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By J. H. M. Thomeer

A method is presented that provides a mathematical description of capillary pressure curves and, probably, of differences in pore geometry of samples. The technique is based on the observation that the location and shape of a capillary pressure curve reflect characteristics of the pore structure of the sample. INTRODUCTION It has been noted1-5 that the observed differences in shape and location of capillary pressure curves reflect some basic properties regarding the pore geometry of the samples. For example, according to basic concepts of capillarity, the following statements can be made regarding the location and shape of a capillary pressure curve.* The location of the curve with respect to the (Vb)pc and PC axes is a measure of the interconnected pore volume and of the cross-sectional area of the pore first entered by mercury, respectively. The shape of the curve depends on the interconnection of the pores and the sorting of the pore sizes. It has been the object of this study to use this information as a starting point in an attempt to find a unique mathematical description of the PC — (Vv)p, relations of different samples. It may be expected that parameters in such a relation can then be used to describe differences in pore geometry of these samples. For a practical description of the PC — (Vb)p, relation, however, it appears desirable to describe each curve (i.e., each sample) by a limited number of parameters so that the curves taken from all samples form a family, each member of which is uniquely determined by one single combination of values of all parameters.

By Benjamin Lustman, Robert F. Mehl

THE study of the high-temperature oxidation of pure metals, intensively pursued experimentally since the pioneer work of Pilling and Bedworth1 and supplemented by the recent theoretical work of Wagner2 is now well advanced. The important field of low-temperature oxidation-i.e., oxidation extending only through the temper color range of thicknesses with the formation of thin oxide layers in the range from o to 1000-2000 Angstroms-has not, however, reached so satisfactory a state, owing largely to the experimental difficulties that attend the formation and study of thin films; most of the work has been performed on abraded specimens whose surface irregularities approximated the thickness of the films formed. It has been pointed out that the rates of oxidation of different crystal faces are different and that the difference may be related to the orientation relationships that obtain between the metal crystal and the superimposed oxide crystal; it has also been suggested that this orientation dependence should manifest itself in rates of oxidation and perhaps also of corrosion in aggregates bearing preferred orientations. 3,4 An attempt to measure the rates of oxidation of different crystal faces of alpha iron demonstrated this difference in rate,4 but the dependence of rate on orientation was not simple; the method of measuring thickness, consisting of a color comparison with barium stearate multi-films of known thickness, was not wholly satisfactory. For these reasons it was felt that a study of the rate of oxidation of single crystals prepared with surfaces as smooth as possible, using a sensitive method giving true film thickness, should be profitable. Copper was chosen because of the ease of reduction of the primary oxide film and because the orientation relationships between metal and oxide and the composition of the oxide films formed at low temperatures are known; for thin films formed at low temperatures, Cu2O alone occurs.22-24 EXPERIMENTAL PROCEDURE Various methods of surface preparation were attempted in order to obtain a surface that would oxidize uniformly and reproducibly. Electrolytic polishing by the method of Jacquet5 and electrolytic and mechanical polishing followed by annealing in vacuum and in purified hydrogen at various temperatures were tested. The procedure finally adopted consisted in a fine metallographic polish followed by an anneal in purified hydrogen at temperatures of 900º to 1000°C. for 12 hr. or more. The surface so produced was very bright and smooth, with no trace of specular etching (though some grain-boundary etching was observed); indeed, fine scratches produced by the final polish were entirely removed by the high-temperature anneal.

