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By W. A. Schaeffer, Sidney A. Justin, Jr. H. D. Easton

Restriction and proration of petroleum production have increased materially the difficulties attendant upon the estimation of reserves, particularly in large, "flush" fields. Such practices preclude the use of decline or other curves, from which, under capacity production conditions formerly prevalent, much could be learned as to the ultimate recovery to be expected from a given field or lcase therein. In restricted fields that would produce at many times the low rate allowed by the regulations in force if allowed to flow without restraint, one is forced to use other information than production performance to predict the volume of oil recoverable. Examples are: at Kettleman Hills, California; the Conroc, Van and East Texas fields, Texas; the Iowa field, Louisiana. It is beyond the scope of this paper to apply a definite method to the determination of the reserves in any actual field, therefore the discussion will be limited to a consideration of available methods and an enumeration of important factors governing the accuracy of such estimates. The problem is to determine not only oil in place but recoverable oil in place, for a given field or tract, which is complex and depends not only on the characteristics of the reservoir but also on the plan of development, the production allocation scheme, the rate of production and many other factors. Many data must necessarily be considered, weighed as to inportance, and assigned quantitative values. Estimates of recovery in prorated fields have been discussed by Brace', Shaw2, Snider3 and others. The wide difference in estimates of ultimate recovery from a number of important recently developed fields demonstrates the inadequacy of

Jan 1, 1935

By H. Biloni, H. R. Bertorello

GruZLESKI and winegard1 have recently reported on the origin and development of the cellular substructure in Sn-Cd eutectic unidirectionally grown with different amounts of constitutional supercooling (CS). This communication deals with the results obtained in a parallel study on the instability of a plane interface in Al-Cu eutectic unidirectionally grown. Similarities as well as differences with the results of these authors1 will be presented. A1-Cu eutectic alloy ingots of 99.999 pct purity were grown unidirectionally under different G/R ratios where G = thermal gradient in the liquid, R = solidification rate. The ingots were cut in slices perpendicular to the solidification axes and the substructure studied on parallel sections following the sense of growth. It was generally found that the last part of the ingot to solidify presented a well developed colony substructure as a result of impurity build up and constitutional supercooling. The results obtained were: 1) When the structure was observed with low niagnification (of the order of 150 to 300 times) the first instabilities were observed at the grain boundaries and node-like structures formed at the junctions of the growth-induced boundaries, as reported by Gruz-leski and Winegard.1 Inside the grains the first signs of instability appear later and correspond to the type shown in Fig. 1; this is a two dimensional cell substructure. ' 2) Figs. 2 and 3 correspond to the evolution from a two dimensional substructure to a cellular type. In the A1-Cu eutectic the boundaries of the two dimensional cell are always perpendicular to the laniellaes instead of parallel as in the Sn-Cd eutectic. 1

Jan 1, 1970

By M. Nicholas, D. M. Poole

The diameters of sessile drops have been found to increase linearly with time in five reacting binary metal systems. The spreading rates of the drops are markedly dependent on temperature and on prior alloying of the solid with the lower melting point metal, hut are independent of the drop volume, wetting atruosphere , solid-surface roughness, and prior alloying of the drop with the substrate metal. A mechanism has been suggested that relates the linear-spreading rate to lateral diffusion of the liquid-metal atoms into the solid at the drop edge. An Arrhenius- type equation has been derived that describes the temperature dependence 0) the spreading rate, and although the agreement between the actual and the predicted pre-exponen-tial terms is poor that between the activation energies is excellent and the variation in the spreading rate of copper on Ni-Cu alloys produced by different extents of alloying can be predicted with considerable accuracy. CHEMICAL interactions frequently change the wetting behavior of solid-liquid systems causing, for example, "secondary spreading1 of sessile drops beyond the size defined by the surface and interfacial tensions of the unreacted components. The kinetics of the contact-angle decreases associated with this spreading are similar for many systems, but few studies have been made with the objective of determining whether the similarities are a reflection of a common mechanism. Some workers2,3 have assumed the secondary spreading is controlled by changes in the liquid surface and liquid-solid interfacial tensions and hence by the composition of the liquid, and contact-angle changes measured by the vertical-plate technique have been used to follow the course of liquid-solid chemical reactions.4 Other processes that have been invoked to explain these time-dependent changes in specific systems include the removal of adsorbed gas from the liquid-solid interface.5 penetration of containment layers on the solid Surface,6 interdiffusion,1,7 reori-entation of the solid surface into a wettable configuration: vapor-phase transport of the liquid onto the solid in advance of the drop,9 and, from vertical-plate studies. capillary flow between oxide layers and the solid surface.10 One of the reasons for the profuseness of these suggestions may be the complexity of the contact-angle change kinetics. However, in an analysis of secondary spreading gold and copper on UC,11 it was found that the diameter of the contact area between the sessile drop and the solid surface showed a simple linear increase with time although contact-angle changes were more complex. To check whether the linearity was merely fortuitous! additional exploratory work was conducted with four reacting metal-metal systems: Au on Ni. Cu on Ni, Cu on Fe, and Ag on Au. Linear spreading was observed in every case even though the kinetics of the contact-angle changes were complex. A further detailed study of the kinetics of linear spreading of five reacting metal-metal systems has been made with the object of determining the mechanism involved. The influence of variables such as temperature, drop volume. and the initial composition of the drop on the linear-spreading rate has been measured and compared with those predicted by a number of possible mechanisms. The systems employed in this study (Cu and Au on Ni and Pt, and Ag on Au) were selected because of the availability of potentially relevant chemical and physical property data. the simplicity of their phase diagrams at the wetting temperatures, and the ease of experimentation. EXPERIMENTAL TECHNIQUES The purities of the metals used in the study were: copper, 99.9 pct; gold. 99.96 pct; nickel, 99.2 pct; platinum 99.99 pct; and silver, 99.999 pct. The wetting tests were performed in a split tantalum tube vacuum resistance furnace of a conventional design. The furnace element was held vertically and was 1 $ in. in diam and 6 in, long. Viewing ports were provided in the water-cooled chamber to enable the specimens to be observed in both the horizontal and vertical planes. The temperature in the hot zone of the furnace could be held at 1500" i 5°C for an indefinite time. The surfaces of the solid-plaque metals were ground flat on Microcut paper and both the sessile drop and substrate metals were ultrasonically cleaned in methyl alcohol prior to their insertion in the furnace. After loading, the furnace was pumped down to a pressure of 2 x 10-5 mm of mercury and degassed for 30 min at 900° to 950°C. The temperature was then increased at more than 100°C per min to that used in the wetting test. The vacuum at the wetting temperature was better than 5 x 10-5 mm of mercury. Dewetting and retraction of the drop on cooling did not occur and the contact-area diameters, therefore, were measured after solidification with a vernier traveling microscope. The diameters quoted later are arithmetic means of ten measurements. The standard error of the mean never exceeded 3 pct and was often less than 1 pct.

