02 pct N, 0.0X* pct Ca, 0.0X pct Si, proximately 0.8 cm diam, 4 cm long and were grown in (100) and (110) directions. A crystal for studies of etch pits was gound to have a face parallel to a {l00} plane by the Bond crystal-orienting technique.7 In order to avoid straining, the crystals were placed on the steel mount with a low-melting organic compound (glycol phthalate) before grinding. Crystals for the bending experiments were ground to have the four side faces parallel to ( 100) planes. The crystals were electropolished8 in 10 pct H2So4 using a current density of about 3 amp per sq cm to remove the strained surface material. The crystals were bent slowly by three-point loading in a stainless-steel jig designed by Sylwestrowicz.9 The end rollers of the jig were 3.8 cm apart. DEFORMATION AT 298°K The bent vanadium crystal, after removal from the jig, had a radius of curvature of 20.4 cm over the 2-cm length close to the center loading roller, where the maximum bending moment occurred. This radius of curvature corresponded to a maximum fiber strain of 0.9 pet. The side faces contained slip bands as shown in Fig. 1. These bands are straight where the strain is high, top and bottom of micrograph, but are curved on either side of the neutral axis in the center. This curvature of the slip bands in the low-stress area may be due to cross slip. The plastically deformed crystal was subsequently electropolished and then electroetched in 10 pct H2SO4 solution, using a current density of 0.25 amp per sq cm. The structure is shown in Fig. 2. The directions of the traces on two adjoining faces were plotted stereo graphically, Fig. 3.* Since there were two sets of

Jan 1, 1968

Iowa State College Ames, Iowa Iowa State Mining Society CARL S. NELSON, President NORMAN S. GEIST, Secretary K. A. PHILLIPS, Faculty Sponsor C. G. DRESSER, Counselor University Of Kansas Lawrence, Kansas University of Kansas Student Chapter of A.I.M.E. WALTER CROOK, President EDWARD C. MISHOU, Secretary E. A. STEPHENSON, Faculty Sponsor GEORGE M. FOWLER, Counselor K. A. SPENCER, Counselor .

Jan 1, 1942

By R. J. Wasilewski

The resistivity of single crystal and of polycrystalline metal has been determined between 77° and 1500°K. At comparable purity, the resistivity of the poly crystalline metal differs from that calculated from the axial resistivity values. The observed anisotropy is briefly discussed. A zone refined titanium rod was obtained from F. J. Darnell.1 The hardness of this material varied between 52 and 64 Bhn, indicative of its high purity. Single-crystal specimens were cut out from a few large grains, elongated predominantly along <1120>. Resistance measurements were taken with specimens immersed in liquid nitrogen, solid CO,, and acetone, and at ice point, and then recorded continuously between room temperature and 1200" to 1250°C, throughout at least one full heating and cooling cycle at a rate of l° to 3°C per min. Four probe measurements were taken using spot-welded Pt wire 0.003 in. in diam as potential terminals, and the electromotive force drop was determined poten-tiometrically. A standard resistance, in series with the specimen, served to determine the dc current (generally about 80 ma) in the circuit. In order to eliminate spurious thermal electromotive forces, the circuit polarity was automatically reversed at 5-min intervals, and the mean of the two adjacent readings taken as the true electromotive force value. The discrepancy between the readings at reversed polarities was generally of the order of a few µ v, as all the spot-welded joints were contained within a volume of some 5 mm cube. The relative resistance (R T/R 273o) variation with temperature is tabulated below, and shown in Fig. 1, as measured during the first heating run. The discontinuous drop in resistance, corresponding to the a — ß transformation, started for both initial orientations at 1170°K; i.e., some 15°K above the accepted value of 882°C (1155°K). Judging by the temperature ranse of transformation—some 30°K for the single crystal and 20°K for the polycrystal-line specimen—this difference is believed caused by the solution of the oxygen present initially on the surface of the specimens. The general trend of the resistance vs temperature shown in Fi,;. 1 is in qualitative agreement with that previously reported for polycrystalline titanium metal. 2,3 Significant anisotropy is, however, indicated by the crossing over of the curves for <1120> and <0001> orientations at 273°, 650°, and 1000°K. This difference is most startlingly shown in Fig. 2, where instantaneous temperature coefficients (l/R273 x dR /dT) are plotted for both the first heat-