Jan 1, 1941

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

THERE has been considerable discussion among A metallurgists and others interested in the development of titanium alloys as to the nature of the fine line markings which appear in the microstruc-tures of unalloyed titanium and a titanium alloys. These markings have been variously called x phase, etching pits, and twins. Figs. 1 to 3 show typical examples of the line markings as they appear, respectively, in high purity iodide titanium, commercial purity titanium rod, and a high purity a alloy containing 0.2 pct N. The commercial purity titanium sample, shown in Fig. 2, contains both line markings and some spheroidal retained-ß phase. The ß phase seen in this micrograph should not be confused with the line marking, since it originates from the iron present as an impurity in the sponge metal. It will be noted that the line markings seem to have a definite orientation pattern with respect to the grains and in titanium noticeably resemble the precipitation occurring in artificially aged high purity Al-Cu alloys. This similarity led to the hypothesis that the line markings observed in titanium and a titanium alloys resulted from precipitation of some unknown phase. With the work of Hägg1 and McQuillan2 as background, there was little reason to suspect hydrogen of being responsible for the line markings. Hagg reported that up to 33 atomic pct H was soluble in a titanium, and McQuillan reported an a solubility of up to 8 atomic pct. Furthermore, McQuillan examined metallographically a 5.1 atomic pct H alloy quenched from 300°C and stated that the structure appeared to be a single-phase a solid solution. Line markings have been observed frequently and were first noted by Jaffee and Campbell3 in 1949. They did not observe them in vacuum-annealed titanium and a Ti-O and Ti-N alloys, but did observe them in Ti-H alloys containing 0.25, 0.5, and 1 atomic pct H. They stated that it was doubtful that the markings were a second phase based on hydrogen, because 1 atomic pct was far from the accepted solid solubility of hydrogen in titanium. Finlay, Resketo, and Vordahl,4 in 1950, concluded that the markings were a true second phase as a result of observations on their etching characteristics. Anderson5 Commenting on these markings in titanium was inclined to associate them with hydrogen, but was loath to call them titanium hydride, because of the reported high solubility of hydrogen. Work at Battelle Memorial Institute for the Navy Bureau of Aeronautics," done concurrently with the work described in this paper, provided information on the experiment converse to that described by Jaffee and Campbell in 1949. This work showed that the amount of line markings in unalloyed titanium could be decreased by vacuum annealing at elevated temperature. It was suggested that this was the result of removal of hydrogen; previously, the data of Jaffee and Campbell9 howed that the markings appeared when hydrogen was added. Recent work at Battelle for the Ordnance Corps, Department of the Army, which is described here, now establishes the identity of the markings as a titanium hydride phase. A sample of high-purity titanium rod 1/4 in. diam, 0.009±0.001 wt pct H (0.43 atomic pct), Fig. 1, was resistance heated in a 0.05 micron vacuum for 41/2 hr at 1500°C. During the early states of heating, the pressure increased to 150 microns, indicating that gases were being evolved. After cooling in vacuum, the iodide titanium rod was analyzed for hydrogen. Vacuum-fusion analysis showed 0.0006 ±0.0003 wt pct H (0.03 atomic pct) to be present.* Metallographic examination of the vacuum-annealed rod showed only a transformed ß structure. There was no evidence of fine line markings, Fig. 4. A section of this vacuum-annealed rod was cold rolled to 0.040 in. thick sheet and annealed for 1 hr

Jan 1, 1953

By H. Siebel, N. A. D. Parlee

MIZIKAR, Grace, and parlee' studied rates of absorption of oxygen in stagnant liquid silver in a new type of open-ended gas-liquid metal diffusion cell, where the capillary diameters used were 1.5, 2, and 3 mm. They reported that the rates appeared to be controlled by the rate of diffusion of oxygen atoms in liquid silver and they used their data to arrive at the following equation as a reasonably good representation of the diffusivity (D) of oxygen in liquid silver: D = (14.7)10-4 exp (-7100 ± 3200)/RT cm2/sec Since this type of diffusion cell offers a promising method of measuring diffusivities of gas atoms in liquid metals, the senior author of this note and his students are carrying on a critical examination of the method, and are attempting to improve and extend the technique. The research reported briefly here was designed to examine more carefully the earlier conclusion1 that the absorption rate is diffusion-controlled, and to find out whether the diameter of the cell could be greatly increased and thus extend the method to systems where gas solubilities and diffusion rates are much smaller than in the case of oxygen in silver. For the purpose of these experiments, the open-ended capillary cell used by Mizikar, Grace, and Parlee was replaced by a small cylindrical crucible (1 to 1.7 cm in diam) containing pure silver (to a depth of 1.3 to 3 cm) resting in the bottom of a closed-ended vertical quartz tube, with an evacuated quartz filler tube just above the crucible to reduce dead volume. The method of measuring the rate of absorption was otherwise very similar to that of Mizikar, Grace, and Parlee and all the same precautions were taken. A much smaller and shorter tube furnace was used for heating, but simi- lar precautions about temperature gradients were observed. This technique was nothing more than the application of a Sieverts apparatus to the measurement of rates of absorption in small crucibles of stagnant liquid silver. In each run the volume of gas absorbed (V) was plotted against the square root of time (vt) and apparent diffusivities were calculated from the slope of the line, as described by Mizikar, Grace, and parlee.' Care was taken to use only the data obtained during the early part of the total absorption period while the cell functioned as one of infinite depth. The results at 1000°C are summarized in Table I and Fig. 1. The following conclusions may be drawn: 1) Diffusion cells up to 1.7 cm in diam yield, within experimental error, the same values for the diffusivity of oxygen (D) as the capillary cells of 1.5, 2, and 3 mm in diam employed by Mizikar, Grace, and Parlee. Cell diameters as large as 1.7 cm are probably not desirable for the most precise work. Intermediate sizes, perhaps 0.5 cm, will be most practical. 2) All absorptions measured were consistent with a model where the rate is controlled by the diffusion of gas atoms in the metal. The fact that runs at absorption pressures ranging from 0.1 to 1 atm (at any one temperature) give