Jan 1, 1967

By Frank M. Brewster

The handling of congealing oils and paraffin is a serious problem in the Appalachian fields, particularly because the small amount of oil produced per well makes the removing of paraffin a very costly operation per barrel. Few operators realize or have any means of knowing just how much production is lost on account of paraffin depositing over the face of the sand and plugging the pores of the sand; but where paraffin has been removed the production increases indicate that this loss has been considerable. Many operators believe that paraffining is confined to the tubing and pumping equipment, but it is evident that the most serious damage occurs on the face of the sand and a short distance back in the pores. This paper is an attempt to disseminate information on methods and processes in use in the Eastern fields for combatting losses of production and operating difficulties caused by deposition of paraffin in the pores, on the walls, on the tubing and on other pumping equipment. Mills1 covers this subject so thoroughly that excerpts, abstracts and quotations from his work have been used freely in this paper. Nature oF Paraffin Mills states: "The so-called paraffin that collects in oil wells, and in the pores of the producing sands immediately around the wells, is generally made up of amorphous wax or uncracked paraffin, asphalt, or other gummy hydrocarbons mixed with more or less water, oil and inorganic silt. Some of the samples of this paraffin collected from oil wells in different fields and examined by the Bureau of Mines contains as much as 20 per cent. by weight of water and inorganic silt, whereas other samples are composed entirely of waxy hydrocarbons and oil. The inorganic silt accompanying this 'paraffin' is mostly fine sand, clayey materials, common salt and finely disseminated precipitates of calcium and magnesium carbonates. Sulfates of calcium, barium and strontium are less common constituents of paraffin.

Jan 1, 1928

By Gerhard Derge, Arthur H. Grobe, Harold Markus

The high corrosion resistance possessed by tin under most circumstances, combined with its generally satisfactory appearance and useful physical properties, has led to many and varied uses for the metal. These uses have been partly limited by the fact that tin is an expensive metal, therefore many applications have been developed in which tin has been employed in combination with lead, either by coating, as in tin-lined collapsible tubes, or by the formation of alloys containing various proportions of tin-rich and lead-rich phases, as tcrne plate. A detailed knowledge of the corrosion characteristics of the tin-lead couple therefore is of general interest and has become specially important at the present time, when every effort is being made to conserve tin as much as possible. The present study has been limited to carbonate solutions with a pH range from 8.4 to 11.2 so that the results may be related to earlier work on the corrosion of tin and its alloys. 1-3,6 In these papers, the effects of a number of anion and cation additions to these solutions have been observed. Apparatus and Method The electrodes for the corrosion cell were cut from rolled sheet about 1/16 in. thick. The length of all specimens was held constant at 7 in., while the width was varied from M to 2 in. These electrodes were fastened to brass electrode supports, which were attached to rubber stoppers fitting into tall-type one-liter Pyrex beakers that contained the electrolyte. The lead electrodes were prepared from Omaha pig* and the tin was rolled from a slab of Chempur.† After cutting to size, the sheets were polished with No. I emery paper and cleaned with carbon tetrachloride. The edges, back and upper parts of the specimen were coated with a synthetic lacquer, which was supplemented with beeswax for the lead electrodes. The binding posts were coated with beeswax after the electrodes had been clamped. The pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicarbonate. Approximately 600 ml. of electrolyte was used in each beaker. The entire assembly was placed in an oil bath thermostatically adjusted to operate at 30°C. + 0.1". Potentials were measured against a saturated calomel electrode connected to the cell by an agar-agar salt bridge. The carbonate solution used in the salt bridge was the same as that used in the corrosion cell. Currents were measured with a milliam-