Jan 1, 1962

By H. H. Kellogg

Available high-fernperatzwe equilibrium measurements and other thermochernical data have been critically reciewed for sulfation reactions of the type: Recommended values for log K and ?Fo as junctions of temperature are given for thirty-six suck reactions involving twenty-six different metals. Methods of calculation and choice between conflict-ing data are discussed. SELECTIVE sulfation now enjoys a considerable renaissance as a metallurgical unit process due, in large part, to the available of the fluid-bed re- actor—a device capable of the close control of temperature and gas composition necessary for a successful sulfation process. An additional need, however, if sulfation chemistry is to be approached in a scientific manner, is a reliable body of data on the equilibrium and kinetics of sulfation reactions in simple and complex systems. This paper offers a critical review and compilation of equilibrium data on pure sulfates (simple systems). The last such review, by K. K. Kelley in 1935:30 has proven itself most useful, but the existence of many new data makes necessary a re-evaluation of the available information. METHODS OF CALCULATION For a simple sulfation reaction such as MS04(c) = MO(c) + SO3 [1] there are two approaches one may take toward establishing the value of ?Fo or K as a function of

Jan 1, 1964

Discussion of the paper of George K. Burgess, J. J. Crowe, H. S. Rawdon, and R. G. Waltenberg, Finishing Temperatures and Properties of Rails. By Albert Sauveur, R. Trimble, William R. Webster, P. H. Dudley, George B. Waterhouse, M. H. Wickhorst, James Aston, E. F. Kenney, A. W. Gibbs, W. A. Aiken, and G. K. Burgess . . 767 Discussion of the paper of Albert Sauveur, Manganese Steel and the Allotropic Theory. By G. K. Burgess and J. E. Stead 787 Discussion of the paper of J. V. Emmons, The Surface Decarbonization of Tool Steel. By Albert Sauveur, Bradley Stoughton, E. G. Spilsbury, Oliver W. Storey, H. O. Hofman, and J. V..Emmons 790 Discussion of the paper of Richard H. Rice, Turbo Blowers for Blast-Furnace Blowing. By S. G. Valentine, W. McA. Johnson, L. Iversen, J. E. Johnson, Jr., Karl Nibecker, W. Trinks, Otto Banner, H. S. Braman, Arthur G. McKee, and Richard H. Rice . . . 794 Discussion of the paper of J. K. Furst, The Plant of the Duplex Process for Making Steel. By W. McA. Johnson, Arthur G. McKee, Henry D. Hubard, and Bradley Stoughton . . 810 Discussion of the paper of E. C. Harder, The Iron Industry in Brazil. By I. C. White and E. C. Harder 813

Jan 4, 1915

By H. M. Chance

The Taviche district is about 12 miles from the town of Ocotlan in the State of Oaxaca, and about 250 miles south of the City of Mexico. Its altitude rises to something more than 5,000 ft.; and although within the tropics (latitude about 17° N.) the climate is mild and salubrious, neither excessively hot in summer nor cold in winter. The phrase, "perpetual spring," which has been applied to it, aptly describes the weather during my stay. Sugar-plantations, bananas and other tropical and semitropical fruits flourish in the valleys, while the hills

Jan 1, 1905

By Olaf Hondrum

CHURN drilling equipment at Bagdad consists of two Bucyrus Erie 27-T model drills and one 22-T drill with gasoline engines. The drilling tools weigh approximately 1600 lb. The holes are drilled with 7-in. bits which are heated in an oil burning furnace and sharpened in an electrically powered bit sharpener. A service truck brings the bits to the drills and takes the dull bits back to the shop. The bits weigh around 250 lb. when new and are handled by drill crews without any mechanical handling device.