Jan 1, 1965

By J. H. Hollomon, J. C. Fisher

THE fundamental problem concerning the fracture of both crystalline and noncrystalline solids is the divergence between the actual and the theoretically computed fracture stresses; the stress required for fracture, computed from the forces between atoms, is many times that actually observed with commercially available materials. Computations have been made1, 2 indicating that the theoretical fracture stress should be from 100 to 1000 times that actually observed. There are other incidental problems that have arisen, perhaps the most important of which is the problem of size effect often observed in the measurement of the fracture stress of non-metallic solids, such as glass. Another effect concerns the relation between deformation and the stress required for fracture. Experiments recently made with pearlitic steels indicate that the tensile fracture stress increases with increasing tensile deformation and decreases with increasing prior compressive deformation. This marked anisotropy of the effect of deformation on the fracture stress is in contrast with the essential isotropy of the flow stress. Early experiments on rock salt crystals by Joffé, et a13 have illustrated the effect of tensile strain in increasing the tensile stress required for fracture. A consistent theory must be constructed that will explain not only the divergence of the measured fracture stress from the theoretical value, the size effect, and the effect of deformation; but will also explain and predict the effects of combined stress, of temperature, of strain rate, and of metallurgical structure. With respect to this last variable, it has now been relatively well established that the carbide particle is the element of structure controlling the fracture of steels. In steels carbide particles vary in shape from plates to spheroids. It has been found that not only does the magnitude of the fracture stress depend upon the size and shape of these particles, but also its dependence upon strain is affected by changes in shape and size of the particles. The precipitate resulting from the age hardening of duralumin also modifies the fracture stress of this alloy. Nonmetallic inclusions greatly lower the fracture stress of all metals. The magnitude of the lowering depends on the size and shape of the included particles. In glass, the major source of the low fracture stress has been fairly conclusively demonstrated by Griffith4 to arise from real flaws or cracks present in the material. He showed that the stress concentration at the end of a defect was of sufficient magnitude to raise the stress at this location to a value comparable with the theoretical strength of the material. If the cracks were reduced in size, Griffith showed that the observed fracture strength increased by virtue of the decrease in stress concentration. He also pointed out that cracks disposed perpendicularly to the applied tensile stress would be more effective in lowering the fracture

Jan 1, 1947

The first record of coal anywhere in the Appalachian regions of which we now know is along the north fork of the Potomac River, above the mouth of Savage River, on a map entitled, A Plan of the upper Part of Potomack River call Cohongorooto Survey'd in the Year 1736. Benj. Winslow1 two "Cole-mines" are shown, one just above Green Island and the other just below Hopwood Run. Winslow was in charge of a surveying party to "Lay out the Bounds of the Northern Neck of Virginia," or Lord Fairfax's Grant, his party locating the liver above the mouth of the Shenandoah, while another party located it below that point, and then around Chesapeake Bay and up the Rappahannock River. The results of the two surveys were combined in a map called, The Courses of the Rivers Rappahannock and Potowmack, in Virginia, as surveyed according to Order in the Years 1736 & 1737, made by Wm. Mayo, which does not show the "cole-mines;" this map was used with the report of the boundary commission which was sent to London in the case before the Privy Council. The boundary line decided upon was surveyed on the ground in 1746, just ten years after the original one. The results of this work were shown on A Map of the Northern Neck in Virginia, According to an Actual Survey begun in the Year MDCCXXXVI, and ended in the Year MDCCXLVI, Drawn by Peter Jefferson And Robert Brooke, Surveyors, which is now in the Colonial Office in London. This map shows the "cole-mines" in the same location as on Winslow's map, and taken from his record, of course, as that part of the survey was not retraced. Faulkner, who examined all of these records in his review of the case in 1832, refers to the notes of the original survey as "No. 10. The original field notes of the survey of the Potomac River, and the mouth of the Shenandoah to the head spring of said Poto¬mac River, by Mr. Benjamin Winslow." While the notes of the 1746 survey are in the London records and photographic copies of them are in several libraries in this county, the notes of the 1736 survey cannot be found anywhere. (For Chas. J. Faulkner's report, dated Nov. 6, 1832, see Kercheval's History of the Valley of Virginia, pp. 160-173. Jas. W. Foster's Maps of the First Survey of the Potomac River, 1736-37, in Wm. and Mary College Quarterly History Mag., April, 1938, gives a complete history