Jan 1, 1942

By Harold Markus, Arthur H. Grobe, Gerhard Derge

The high corrosion resistance possessed by tin under most circumstances, combined with its generally satisfactory appearance and useful physical properties, has led to many and varied uses for the metal. These uses have been partly limited by the fact that tin is an expensive metal, therefore many applications have been developed in which tin has been employed in combination with lead, either by coating, as in tin-lined collapsible tubes, or by the formation of alloys containing various proportions of tin-rich and lead-rich phases, as tcrne plate. A detailed knowledge of the corrosion characteristics of the tin-lead couple therefore is of general interest and has become specially important at the present time, when every effort is being made to conserve tin as much as possible. The present study has been limited to carbonate solutions with a pH range from 8.4 to 11.2 so that the results may be related to earlier work on the corrosion of tin and its alloys. 1-3,6 In these papers, the effects of a number of anion and cation additions to these solutions have been observed. Apparatus and Method The electrodes for the corrosion cell were cut from rolled sheet about 1/16 in. thick. The length of all specimens was held constant at 7 in., while the width was varied from M to 2 in. These electrodes were fastened to brass electrode supports, which were attached to rubber stoppers fitting into tall-type one-liter Pyrex beakers that contained the electrolyte. The lead electrodes were prepared from Omaha pig* and the tin was rolled from a slab of Chempur.† After cutting to size, the sheets were polished with No. I emery paper and cleaned with carbon tetrachloride. The edges, back and upper parts of the specimen were coated with a synthetic lacquer, which was supplemented with beeswax for the lead electrodes. The binding posts were coated with beeswax after the electrodes had been clamped. The pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicarbonate. Approximately 600 ml. of electrolyte was used in each beaker. The entire assembly was placed in an oil bath thermostatically adjusted to operate at 30°C. + 0.1". Potentials were measured against a saturated calomel electrode connected to the cell by an agar-agar salt bridge. The carbonate solution used in the salt bridge was the same as that used in the corrosion cell. Currents were measured with a milliam-

Jan 1, 1942

By S. Shapiro, G. Krauss

The strutural and cr~stallo~aphic features of the plates of austenite produced by the martensite to aus-tenite or reverse martensitic tramformation have been determined in an Fe-33 wt pct Ni alloy. Micro-focus X-ray techniques and single-surface trace analysis 072 bulk samples yielded two distinct habit planes, (0.174, 0.309, 0.~35)~ and (0.375, 0.545, 0.749jM. The former plane uas the one predorninantly observed and its existence was verified by transn~ission electron microscopy. The orientation relation-ship between the reversed austenite and the parent martensite was approximately the same as the Nishiyamna and other relationships reported for the direct tramformation. Replica and thin-joil obser-vations show that both high densities of tangled dis-locations and occasional twins constitute the fine structure of the reversed austenite. Application of the phenomenological theory to a variant of the predominant habit plane defines an irrational plane and direction for the second shear in accordance with the comnplexity of the fine structure. The shear accompanying the reverse martensitic transformation is at least 0.51, the maximnum value of- the tangent oJ the tilt angle measured on surface replicas. A mechanism relating the fine transformation twins in martensite to the nucleation of reversed austenite of the predominant habit is proposed. The reversal of Fe-Ni martensite takes place both at the edges of martensite plates and in a piecewise fashion within them.' The shear-type nature of the reverse transformation is verified by the surface relief which accompanies both edge-type reversal2 and the fragmentation of plates of martensite' as a result of rapid heating above the A, (austenite start temperature). The orientation relationship between the edge-type reversal product and the parent martensite, as determined by transmission electron microscopy, is reported to be within 4 deg of either the Kurdyumov-Sachs or Nishiyama relationships,' but there is no work at present in the literature relating to the crystallography of the platelike reversed austenite. The fine structure of reversed austenite after heating to 50°C above the Af is reported4 to be composed primarily of tangled and jogged dislocations in concentrations up to 10" per sq cm. A replica investigation of partially reversed Fe-Ni martensites5 corroborates the increase in dislocation density following reversal and presents indications of other possible modes of fine structure. This paper reports on an investigation performed to examine in detail the morphology and crystallography of the plates of reversed austenite and the shear which accompanies their formation in a matrix of Fe-Ni martensite. EXPERIMENTAL PROCEDURE Discs of a high-purity Fe-32.9 wt pct Ni single crystal served as the starting material. The single crystal had been produced in the course of an earlier investigation6 and the carbon content was determined at the time to be 0.006 wt pct. The M,, and the A,, were respectively -120" and 300°C. Partial transformation to martensite was performed at -125°C and reversal of some of the martensite was accomplished by heating in the temperature range 340" to 355°C. Most samples were heated to the reversal temperature by immersion' in a salt bath for 2 min. For surface-relief studies some polished and etched Samples were heated in a tube furnace for ten min in a hydrogen atmosphere maintained over the samples throughout the heating and cooling cycles. Samples were prepared for metallographic examination by electropolishing and etching with an HC1-HNOs-H20 et~hant.~ On one of the surface-relief samples two sets of fiducial scratches were placed on the etched sample by drawing it over a slurry of 0.06 p alumina on a "microclothJ'. The orientations of individual plates of martensite were determined by X-ray analysis. A Rigaku-Denki microbeam X-ray generator in conjunction with a Micro-Laue camera with facility for precision location of the sample in front of the beam was employed for this purpose. The collimator size was 30 p and the specimen to film distance was 5 mm. The Laue photograms were enlarged to an equivalent 3-cm specimen to film distance for analysis. The orientation of each of the plates of martensite was compared to that of the parent austenite and the relationship be -tween the two phases was, in all cases, within a few degrees of those predicted for the direct transformation. The orientation relationship between one of the larger plates of reversed austenite and its parent martensite was determined in a similar manner. The habit plane of the islands of reversed austenite in the X-rayed plates of martensite was determined by a single-surface trace analysis. Each reversal island had with the parent phase one comparatively straight boundary which was presumed to represent the habit plane trace. The pole locus technique7 was applied to traces from six different plates of martensite to determine the indices of the habit plane. A 40-cm stereographic net was employed for this analysis The morphology and fine structure of the reversed austenite were studied by electron microscopy of pre-shadowed direct carbon replicas,5 and the macroscopic shear was evaluated by a two-stage replica technique similar to that employed in electron fractog-