Jan 10, 1950

(Under this heading will be published notes sent to the Secretary of the Institute by members or other persons introduced by members.) No. 488.-Mining engineer, member, technical graduate, married, age 38, desires position of superintendent or assistant superintendent. Has had 15 years&apos; practical experience as miner, millman, machinist, surveyor, engineer, foreman, and superintendent in the West, Southwest, and Mexico. Speaks Spanish. Now employed as superintendent of copper property in Southwest. Can give the best of references. Minimum salary $250. Available after Sept. 1. No. 495.-Member, age 36, married, technical, 10 years&apos;. all round

Jan 12, 1918

By C. Fairhurst, B. C. Haimson

Pink Tennessee Marble was tested for wedge bit penetration characteristics at static and dynamic (10 - 250 ft/sec) loading rates. No significant differences were found within the dynamic range as far as the energy required to remove a unit crater volume and the force used to cause a certain penetration. Under static loading, however, both the energy and the force required were significantly lower. Tests run on bits of varying width indicated that as the wedge bit narrowed to an almost conical shape, the energy used per unit crater volume became considerably lower.

Jan 1, 1971

By Henry Seltz, Cyril Wells, Hugh J. MacDonald

Several investigators have measured the heat capacity of cementite, using different methods of attack, but the agreement between the values obtained cannot be considered good. Naeserl has made measurements of "average heat capacities" of iron carbide between 1026" and 85" K., using a water calorimeter. His computed true specific heat at 78.1" K. is 11.22 cal. per gram-formula mass, which, if correct, is much too high for any reasonably accurate extrapolation to 0" K. The cementitc used by Naeser was obtained from a steel containing 0.9 per cent carbon, by electrolytically dissolving out the iron in a neutral bath of ferrous chloride. The cementite remained as a coarse, crystalline, gray powder. Andes2 has measured the specific heat of iron carbide, from 102" to 323" K., as it exists in steel. The specific heats of several slugs of steel of known iron carbide content were determined, and the specific heat of the iron carbide (Fe3C) calculated by plotting specific heat versus percentage of carbon, and extrapolating to pure Fe3C (6.7 per cent C). The heat-capacity values for temperatures below 100" K. were obtained by comparing the temperature-specific heat curve for Fe3C to that of Fe. Since the two were very similar in the range examined experimentally and approach more closely at low temperatures, it was assumed that near the absolute zero the form of the curve for Fe3C would be similar to that of Fe. Andes calculates for the entropy of Fe3 C,S298 = 23.55 e.u. The heat of formation of Fe3C has been studied by several workers. Kelley3 has reviewed these measurements and calculations, and selects those of Roth* and Naeser6 as worthy of most consideration. Roth has given AH = 5400 cal. + 30 per cent as a result of his own and other work. Naeser has determined the heat of formation from Fe and different forms of carbon, and for graphite (0) he finds AH = 5600 cal. Kelley accepts the rounded figure AH = 5500 as the heat of formation at 298.1" K., but this value is quite uncertain.

Jan 1, 1940

By Henry Seltz, Hugh J. MacDonald, Cyril Wells

Several investigators have measured the heat capacity of cementite, using different methods of attack, but the agreement between the values obtained cannot be considered good. Naeserl has made measurements of "average heat capacities" of iron carbide between 1026" and 85" K., using a water calorimeter. His computed true specific heat at 78.1" K. is 11.22 cal. per gram-formula mass, which, if correct, is much too high for any reasonably accurate extrapolation to 0" K. The cementitc used by Naeser was obtained from a steel containing 0.9 per cent carbon, by electrolytically dissolving out the iron in a neutral bath of ferrous chloride. The cementite remained as a coarse, crystalline, gray powder. Andes2 has measured the specific heat of iron carbide, from 102" to 323" K., as it exists in steel. The specific heats of several slugs of steel of known iron carbide content were determined, and the specific heat of the iron carbide (Fe3C) calculated by plotting specific heat versus percentage of carbon, and extrapolating to pure Fe3C (6.7 per cent C). The heat-capacity values for temperatures below 100" K. were obtained by comparing the temperature-specific heat curve for Fe3C to that of Fe. Since the two were very similar in the range examined experimentally and approach more closely at low temperatures, it was assumed that near the absolute zero the form of the curve for Fe3C would be similar to that of Fe. Andes calculates for the entropy of Fe3 C,S298 = 23.55 e.u. The heat of formation of Fe3C has been studied by several workers. Kelley3 has reviewed these measurements and calculations, and selects those of Roth* and Naeser6 as worthy of most consideration. Roth has given AH = 5400 cal. + 30 per cent as a result of his own and other work. Naeser has determined the heat of formation from Fe and different forms of carbon, and for graphite (0) he finds AH = 5600 cal. Kelley accepts the rounded figure AH = 5500 as the heat of formation at 298.1" K., but this value is quite uncertain.