Jan 1, 1942

By H. Landssberg

Subsidence caused by mining operations has been a matter of interest for the mining engineer for just 111 years, since the Belgian committee for study of subsidence in the city of Liege submitted its first report in 1825. This interest is fairly expressed in the enormous amount of literature that has since appeared on this subject. A bibliography, probably far from being complete, which preceded this study as a preliminary survey, comprises more than 800 titles. In spite of this fact the problem remains today as acute as it has ever been. The questions of as good a recovery as possible of the national resources, the safety of the operations, and the protection of private and public property are the important angles from which to look at the problem. The Problem To systematize an investigation regarding the effects of mine excavations two different aspects have to be dealt with: (1) the subsidence of the immediate roof above the workings, affecting the safety of the workers and the progress and efficiency of the operations; (2) the subsidence of the surface, which is also, from the point of time, the second event. The immense importance of surface subsidence as regards the impairment of surface structures of every kind in a mining area is self-evident. Both effects result from reactions of the strata overlying the excavations and they depend mainly on the extent of the excavations and the structure and geological condition of the strata. It has been stressed repeatedly, in this country principally by G. S. Ricel,† that for the understanding of the phenomenon of subsidence accurate surveys are the most urgent necessity. In the past, however, at least in the normal course of mining operations, these surveys have been very crude. The control of the roof in the mine is left to the observation of the behavior of the timber, warning cracks and sounds in roof and walls and to the general judgment and experience of the worker and his supervisors. In any given case this may or may not be sufficient to prevent fatalities but certainly it does not give any accurate information as to what is happening in roof and strata. On the surface, principally in endangered areas, surveys have been conducted more frequently, but also in this case usually weeks or even

Jan 1, 1936

By H. Landssberg

Subsidence caused by mining operations has been a matter of interest for the mining engineer for just 111 years, since the Belgian committee for study of subsidence in the city of Liege submitted its first report in 1825. This interest is fairly expressed in the enormous amount of literature that has since appeared on this subject. A bibliography, probably far from being complete, which preceded this study as a preliminary survey, comprises more than 800 titles. In spite of this fact the problem remains today as acute as it has ever been. The questions of as good a recovery as possible of the national resources, the safety of the operations, and the protection of private and public property are the important angles from which to look at the problem. The Problem To systematize an investigation regarding the effects of mine excavations two different aspects have to be dealt with: (1) the subsidence of the immediate roof above the workings, affecting the safety of the workers and the progress and efficiency of the operations; (2) the subsidence of the surface, which is also, from the point of time, the second event. The immense importance of surface subsidence as regards the impairment of surface structures of every kind in a mining area is self-evident. Both effects result from reactions of the strata overlying the excavations and they depend mainly on the extent of the excavations and the structure and geological condition of the strata. It has been stressed repeatedly, in this country principally by G. S. Ricel,† that for the understanding of the phenomenon of subsidence accurate surveys are the most urgent necessity. In the past, however, at least in the normal course of mining operations, these surveys have been very crude. The control of the roof in the mine is left to the observation of the behavior of the timber, warning cracks and sounds in roof and walls and to the general judgment and experience of the worker and his supervisors. In any given case this may or may not be sufficient to prevent fatalities but certainly it does not give any accurate information as to what is happening in roof and strata. On the surface, principally in endangered areas, surveys have been conducted more frequently, but also in this case usually weeks or even