Jan 1, 1968

By J. W. Sandelin, L. S. Birks

The group five metals, vanadium, niobium, and tantalum all show cold-rolled textures of {100)(011) and {112)(0ll) with a preference for the (100) in vanadium and niobium and for the {112) in tantalum. Recrys-tallization texture of (100) and (111) was reported1 for vanadium after annealing (no temperature stated). For tantal~m ,~ annealing below 1200°C strengthened the (112) texture but the (111) texture increased and was predominant as the annealing temperature was raised to 2500°C. Annealing niobium up to 1100°C strengthened the ( 100) texture and developed a weak (111) texture.' In the present work niobium has been annealed up to 2000°C. Nearly 70 pct of the grains showed {111) texture with only a weak (112) component and an insignificant (100) component remaining. In addition, double-crystal rocking curves were used to follow the increase in crystal perfection of the grains with increased annealing time. Material and Treatment. Samples i by 4 in. were sawed from & -in.-thick cold-rolled niobium sheet obtained from Wah Chang. Chemical analysis of the material showed it to be 99.4 pct pure with tantalum as the major impurity. Individual pieces were annealed for 2, 15, 30, and 60 rnin in a vacuum of 10'* Torr using an rf generator. They were etched until the grain boundaries were well-defined, Fig. 1. Average grain size varied from 1 mm for 2 min annealing to 2 mm for 60 rnin annealing. Experimental Results. Preferred Orientation. The orientations of 97 of the 117 grains in the specimens of Fig. 1 were determined by back-reflect ion Laue patterns. A General Electric 10-cm-diam cylindrical camera was used rather than the conventional flat camera in order to record more of the low-index spots. The method proposed by Forest, Barton, and schieltz4 was used to transform the cylindrical film patterns to standard stereographic projections. Table I gives the compilation of data. Even 2 rnin anneal at 2000°C is sufficient to yield a strong (111) preferred orientation, and the percentage of grains with this orientation increases steadily with annealing time at the expense of all other orientations. Crystal Perfection. X-ray topographs were taken of each specimen in both the (111) and (112) orientation using the method described by Birks and Grant.' As the anneal time increases, the grains become larger and the individual reflections become slightly more uniform in intensity, indicating an increase in crystal perfection. For a more quantitative measure of crystal perfection, it was necessary to measure the double-crystal rocking curve. The spectrometer employed was a Gaertner instrument of Compton design. LiF was chosen for the first crystal because the (400) reflection with d spacing of 1.05 AU is a good match to the (222) niobium reflection with d spacing of 0.95 AU. CuKp radiation was used in order to further reduce the d spacing mixmatch correction.' A variable aperture was placed between the LiF and the niobium specimen so that a single grain or even a small portion of a grain could be examined. Fig. 2 shows typical rocking curves for the four annealing times. For the 2-min specimen, a single peak is observed with 10' of arc full-breadth at half maximum. As the annealing time is increased to 15 or 30 min, several sharper peaks of 40 to 80" breadth can be seen within a single grain. After 60 rnin anneal only a single peak of about 30" is observed. Table I1 shows the corrected rocking curve breadths and the dislocation densities, ND. The latter were calculated from the equation7 where W is the corrected rocking curve breadth at half maximum in radians and b is the effective Burger's vector. For (110)(111) slip in niobium, b is 2.86 AU. Discussion. The annealing of cold-rolled niobium at 2000°C causes rapid preferential growth of grains with {ill} orientation. After only 2 rnin annealing time, 35 pct of the grains have the (111) orientation, and after