Jan 1, 1940

By Harry Seltz

SEVERAL investigators have measured the heat capacity of cementite, using different methods of attack, but the agreement between the values obtained cannot be considered good. Naeser1 has made measurements of "average heat capacities" of iron carbide between 1026° and 85° K., using a water calorimeter. His computed true specific heat at 78.1° K. is 11.22 cal. per gram-formula mass, which, if correct, is much too high for any reasonably accurate extrapolation to 0° K. The cementite used by Naeser was obtained from a steel containing 0.9 per cent carbon, by electrolytically dissolving out the iron in a neutral bath of ferrous chloride. The cementite remained as a coarse, crystalline, gray powder. Andes" has measured the specific heat of iron carbide, from 102° to 323° K., as it exists in steel. The specific heats of several slugs of steel of known iron carbide content were determined, and the specific heat of the iron carbide (Fe3C) calculated by plotting specific heat versus percentage of carbon, and extrapolating to pure Fe3C (6.7 per cent C). The heat-capacity values for temperatures below 100° K. were obtained by comparing the temperature-specific heat curve for Fe3C to that of Fe. Since the two were very similar in the range examined experimentally and approach more closely at low temperatures, it was assumed that near the absolute zero the form of the curve for Fe3C would be similar to that of Fe. Andes calculates for the entropy of Fe3C, S298 = 23.55 e.u. The heat of formation of Fe3C has been studied by several workers. Kelley&apos; has reviewed these measurements and calculations, and selects those of Roth4 and Naeser5 as worthy of most consideration. Roth has given ?H = 5400 cal. ± 30 per cent as a result of his own and other work. Naeser has determined the heat of formation from Fe and different forms of carbon, and for graphite (ß) he finds OH = 5600 cal. Kelley accepts the rounded figure ?H = 5500 as the heat of formation at 298.1° K., but this value is quite uncertain.

Jan 1, 1939

By R. L. Skaggs, R. A. Molsberger

DARKEN1 has pointed out that in most binary liquid metal systems the thermodynamic behavior is relatively simple in the terminal regions. Between the terminal regions. the thermodynamic behavior is more complex. To describe this behavior. he has defined the stability and the excess stability as shown: Qualitatively, an inflection in the free energy of mixing curve results in a change in sign, from positive to negative, of the stability function and is associated with a phase separation. Conversely, a large, positive stability over a narrow composition range is indicative of compound formation. Darken has shown a number of binary systems where the excess stability is constant in the terminal regions and varies sharply in between. The work described in this communication was undertaken to study the variation of stability and excess stability in a binary system as a function of temperature. In addition, this work provides means for the direct comparison of previously existing equilibrium (activity) and calorimetric (molar heat of mixing) data on the Hg-Sn system. Hildebrand2 measured the vapor pressure of mercury over Hg-Sn alloys at 595°K. Calorimetric studies were made by Kawakami3 at 523°K and by Kleppa4 at 423°K. In this work, the equilibrium vapor pressure of mercury was measured over a series of Hg-Sn alloys at 453" and 503°K by use of fused salt manometer with one arm exposed to mercury vapor. Deflections of the fused salt manometer were balanced by argon pressure on the other arm. Argon pressure was subsequently measured with a dibutyl phthalate manometer. Tin activities were determined by graphical integration of the Gibbs-Duhem equation making use of the familiar Darken5 a function. The activities of mercury and tin showed positive deviation from Raoult&apos;s law at 453 and 503°K as Hildebrand observed at 595 K. In Fig. 1 are plotted log activity of mercury and tin vs reciprocal temperature. The plot contains activities obtained from calorimetric studies. Hult-gren6 has calculated activities from Kleppa&apos;s4 data, and Kubaschewski7 has similarly treated Kawakami&apos;s7 data. Presumably. in each case a regular solution was assumed. For regions where a two-phase field