Jan 1, 1936

Jan 1, 1889

By J. T. Williams

The equilibria in the V-Zr alloy system were investigated by solidus temperature determinations, thermal analysis, dilatometry, electrical resistance measurements, microscopic examination, and X-ray diffraction analysis. There is a eutectic reaction at 1230°C between a compound, V2Zr, and a solid solution containing 10 pct V in ß zirconium. V2Zr decomposes at 1300°C into liquid and a solid solution containing about 10 pct Zr in vanadium. The eutectic composition is probably about 30 pct V. A eutectoid reaction between V2 Zr and a zirconium takes place at 777°C at a very high rate. The eutectoid composition is 5 wt pct V. The limit of solubility of zirconium in vanadium was estimated to be 5 pct at 600°C. No attempt was made to determine the liquidus for the system. THE recent availability of large quantities of high purity zirconium has stimulated the study of zirconium binary systems. The equilibrium diagram for the V-Zr system has received little attention, however. Wallbauml appears to have made the first report concerning the equilibria in these alloys. He reported the existence of a compound, V2Zr, having the MgZn2 ((214) type of structure with a, = 5.277 kX and c° = 8.647 kX. Anderson, Hayes, Roberson, and Kroll2 made a survey of some potentially useful zirconium binary alloys and found that zirconium probably dissolves a small amount of vanadium. They reported the probable existence of a compound between the two elements and suggested that the zirconium-rich solid solution undergoes a eutectic reaction with this compound. Pfeil," in a critical review of the existing information, estimated that the solubility of vanadium in zirconium is less than 4.7 pct and probably less than 1.8 pct. Rostoker and Yamamoto' proposed a partial diagram for the V-Zr system in a survey paper on vanadium binary alloys. Their diagram indicates the compound, V,Zr, a eutectic reaction at 1360°C, a peritectic reaction at 1740°C, and a limit of solubility of zirconium in vanadium of about 3 pct. They obtained no information on the equilibria in the zirconium-rich alloys. In view of the potential utility of the V-Zr alloys and the incomplete knowledge concerning the equilibria in the system, an attempt was made to establish the constitutional diagram. Preparation of the Alloys Raw Materials: The vanadium for making up these alloys came from the Electro Metallurgical Corp. Zirconium came from two sources. In the beginning of the investigation, sponge zirconium from the Bureau of Mines was used in making some of the alloys. Later, iodide metal made at the Westinghouse Atomic Power Development Laboratories became available. This material was used in the preparation of all the dilatometric and resistance specimens and about two-thirds of the solidus temperature specimens. A typical manufacturer's analysis of the vanadium is shown in Table I. No other analysis of the vanadium was made. The metal contained a dispersed second phase and did not have a sharp melting point. Typical results of spectrographic analysis of the Westinghouse zirconium are shown in Table 11. These data indicate a very high purity. The Bureau of Mines sponge metal was probably less pure but had good ductility. Melting: All of the alloys used in the investigation were made by melting pieces of vanadium and zirconium together in a dc electric arc furnace similar to those of Geach and Summers-Smith, craighead, Simmons, and Eastwood," and others. Melting was done in an atmosphere of helium scavenged of residual air by the preliminary melting of a separate charge of zirconium. Each ingot was turned over and melted at least three more times before removal from the furnace to aid in the attainment of homogeneity. Alloys prepared for use in the investigation are listed with the results of solidus determinations in Table III with the exception of the following compositions upon which no solidus determinations were made: 0.29, 0.54, 4.57, and 5.55 pct V. Analysis: The weight of each ingot made from iodide zirconium was within 0.1 g of the total weight of the initial charge, about 90 g. Since each component of each charge was weighed to the nearest 20 mg for amounts less than 10 g and to the nearest 0.1 g otherwise, the gross composition of an ingot could be calculated accurately. Chemical analysis for the vanadium content of several alloys agreed

Jan 1, 1956

By G. A. REINHA

GEO. F. COMSTOCK,* Niagara Falls, N. Y. (written discussion?).-On studying this paper it has occurred to the writer that possibly it was the drilling of the test cores that produced the strains which affected in-juriously the authors' unrested bars. They found that the machining had only a slight effect, but did they also investigate the effect of the drilling by trying rest applied to the bloom sections before the cores were drilled from then? The writer has heard of a similar effect of rest after machining on test bars from castings, and it would seem more reasonable that the ductility was increased because the rests relieved strains pro-duced in chilling the test cores from the blooms, than because of any peculiar combination of solidification and rolling strains in the blooms which did not exist in smaller billets.