Jan 1, 1968

By A. W. Dana, F. J. Shortsleeve, A. R. Troiano

The phenomenon of flake formation which may occur during cooling or room temperature aging of large steel sections is caused by a combination of hydrogen and stress. As such, the transformation characteristics of austenite in a particular section play a major role in the occurrence of flakes. Isothermal and continuous cooling studies demonstrated that flake formation is particularly sensitive to nature, distribution, and relative proportions of the microconstituents in the cooled sections. In the absence of transformation stresses, abnormally high hydrogen contents could be tolerated without flaking. Flakes were not found in the absence of transformation stresses. No correlation existed between average hydrogen content and flake formation where cooling stresses were low. Hydrogen in the steel was a necessary but not sufficient condition for flake formation. DESPITE a long history of laboratory and commercial investigations, the mechanics of hairline crack or flake formation in large steel sections remains unresolved. Recent publications1-5 emphasize that flaking is still a serious problem.* immediate cause of flaking is the pressure exerted by entrapped hydrogen gas that collects in small internal cavities or voids during cooling. When the temperature of steel is low enough to preclude extensive plastic flow, the cavity pressures cause local brittle fractures (flakes). 2—The microsegregation and transformation stress theory. According to this theory, flaking results from stresses arising from the volume changes accompanying the formation of martensite and/or low temperature bainite after a large portion of the section has transformed at elevated temperatures. The proponents of the hydrogen theory suggest that stresses from other sources may be additive to the stresses produced by hydrogen and may, in some cases, provide the increment of stress necessary to produce flakes. However, the critical aspect of this theory is that no stress, except that produced by hydrogen pressure, is believed to be sufficient in itself to produce flakes. For practical considerations, this means that the only safe thermal cycle is one that reduces the hydrogen content to some low critical level below which flaking will not occur regardless of the state of transformation. On the other hand, the transformation stress theory does not rule out the embrittling effect of hydrogen. This theory simply proposes that flaking does not occur in the absence of transformation stresses. With the transformation stress theory as a basis, commercial antiflaking cycles would be designed to complete the transformation of austenite prior to cooling to ambient temperatures. Both of these theories appear compatible with industrial experience. Antiflaking cycles, such as cooling at extremely conservative rates or soaking for periods of time in the upper subcritical temperature ranges prior to cooling to ambient temperatures, may allow the following: 1—diffusion of hydrogen out of the section and, as a consequence, reduction of the hydrogen content to some safe minimum value (hydrogen pressure theory) and 2—complete decomposition of the austenite at rela-

Jan 1, 1956

By E. T. Turkdogan

This is a compilation and a critical review of the data on the Fe-Ca-0 ternary system. Using the results on the reductiorz-equilibria, an oxygen potential diagram is drawn for the greater part of the system. A number of univariant systems and invariant points, not determined experimentally, are evaluated by making use of the theorem on univariant curves intersecting at an invariant point. The formation of solid solutions and ternary compounds and the crystal structures of some of the phases in the composition-diagram are given for a feu! temperatures. DURING the past thirty years there has been a continued interest in the study of the Fe-Ca-0 system. A detailed literature survey made by white1 in 1943 indicated that further work was required to clarify the phase relationships; in fact, the work carried out in the subsequent years, reviewed by Burdese2 in 1954, made a valuable contribution to a better understanding of this subject. Most of the data were obtained by the step-wise reduction of mixtures of iron oxides and calcium ferrites. However, there is some uncertainty about the phase relationships in this system, arising mainly from insufficient use of thermodynamic concepts in the construction of phase diagrams. In this paper an attempt is made to establish the invariant points from the available data. OXYGEN POTENTIAL DIAGRAM Schenck and coworkers3,4 were the early investigators who studied part of this system by the step- wise reduction method and suggested the formation of two ternary compounds, CaO.FeO.Fe2O3 and 2Ca0.5Fe0.2Fez03, the latter being referred to as point X. They also deduced from their results that the phases Y (8.74Ca0.32.5Fe0.8.74Fe2O3 and Z (2.02CaO-97.98FeO) were formed near the w?stite corner of the system. Martin and voge15 postulated the existence of the compounds CaO.9FeO and 4Ca0.3Fe3O4; the former is very close to the composition of point Z and the latter to that of CaO.FeO-Fe2O3. The most valuable contribution to the presen knowledge on this system was made by Cirilli and Burdese6-8 who showed by X-ray and chemical anal yses that there were two ternary compounds, CaO-Fe0.Fe2O3 and CaO.3FeO-FezO3; the former is the same as that suggested by Schenck et al. and the latter is close to their point X. The results of Cirilli and Burdese show that the phases Y and Z postulated by Schenk et al. are solid solutions of calcium oxide in w?stite. In most of the above-mentioned reduction-equilibria measurements carbon monoxide-carbon dioxide mixtures were used and in a few cases hydrogen-water vapor mixtures were employed. Using the