Jan 1, 1970

By H. E. Criner, M. G. Driessen

Maurice Rey—The influence of cyclone diameter upon the fineness of separation is an important point which, however, cannot be discussed adequately if the injection pressure or the rate of flow are not specified. Perhaps some light can be thrown on the matter by using the formulas derived by Dahlstrom. Let us consider several geometrically similar cyclones where the apertures e and b are equal and proportional to the diameter D and which are operated with the same pressure drop. Eq 8 of Dahlstrom&apos;s paper can be written: Q Q = K D&apos;. " or. if F is constant: Q = K D18 K is a constant of proportionality. Introducing this value of Q in eq 13 gives elimination efficiency = K D ,41 Elimination efficiency, in the terminology of Dahl-strom, means the diameter of particles, in microns, which divide equally between the underflow and the overflow. This denomination is regrettable and it would be preferable to call it diameter of separation or characteristic size or any other name connoting a size rather than an efficiency. Whatever the name used, the above equation shows a slow increase in the fineness of separation when the diameter of the cyclone decreases. For example, if a 14-in. cyclone gives a 400-mesh separation (37 microns), geometrically similar cyclones, having the same pressure drop will give separations at the sizes shown below.

Jan 1, 1951

By M. G. Driessen, H. E. Criner

Maurice Rey—The influence of cyclone diameter upon the fineness of separation is an important point which, however, cannot be discussed adequately if the injection pressure or the rate of flow are not specified. Perhaps some light can be thrown on the matter by using the formulas derived by Dahlstrom. Let us consider several geometrically similar cyclones where the apertures e and b are equal and proportional to the diameter D and which are operated with the same pressure drop. Eq 8 of Dahlstrom&apos;s paper can be written: Q Q = K D&apos;. " or. if F is constant: Q = K D18 K is a constant of proportionality. Introducing this value of Q in eq 13 gives elimination efficiency = K D ,41 Elimination efficiency, in the terminology of Dahl-strom, means the diameter of particles, in microns, which divide equally between the underflow and the overflow. This denomination is regrettable and it would be preferable to call it diameter of separation or characteristic size or any other name connoting a size rather than an efficiency. Whatever the name used, the above equation shows a slow increase in the fineness of separation when the diameter of the cyclone decreases. For example, if a 14-in. cyclone gives a 400-mesh separation (37 microns), geometrically similar cyclones, having the same pressure drop will give separations at the sizes shown below.

Jan 1, 1951

By H. H. Johnson, Eric W. Johnson

A newly developed ac technique was used to measure the electrical-resistivity changes associated with both cyclic stressing and subsequent annealing of high-purity and OFHC copper. The early stage of push-pull fatigue was explored at 293° and 4.2°K, with stresses chosen for an expected fatigue life of 2 to 8 X 105 cycles. For high-purity copper, fatigue at 293°K was accompanied by an initial increase in resistivity. After about 5000 stress cycles, no further increase was observed. Annealing studies showed that the resisticity increment could be accounted for solely in terms of an increased dislocation density, to about 2 x 1010 disl pev sq cm. Fov 42°K fatigue, however, the resistivity increased continually, with no evidence of saturation, as approximately (No. of stress cycles)1/4. This is intevpreted to result from both dislocation multiplication and vacancy production; estimated vacancy concentrations are 10-4 to 10-9. The continuous resistivity increase was inhibited by interspersed annealing treatments at 293°K, which also raised the level of the stress-strain curve. These effects are attributed to annealing of vacancies into dislocation loops. In contrast, OFHC copper fatigued at 4.2°K showed saturation of electrical vesistivity after only a few hundred cycles, and it appeared that vacancies annealed out completely between 77° and 293°K. MaNY observations suggest that both dislocation multiplication and point-defect production are important aspects of fatigue deformation. An increase in dislocation density with number of stress cycles has been demonstrated or implied by several experimental techniques, including optical metallography with lithium fluoride,&apos; electron microscopy with copper,2 thermal conductivity of Cu-Zn alloys,3 and peak-stress measurements during cycling at constant plastic strain amplitude.4,5 At low amplitudes and/or stresses saturation of fatigue hardening and dislocation density occurs early in the expected fatigue life,4-6 frequently by a few hundred cycles. The evidence for point-defect production is somewhat less extensive, but it is nonetheless persuasive. Rosenberg7 reported briefly that, for equal stresses, copper fatigued at liquid-hydrogen temperature displays an increase in electrical resistance some ten times that which accompanies unidirectional stressing. Further, the extra resistance saturates after a few hundred stress cycles, and does not anneal significantly until a temperature of about 170°K is attained.&apos; Point-defect production during fatigue is also suggested by 1) the softening during cyclic stressing of initially strain-hardened polycrystal-line copper9, 2) the strong temperature dependence of the yield strength of fatigue-hardened mono- and polycrystalline copper,579"0 and 3) the influence of intermediate annealing upon slip-band formation in copper fatigued at 90°K.8 It is evident that characterization of the fatigued state requires a knowledge of both point-defect and dislocation densities. For this purpose electrical-resistivity measurements are useful, but they are difficult to perform because of geometric limitations. Push-pull fatigue is necessary to obtain a macroscopic ally uniform deformation over the specimen cross section; however, the specimen must then have a low slenderness ratio to avoid plastic buckling, while the standard dc resistivity technique requires a very slender specimen for