Jan 11, 1919

By F. Brons, W. C. Miller

Pressure information for use in material-balance calculations is obtained, where possible, from pressure build-up surveys in shut-in wells. Using proper extrapolation methods, static pressures are obtained which, by averaging, give the field static pressure. Often, particularly in fields with a large number of wells, only spot pressure readings are available. A graphical method is presented here which enables the determination of the corrections which must be applied to the spot readings to give an estinzate of the static pressure. Although the static pressures thus obtained are not so reliable as those from build-up surveys, they are more nearly correct than the spot readings themselves for use in material-balance calculations. INTRODUCTION The average static pressure in a bounded reservoir is determined from a number of individual-well pressure measurements. Where pressure build-up curves are available, extrapolation methods such as described in Ref. 3 may be used to determine the static pressure in the drainage area of each individual well. The possibility of using pressure build-up curves presupposes that each well being surveyed is closed in during a certain period and that, during this time, a pressure recorder is left suspended in the hole. For surveys in fields with a large number of wells, this is usually not feasible for economic and other reasons. Either a large number of pressure recorders would have to be used simultaneously or, using a limited number of recorders, the time interval needed to complete a field-wide survey would be too long. The data obtained for this incomplete coverage are insufficient to permit reliable averaging of the few calculated static pressures over the entire reservoir. In many such cases another type of pressure information is available, i.e., spot pressure readings. During this type of pressure survey all wells are closed-in simultaneously and, after a reasonable shut-in time (e.g., three days), pressure readings are taken by running the recorder in and out of each successive well. These surveys, which are less expensive, are often taken at regular intervals, say once or twice a year. In fact, such surveys are required by the state regulatory bodies in many portions of the united States. These spot readings are normally lower than the static (fully built-up) pressure due to the relatively short shut-in time. No direct means of extrapolating such a reading to the static pressure is available because no pressure build-up record is obtainable. Consequently, these data are inferior to pressure build-up information as a basis for estimating the stabilized reservoir pressure in the drainage area of a specific well. For the common case where abundant spot readings but only a few pressure build-up surveys are available, our studies suggest that it may be possible to design a program which will combine the two types of information and provide an estimate of the average reservoir pressure that is more reliable than that obtainable solely from either set of data. in time) gives a point marked p. The actual static pressure at the time the well was shut-in is marked by p.. The illustration shows that, even if a build-up curve is available and can be extrapolated, a correction

By D. Turnbull, J. H. Hollomon

IN the most general sense, solidification refers to the formation of crystalline material from either a gas or a liquid. However, in this symposium, only the formation of crystals from liquids will be considered. Thus, in our present study the problem of solidification becomes that of determining the mechanism of the transition from a liquid to a crystalline solid, and our particular interest is in the transformation of metals from the liquid to the crystalline state. Metal liquids are seldom composed of only one kind of atom. Often solute atoms are added intentionally to make an alloy, or they may be present accidently because of incomplete purification. Furthermore, there may be small solid particles of various other crystals present in the liquid. Such small crystals may persist if their melting points are higher than any temperature to which the liquid is heated. Prior to solidification, the liquid metal usually is poured from one container to another. The second container, called the mold, usually is at a lower temperature than the container, or the crucible, in which the metal is liquified. The first solid that forms upon contact with the mold generally is of a different composition than the liquid, usually containing fewer foreign atoms or dissolved impurities. Heat is evolved upon solidification and is dissipated through the surroundings. Tree-like crystals, or dendrites, grow from the container walls and branch into the melt, enriching the remaining liquid in impurity atoms. In some alloys the remaining, relatively impure liquid continues to solidify until no liquid remains and the branches of the original crystal are cemented together. In other alloys, particles with a second type of crystal structure appear before solidification is complete. First the nature of the liquid and the solid states will be considered and then the mechanism of the initial formation of crystals from pure and alloy liquids. Later the problem of the growth of these crystals and the complexities of solidification in a mold, where the temperatures are not uniform and the composition of the melt changes continuously, will be discussed. LIQUID AND CRYSTALLINE STATES A liquid is an aggregate of atoms arranged with no apparent regularity (over distances of more than a few atom diameters). Nevertheless, any given atom generally has a definite number of nearest neighbors at definite distances, and thus order may be said to exist over a short range. In a crystal, on the other hand, a regular array of atoms continues for many hundreds or thousands of atom diameters, and a long-range order is apparent. Thus, a crystal having long-range order can be reproduced by linear translations for 10-5 cm or more of some fundamental unit possessing short-range order. A crude illustration of the difference between liquid and crystalline structures can be obtained by comparing the possible arrangements of oranges in a crate. If the oranges are simply dumped into the crate haphazardly until it is filled, the oranges will represent a static model of a liquid.