Jan 1, 1962

By Ashok K. Sinha

During the course of an in~*estigation into the occurrence of ordered AB3 structures, the following new phases have been found —CrRh3 (AuCu3 type), CrCo3 (MgCd3 type), HfCo4 (Ths Mn23 type), and WPt, MoPh type). The composition of the TiPt3-x phase (TiNi, type) is close to Ti23Pl77. The alloy chenzistry of transition rnetal AB3 structures is rezliewed in the light of electron concentration correlations of hex-agonality recently obtained for quasi-binary alloys. The relatizte colurne contraction in the AB3 structures increases with increasing difference in volume of the conzponents. A family of ordered close-packed layered structures is formed by stacking identical layers of composition AB, in various sequences, such that the coordination is twelvefold throughout and there are no A-A contacts. Previous work' on quasi-binary AB3 alloys has led to the conclusion that the stacking sequence of the AB, structures changes with increasing radius ratio RA/RB from a purely cubic, through different mixtures of hexagonal and cubic stacking to a purely hexagonal stacking. However. for binary AB3 alloys, a correlation between the type of the crystal structure and the position of the components in the various volumns of the periodic table has been noted.2-5 It has been noted6 that this correlation appears to hold even though the radius ratio RA/RB may vary over a considerable range with the location of the components in the three long periods. Another study7" of several quasi-binary systems led to the conclusion that an increase in hexagonality of the stacking is associated with increase in the electron concentration e/a. as defined by the average per atom of the total number of electrons outside the inert gas shells. In apparent conflict with this conclusion, it is known that seven binary alloy structures isotypic with TiNi3 which is 50 pct hexagonal occur at a higher electron concentration (e/n = 8.5) than that (e/a = 8.25) for the 100 pct hexagonal MgCd3 type structure present in seven binary AB3 alloys. Table 111. In the present work, an investigation into the occurrence of binary AB3 structures in transition metal alloys was made, and a survey of binary AB3 structures is presented. EXPERIMENTAL The starting materials were pure metals of 99.9 wt pct purity. The alloys were arc-melted under partial pressure of argon and annealed in sealed silica capsules lined with molybdenum foil under argon at- mosphere. The total weight loss upon melting and subsequent annealing was always less than 1 pct and hence the alloys will be referred to by their intended (unanalyzed) compositions. Wherever the constitution permitted. the alloys were given a homogenizing treatment at 1200°C (3 days) prior to annealing. Unless otherwise stated all alloys were annealed at 900°C for 1 week and water-quenched. Sometimes the final annealing treatment was carried out on powders to accelerate the attainment of equilibrium. X-ray powder patterns were taken using a Guinier-de Wolff focusing camera (CuK, radiation) or an asymmetrical focusing camera (Co or CrK, radiation). For lattice parameter determination. internal silicon standards were employed. The intensity calculations were made using a Fortran IV program written by Jeitschko and parthe.9 RESULTS Twenty AB3 and three AB4 alloys were investigated. Table I lists the crystallographic data on some of the intermediate phases encountered in the present work. Table II contains the X-ray data for HfCo, (Th,,Mn,, type). The positional parameter, x. was assumed to be 0.378. the value for Th6Mnn2310 The X-ray pattern of ZrCo, was very similar to that of HfCo, and the previous structure determination of ZrCo, by Kuzma el al." was confirmed. Ordering in the alloy CrCo could be ascertained by the presence of only one weak super lattice line (101). the others being too weak presumably owing to the small difference in the scattering powers of chromium and cobalt. This line was observed in the X-ray pattern of powder from the massive sample annealed at 830°C (7 days) after the powder had been reannealed at 600°C (24 hr). The diffraction pattern of the powder similarly reannealed at 830°C (24 hr) contained only the lines due to a mixture of hcp and fcc Co(Crj solid solutions. Therefore, it appears reasonable to assume that O2 and/or N2 contamination which would be less likely to occur during the 600°C anneal was not responsible for the observed weak reflection. Also. this reflection cannot be identified with any of the strong lines of the neighboring s phase which is present in the Co-Cr system at higher chromium contents. The composition corresponding to the TiNi3 structure observed by Raman et al.12 in the two-phase alloy Ti,zt,, has been established in the present work as being between There was satisfactory agreement for the low-angle lines (up to d = 1.997A) between the observed diffraction pattern of TiCua and that calculated assuming the ZrAu, structure. as recently proposed by Pfeifer-et a1.I3 However. some of the superlattice lines. e.g., at d = 1.937 and 1.919A. predicted by the ZrAu, structure were not actually observed eve? though neighboring lines. at d = 1.947 and 1.986A. of comparable calculated intensity were present. The ZrAu

Jan 1, 1970

By Samuel S. Wyer

Discussion of the paper of SAMUEL S. WYER, presented at the New York meeting February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 263 to 279. DAVID T. DAY, Washington, D. C.-I would like to ask whether the court decisions quoted in the paper are general, or do they represent one side of the case; if so, are there any decisions that represent more than one side of the case? Are they of general application, or do they affect only one side? Also, what is the difference between a pump and a compressor from the standpoint of the natural-gas industry? I notice stress is laid on the word "pump" in. connection with some of the legal decisions, and then it is stated. that they must not pump or compress above 300 lb. The question is, is a pump a compressor and a compressor a pump, under certain conditions? SAMUEL S. WYER, Columbus, Ohio.-Answering the first question, I will say that the decisions cover both sides of the case very thoroughly, and are uniformly on the side that a company is justified in the use of gas compressors; in other words, there are no decisions holding it to be illegal to use gas compressors, with the exception noted in Indiana, Kansas, and Oklahoma where you cannot go below atmospheric pressure. In regard to the second question, I think the engineers and the gas operators themselves are responsible for the confusion. It is because the use of the term "pump" is almost universal, and so many people have obtained the idea that the primary function of a gas compressor is to pump air into the gas, in order to increase the consumers' gas bills. I appreciate that it is very hard to draw a clear line of demarcation. between a pump and a compressor. The distinction I have always made myself, and which I think is a logical one, is that you do not get the pumping action until you get below atmospheric pressure. As far as the compression end is concerned, there is only one State, namely, Indiana, that has any statutory limitation with regard to how high the pressure may be increased in order to put the gas into the transmission lines. The State law in Indiana limits the maximum pressure to 300 lb. per square inch.