Jan 1, 1965

By G. B. Craig, H. E. Rosinger, W. J. Bratina

NUMEROUS studies have been reported on how the mechanical properties of a bcc metal are affected by interstitial solute atoms in the temperature range where appreciable diffusion occurs in finite time. Only recently, though, has work on an "interstitial-free" iron been reported, this by Leslie and sober,&apos; on an Fe-0.15 pct Ti alloy. The data was limited to a maximum temperature of 296°K. This work presents a systematic study of the flow stress and the activation volume of a similar material as a function of plastic deformation over the temperature range 253" to 473°K. The material studied was Ferrovac E iron containing 0.01 wt pct C and 0.0002 wt pct N annealed at 870°C for 1 hr, and the same iron with an addition of 0.15 wt pct Ti annealed at 870°C for 80 hr; cooling rates being 75°C per hr. In the latter alloy depletion of interstitials in the a-iron matrix associated with the second phase formation was expected. The temperature dependence of the flow stress was measured at 6 = 3.33 x 10-5 sec-1 from 253" to 473°K as a function of the deformation in 0.01 intervals from 0.03 to 0.12 strain. Results for two strains, 0.03 and 0.09 are shown in Fig. 1. The flow stress increased and reached a maximum in the Ferrovac E iron with increasing temperature, but showed a consistent gradual decrease in the Ferrovac E-0.15 pct Ti alloy. A yield point and Luders region, observed in Ferrovac E, was absent in the Ferrovac E-0.15 pct Ti alloy. Also, the Ferrovac E exhibited a serrated stress-strain behavior in the temperature range 330" to 400°K; dynamic strain-aging characteristics were absent for the titanium alloy. The activation volume was determined over the same temperature range by the method of stress relaxation at constant strain. Results are shown in Fig. 2. At the temperatures of serrated stress-strain behavior in Ferrovac E the activation volume was found to increase toward infinity and, as the temperature rose, to decrease, to about 100 to 200 v/b3. By contrast, the activation volume for the Ferrovac E-0.15 pct Ti alloy tended to increase continuously from the initial value of approximately 300 at 300°K to more than 800 at 473°K. Above 400°K, then, the corresponding activation volume values of Ferrovac E were less than that of the Ferrovac E-0.15 pct Ti alloy. The activation volumes, Fig. 2, appear to depend on dislocation-interstitial interaction in Ferrovac E and on dislocation-dislocation interaction in Ferrovac E-0.15 pct Ti alloy. The gradual increase in the latter metal is associated with thermally activated motion of dislocation segments.&apos; The decrease of the activation volume in Ferrovac E above 400°K is probably related to the diminishing effect of interstitials on dislocations. Here, the interstitials can be moved along with a dislocation without appreciable drag. As indicated in Fig. 1, removal of interstitials