Jan 1, 1951

By C. W. Hill

IN a previous article preliminary experiments were described, indicating the possibilities of a quantitative spectroscopic method for the determination of small amounts of lead in copper, which would be accurate and rapid, and could be carried out in the refining plant by one not skilled in chemical analysis. The present paper deals with the development of the method in the factory, giving the details of apparatus and its standardization, and presenting a comparison of the accuracy of the method with that of the standard electrolytic determination. (For variations and other applications of the method, the reader is referred to the first article.) FIG. 1.-STEPS IN THE ELIMINATION OF LEAD. (The lead line, at point 105.8 in the violet portion of the spectrum, is seen between the two copper Lines,-102.29 and -106.29, lying close to the latter. The crowded faint lines are due to the carbon are.) 1. OUTLINE OF METHOD A carefully weighed sample (0.4 gm.) of the copper to be tested is placed in a cavity in a graphite positive electrode. An arc capable of

Jan 10, 1918

Mr. Brown : .That part of the Standard Company's plant which has been added since the publication of Mr. Leggett's paper, and is described in mine, renders the single-phase, alternating system, which Mr. Hale has called " unelastic," much more elastic than it had been. The original plant at Bodie was substantially the same as the Telluride plant mentioned in his paper. The machines came from the same shops, and were practically the same; but while the Telluride Company has changed completely to a polyphase system, the Standard Company has retained its original plant, but has belted on a directcurrent generator at the receiving end, thereby converting the water-power into electricity, electricity into power, the power into electricity, and finally again electricity into power for use in the mines. This is a roundabout course, to be sure, but it shows that there are possibilities even in the out-of-date single-phase system. The only point perhaps, that deserves particular notice with respect to the hoist is the fact that the rheostat, or starting-resistance, was not built originally

Jan 1, 1897

By John J. McKetta. Jr., Louis B. Lesem, George H. Fancher

The proration of oil produced in the field frequently is based partially or entirely upon the gas-oil ratio of wells. The measurement of the gas-oil ratio is one of the more important field tests in regulatory and pro-ration work, and the test always should be conducted according to standardized methods and procedure. Obviously, the gas-oil ratio and the volume of gas produced by a well depend upon many factors but should be independent of the method of measurement and of the devices used to measure gas and oil. Consequently, the volume of gas accompanying a barrel of oil produced by a well may be measured by any reliable and accurate device or instrument. Frequently either a critical flow prover or an orifice well tester is used for this purpose, and for a particular well the same rate of flow of gas should be obtained regardless of whether a critical flow prover or an orifice well tester is employed in the test. In Texas, when using either instrument, either Capacity Table 1 or 5' is employed in making the necessary computations. If the tables are used, a discrepancy always is found whenever the two instruments are compared by extrapolation to the same conditions of flow. Clearly, Tables 1 and 5 must be at fault in some respects. The orifice well tester and the Bureau of Mines type of critical flow prover are essentially the same instrument; both devices utilize a square-edged orifice 1/8 in. in di-ameter as the primary element, and both freely discharge gas to the atmosphere. Tables for the orifice well tester' have been published in the ranges of 0 to 15 in, of water and 0 to 40 in. of mercury (Hg) differential in pressure. Coefficients for the critical flow prover have been published for differentials in pressure greater than 75 psia. An extrapolation of either differs from the other set of data as much as 18 per cent at some points. No immediately obvious reasons for the discrepancy was found, and data available from the literature were insufficient to effect reconciliation. Consequently, a series of experiments was performed to check the available data and to determine discharge coefficients for the two devices in an overlapping range of differential pressure. The correlating equation used in preparation of tables such as Tables 1 and 5' is the so-called hydraulic equation, Q = C1 vh .....(1) The tables cover orifice sizes from 1/8 through 1 1/4 in. A second set of tables, for use with greater differentials in pressure, apply only to the 3/4, 1, and 1 1/4-in. orifice plates over a pressure range of 0 to 40 in. of Hg. The correlating equation used in preparation of the tables is Q = C2 vH(29.32 + 0.3H)/G . (2) Each of these equations is valid only for the range to which it has been applied, and neither equation is valid for extrapolation. Theoretical equations for flow through an orifice are based upon assumptions of fractionless flow and an emergent jet the size of the orifice. A multiplier, C,, called the discharge coefficient, is inserted into the theoretical expression to compensate for both frictional losses and the contraction of the jet experienced in the plane of the orifice. Buckingham3 shows that C, should vary with the ratio of upstream to downstream pressure for flow of a compressible fluid at any average linear velocity through the orifice less than the velocity of sound. Work published by the National Advisory Committee for Aeronautics4 indicates that the variation continues into the so-called critical flow region until the vena contracta coincides with the plane of the orifice. The NACA work, however, does not indicate a leveling off of the coefficient. The work of the Bureau of Mines5 for the critical flow prover was based on differential pressures greater than 75 psi and indicates that the discharge coefficient, Cd, is constant in this region at a value of about 0.86.