Jan 5, 1916

By J. E. Gosline

In any theory of a hydrodynamic nature dealing with the vertical flow of gas-liquid mixtures in pipes, the two factors that present the greatest difficulty are the relative motion between the phases and the energy loss resulting from turbulence work. The former has generally been referred to in the literature as "slippage" and the latter as "friction." A third factor of importance is the nature of admixture between liquid and gas for both the relative motion between the phases as well as the turbulence work are functions of the type of mixture. Although much work of a general nature has been performed on the vertical flow problem, there have been very few attempts made to study experimentally the factors involved in the phenomenon individually. Of these, perhaps the most notable is the work of Moore and Wilde1 on slippage. Some writers on the subject have assumed that over a wide range of operating conditions the controlling type of mixture is one in which gas bubbles of uniform size are distributed throughout the liquid, and that the data obtained from experiments on the motion of single bubbles through various liquids may be used in evaluating the slippage. Ver-sluys2 has further assumed another controlling type of mixture in which the liquid occurs as a dispersed phase within the gas and applies data on the fall of drops of water in air to calculating the relative velocity. It was for the purpose of studying the applicability of data on single bubble motion to the slippage factor and to further observe the nature of mixtures that a research program was conducted at the University of California during 1932 and 1933. These experiments formed a basis for

Jan 1, 1936

By L. Dudley Stamp

On April 1, 1937, Burma, formerly a province of the Indian Empire, was formally separated from India and became an independent unit of the British Commonwealth. In future, therefore, statistics of oil production in India will exclude Burma and those for Burma will be separately published. The last few years have been marked by noteworthy, almost spectacular, developments in the oil fields of Burma and the Punjab. In Burma these developments have been the proving of unexpected extensions of the existing fields and not the discovery of entirely new fields. The new extensions are important not only to Burma in giving a new lease of life to her fields, but also in general as stressing some interesting geological aspects hitherto neglected. Production The production of crude oil in Imperial gallons has been: Burma India 1934 254,760,070 67,265,210 1935 251,338,974 . 71,323,362 1936 265,656,393 69,241,504 1937 (eat.) 270,000,000 70,000,000 The Chindwin Fields.—The small field at Indaw continues to produce steadily about 3,000,000 gal. a year, but no really deep test has yet been successfully carried out and resources are thus not yet fully known. The remote location of the field, inaccessible except by river and situated 22 miles from the Chindwin 270 miles up that river from its junction with the Irrawaddy, has not encouraged active exploitation. The field is worked exclusively by the Indo-Burma Petroleum Co., Ltd. (I.B.P.), using now an automatic gas-lift system, and the company formerly refined the oil at a small refinery at Pantha on the river near by. The chief market was for kerosene in upper Burma. The refinery has now been closed. The oil is stored on the field during the low-water season

Jan 1, 1938

By J. E. Gosline

In any theory of a hydrodynamic nature dealing with the vertical flow of gas-liquid mixtures in pipes, the two factors that present the greatest difficulty are the relative motion between the phases and the energy loss resulting from turbulence work. The former has generally been referred to in the literature as "slippage" and the latter as "friction." A third factor of importance is the nature of admixture between liquid and gas for both the relative motion between the phases as well as the turbulence work are functions of the type of mixture. Although much work of a general nature has been performed on the vertical flow problem, there have been very few attempts made to study experimentally the factors involved in the phenomenon individually. Of these, perhaps the most notable is the work of Moore and Wilde1 on slippage. Some writers on the subject have assumed that over a wide range of operating conditions the controlling type of mixture is one in which gas bubbles of uniform size are distributed throughout the liquid, and that the data obtained from experiments on the motion of single bubbles through various liquids may be used in evaluating the slippage. Ver-sluys2 has further assumed another controlling type of mixture in which the liquid occurs as a dispersed phase within the gas and applies data on the fall of drops of water in air to calculating the relative velocity. It was for the purpose of studying the applicability of data on single bubble motion to the slippage factor and to further observe the nature of mixtures that a research program was conducted at the University of California during 1932 and 1933. These experiments formed a basis for

Jan 1, 1936

By Samuel Wyer

THE art of natural-gas compressing is now over 25 years old, and has grown at practically the same rate as the increase in domestic natural-gas consumers. There are now over 200 natural-gas compressing stations in North America, aggregating more than 320,000 hp. of compressor capacity and representing a property value of more than $22,000,000, and compressing more than 85 per cent. of all the gas used. The age and magnitude of the art make it evident that the use of gas compressors is a recognized integral part and universal custom of the natural-gas business. The public also is not without its rights and vital interests in this problem. Approximately 1,700,000 domestic natural-gas consumers in North America are dependent upon gas compressors for their natural-gas service. That is, if the use of compressors were to be prohibited, the majority of these consumers would be unable to secure adequate natural-gas service. Each consumer represents between four and five persons, and it therefore follows that the comfort and well-being-as far as natural-gas service is concerned-of at least 8,000,000 persons would be affected if the use of natural-gas compressors should be prohibited. These 1,700,000 consumers have invested, in services, house piping, fixtures, and appliances, an average of about $90 each, or an aggregate of $153,000,000, which is much more than the companies' investment in gas compressors. Furthermore, in all cases where the rate paid by the consumers is fair to the gas company-considering the value of the service rendered by the gas company-the consumers are entitled to continued service and protection of the investment they have made on the faith that the gas service would be continued in the future.