Jan 1, 1970

By P. Niessen, S. J. Bercovici

RECENTLY Aust et al.&apos; proposed a model of non-equilibrium grain boundary segregation based on a vacancy gradient induced uphill diffusion process of solute to grain boundaries. According to their proposal, solute atoms which are attracted to vacancies would, during the cooling of a sample, migrate with vacancies toward grain boundaries (vacancy sinks) and thereby enhance the solute concentration in boundary regions. For solute atoms which are not attracted to vacancies no such boundary solute enrichment would be expected. These concepts were given experimental support by boundary and bulk mi-crohardness measurements of various thermally treated dilute zinc and lead alloys and also doped aluminum oxide. The underlying assumption in their work was that solute enrichment in boundary regions is indicated by higher microhardness values. From thermodynamic considerations1&apos;2 it appears that the solid-liquid solute distribution coefficient (K), defined as the concentration of solute in the solid to the concentration of solute in the liquid at equilibrium, indicates whether attractive or repulsive forces exist between vacancies and solute atoms. K < 1 indicates a solute-vacancy attractions, K > 1 indicates no, or a repulsive, vacancy-solute interaction. This note is to report on observations of different grain boundary etching phenomena in high purity zinc alloys. These phenomena appear to depend on whether a K < 1 or K > 1 solute is present. In experiments designed to measure directly the solute enrichment in grain boundary regions, samples of zone refined zinc with 0.1 at. pct solute additions were cooled from 380°C at a rate of 3°C per min. A surface layer of approximately 50 was then removed from the samples by chemical polishing. The samples&apos; surfaces were then protected by a chromating treatment such that in a subsequent etch only grain boundary regions were dissolved. The dissolved regions were approximately semicircular troughs, 10 µ in width. The grain boundaries were usually in the middle, i.e., at the bottom, of this trough. For zinc containing the K < 1 solutes cadmium and aluminum, the grain boundary was always indicated by a ridge as shown in Fig. 1. For pure zinc, and zinc containing the K > 1 solutes copper and gold, a groove at the bottom of the trough indicated the boundary position, Fig. 2., To test if these different grain boundary etching behaviors were possibly connected with the segregation process discussed above, the Zn-Cd alloy was again heated to 380°C and quenched into brine. After surface protection and etching it was found that this specimen no longer exhibited the grain boundary ridges but rather grain boundary grooves as shown in Fig. 2. It would appear, therefore, that the boundary ridge is a consequence of a process occurring during the slow cooling of the samples. From absorption spectrophotometric analysis it was found that for slowly cooled samples containing K < 1 solutes, the solute/zinc ratios of the material from the boundary trough were consistently considerably higher than the solute/zinc ratios of the bulk alloys. This boundary region solute enrichment was not observed in quenched samples. It is concluded therefore, that the boundary ridge shown in Fig. 1 is directly or indirectly connected with nonequilibrium solute segregation.

Jan 1, 1970

By Tom Westgarth

As papers are placed before you upon large gas-engines in Belgium and Germany, it was considered that some information should be given upon the same subject in Great Britain. I therefore agreed to compile these notes, which I have made very short in view of the somewhat full nature of the other papers presented to this meeting, and considering the complete nature of the many publications which have been made recently upon the subject of large gas-engines. I give below Tables I. to VI., showing the number and particulars of large gas-engines which have been built or are building by British makers, and in view of the growing size of gas-engines I have concluded that engines of less than 500 h.p. cannot now he included in the category of large gas-engines, and therefore I have not considered engines under that power. Table I.—-" Oechelhauser " Type Gas-Engines. Built or Building by William Beardmore Co., Limited, Glasgow Indicated ! Engines. Horse-Power Type. Nature of Work. Gas Used. 6 2,500 Twin cylinder. Dynamo. Producer. 1 in Single cylinder. Rolling-mill. Producer. 4 1,250 Twin cylinder. Dynamo. Producer. 2 1,250 Single cylinder. Dynamo. Producer. 4 625 Single cylinder. Dynamo. Producer. 1 625 Single cylinder. Rolling-mill. Producer. 1 625 Single cylinder. Air compressor. Producer. 2 500 Single cylinder. Air compressor. Producer. 7 500 Single cylinder. Cement-mill driving Producer. Total, 28 engines ; 32,600 indicated horse-power. * Presented at the Joint Meeting of the Iron and Steel Institute and the American Institute of Mining Engineers, London, July, 1906, and here published under a mutual agreement between the Councils of the two Institutes.

Jan 1, 1907