Jan 1, 1958

G. B. WATERHOUSE,* Buffalo, N. -Y. (written discussion?).-One of the most essential features of rail manufacture is the production of rails that will give good service and be free from failures. To this end rails are made to careful specifications and their manufacture is controlled by rigid inspection on the part of both the producing mill and the railroad or its representative, such as the Hunt special inspection referred to in the paper. Captain Hunt refers to the crescent-shape base failures and describes them as ruptures in the rail flanges extending from the outside inward toward the web. This is hardly correct and may be misleading. It has been shown, over and over again, that the base breaks originating in seams invariably start at the center of the rail base; and run longitudi-nally in varying lengths from 3 to 12 in. and sometimes longer. Most of them are from 5 to 8 in. long and then curve outward to the edge of the flange. The split at the center of the base may exist for an indefinite time and not be discovered until the break shows on top of the flange or the piece of flange breaks off. The. stresses that cause the break are explained in two ways: (1) by the eccentric bearing of the rail base, that is taking contact at one side or edge and bringing excessive strain at the center of the base which starts fracture in any seam that may he present at that point; (2) the split may be due to cross strain in the base where this member is thrown into. compression, as happens where a pair of trucks are on opposite sides of the cross tie or rail-base hearing, and the head is put in tension. A careful study of "split base breaks" shows that fully 95 per cent. occur on the tie bearing, which is further evidence that the above de-scribed causes for the initial break are probably correct. These split base breaks are almost invariably progressive, but always start at the center of the rail-base running longitudinally.

Jan 12, 1919

By E. W. McAllister

THE decision of the California Oil Umpire's1 office to accept well potentials established from subsurface-pressure data has brought to the attention of many operators for the first time the application of such data to production problems. This paper reviews the development and application of subsurface-pressure data in Kettleman Hills, where these data have been used in production work since 1932. The Kettleman Hills field was discovered in October 1928. The first subsurface-pressure surveys were made early in 1932 and by the middle of 1933 the two major operators in the field were making routine pressure runs in their respective wells. Shortly thereafter, these companies agreed to exchange pressure data, and later a third company entered into the agreement. This made it possible to analyze the effects upon the reservoir pressure of past production practices, which are discussed in the latter part of the report. It is interesting that many of the applications of subsurface-pressure data discussed herein were anticipated by C. L. Clarks and C. B. Kimberlin‡ in a reports dated March 1933. PRODUCTIVITY INDEX In the majority of individual well problems involving the use of subsurface pressure data, it is necessary to use a factor known as the "productivity index," which indicates the ability of a well to produce and represents the number of barrels of oil or oil and water per day that will enter the well bore for each pound per square inch pressure drop made opposite the producing interval of the well. The productivity index may be determined from pressure and production data for one or more rates of flow and a static or shut-in pressure survey or from production and pressure data for two or more rates of flow. Productivity indices may be based upon either net oil or total fluid production. All indices referred to in this report are based upon net oil. The value of the productivity index for Kettleman Hills wells decreases generally with time and it is not uncommon for the index to vary in value at any specific time for various rates of flow. The decline of the productivity index may be attributed partly to the loss of reservoir pressure. As. the reservoir pressure decreases, gas originally in solution is released from the oil, congesting the flow of fluids through the formation and increasing the viscosity and surface tension of the oil; thus the flow resistance of the fluids through the formation is increased, resulting in a decrease of the productivity index. For convenient reference, the productivity indices for each well are plotted against time and a curve is drawn through the points showing the trend of the average index value. Plotted on Fig. I are index values for five

Jan 1, 1941

For the year ending February, 1919 PRESIDENT SIDNEY .J. JENNINGS NEW YORK, N. Y. PAST PRESIDENTS L. D. RICKETTS, NEW YORK, N. Y. PHILIP N. MOORE, ST.Louis, Mo. FIRST VICE-PRESIDENT C. W. GOODALE BUTTE, MONT. TREASURER GEORGE C. STONE, : NEW YORK, N. Y. SECRETARY' EMERITUS ROSSITER W. RAYMOND NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON, NEW YORK, N. Y.

Jan 10, 1918

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'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's4 data, and Kubaschewski7 has similarly treated Kawakami's7 data. Presumably. in each case a regular solution was assumed. For regions where a two-phase field

Jan 1, 1970