Jan 2, 1916

By J. C. Swartz

New measurements of graphite and cementite solubilities in ferrite have been obtained to resolve disagreements among previous data. To measure graphite solubility, specimens of iron were equilibrated with rarious carburizing atmospheres at temperatures be-twee~z 480" and 1435°C. The carbon activity of each atmosphere relative to graphite was taken from published data. After quenching from each equilibration treatment the concentration of carbon (typically 10 pprn by wt) was determined from the height of the Snoek peak in the internal friction spectrum. A few inclividual analyses by combustion support the reszdts of Smith on the solubility of graphite near the eutectoid temperature. Combination of these combustion and internal friction analyses determines In a, (at 0.01 wt pct) = 24,000/RT - 12.72, where a, is the activtity relative to graphite in ferrite at fixed cornposition. The same specimens were used to determine the solubility of self-stressed cementite precipitates. The results indicate solubilities of 6.3, 23.2, and 68 pprn carbon by wt at respectively 400°, 500". and 600°C. The once large discrepancy between the cementite solubility determined by internal frictiori and that calculated from flee energy data has been almost completely resolved. A recent study1 (hereafter designated I) on the solubility of cementite in a iron did not fully resolve the disagreement among previous data. The remaining disagreement is illustrated by the phase diagram in Fig. L The data of I are represented by the line labeled "stress-free" cementite. They determine a heat of solution of cementite of (14.8 * 0.2) kcal per mole which contrasts with the (20 * 1) kcal per mole derived from Smith's graphite solubility2 and the formation energy of cementite.3 Toward resolving this disagreement we have obtained new data on the solubilities of graphite and cementite. METHODS As in I the Snoek peak in the internal friction spectrum was used to measure the concentration of carbon dissolved in ferrite. This method relies on the relation C=kQ-1 [1] in which C is the concentration of dissolved carbon, Q-I is the Snoek peak height, and k is a proportionality factor which is a function of the peak temperature, polycrystalline texture, and other parameters characteristic of the ferrite lattice. To determine true heats of solution via Eq. [1], it is necessary to establish that k is independent of the temperature from which the specimen is quenched. Some evidence on this point is contained in a separate report.* Additional evidence is shown by the data points in Fig. 1. These represent the Snoek peaks of two specimens carburized to about 10 ppm C, copper plated, and quenched first from 888º then from 588°C. The copper plate was removed before each Snoek peak measurement. These data show that there is no detectable dependence of k on quenching temperature. The solubility of graphite was determined by repeatedly carburizing various specimens of iron wire with gas mixtures of known carbon activity relative to graphite. To cover a wide temperature range within the a phase boundaries it is desirable to use as low a carbon concentration as is compatible with reasonable precision. With the present internal friction apparatus the best compromise of these desires is a concentration near 10 wt ppm. The dashed line in Fig. 1 was used to approximate the activity of carbon* for

Jan 1, 1970

By L. O. Howard

MUCH work has been done recently on the lead-antimony system1 in connection with lead-rich alloys of commercial importance containing less than 20 per cent. antimony. Dean, Zickrick and Nix have called attention to the perpetuation in the literature of several erroneous data, such as a eutectic temperature of 228° C. at 12.5 per cent. antimony, instead of 247° at 13 per cent. The series is given as a classic example of a straight eutectiferous series in such late books as those of Heyn and Grossmann,2 Jeffries and Archer,3 Guillet and Portevin4 Pulsifer,5 Rosenhain,6 and Liddell,7 as well as the somewhat earlier works of Hofman (1918), Wang (1909) and Williams (1920). The work of Dean has definitely showed a solid solution of antimony in lead at about 2.5 per cent. antimony. While lecturing to a class in general metallurgy at the University of Idaho, the writer had the students prepare a series of lead-antimony alloys for the purpose of illustrating methods of thermal analysis. Proper proportions of powdered antimony (sold as C.P.) and test lead were mixed and melted in graphite crucibles under a reducing cover. Cooling

Jan 1, 1928

By L. O. Howard

Much work has been done recently on the lead-antimony system1 in connection with lead-rich alloys of commercial importance containing less than 20 per cent. antimony. Dean, Zickrick and Nix have called attention to the perpetuation in the literature of several erroneous data, such as a eutectic temperature of 228° C. at 12.5 per cent. antimony, instead of 247° at 13 per cent. The series is given as a classic example of a straight eutectiferous series in such late books as those of Heyn and Grossmann, 2 Jeffries and Archer,3 Guillet and Portevin,4 Pulsifer,5 Rosenhain,6 and Liddell,' as well as the somewhat earlier works of Hof-man (1918), Wang (1909), and Williams (1920). The work of Dean has definitely shown a solid solution of antimony in lead at about 2.5 per cent. antimony. While lecturing to a class in general metallurgy at the University of Idaho, the writer had the students prepare a series of lead-antimony alloys for the purpose of illustrating methods of thermal analysis. Proper proportions of powdered antimony (sold as C.P.) and test lead were mixed and melted in graphite crucibles under a reducing cover. Cooling

By C. D. King

THIS year the American Institute of Mining and Metallurgical Engineers celebrates its seventy-fifth anniversary as well as the same anniversary of iron and steel in this country as we now know it. The society's span of life comprehends the very beginning and gradual development of the present-day iron and steel industry and its TRANSACTIONS are rich with the trials and achievements of the pioneers in this field. It is difficult to believe that in the first year of the Institute's existence there was produced in this country only 84,000 net tons of ingots, of which only 2000 tons was made by the open-hearth process; that the bessemer process was just barely beginning; that charcoal and anthracite were virtually the only blast-furnace fuels; that Mesabi ores had not been used in blast furnaces, and such pig iron as was then made was produced at a number of small units, each adjacent to its ore and fuel supply. The growth from 84,000 net tons production of steel ingots to 95,500,000 tons in 1945 eloquently tells the story of America's industrial growth.

Jan 1, 1947