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By H. G. Landua, Leah L. Naugle, H. H. Lowry

Evidence has been accumulating in recent years, in part from the work of the Coal Research Laboratory, that coals belong to a family of natural polymers and that even in complex reactions the differences between coals are quantitative and not qualitative. This point of view leads to the expectation that if a series of coals were subjected to a closely controlled set of experimental conditions the results obtained should be related to the chemical analyses of the individual coals. The data accumulated over the past 10 years by the Bureau of Mines in its ('Survey of Coke-, Gas-, and By-Product-Making Properties of American Coals," in what has come to be recognized as the Bureau of Mines-American Gas Association (BM-AGA) carbonization assay test,l-l2 offer an unusual opportunity to check this conclusion. The present paper reports an analysis of the data on the first go coals and coal blends— including coals numbered I to 55B, inclusive —which have been carbonized according to a standard procedure at intervals of 100°C. from 500° to 1100° in either or both 13 or 18-in. cylindrical retorts.13 In Table I are given the name of the seam from which the sample was obtained, the analytical data used, and the reference to the original publication of the Bureau of Mines. The coals range in fixed carbon from 46.2 to 79.0 per cent, in volatile matter from 15.4 to 41.3 per cent, in ash from 2.1 to 15.9 per cent, in moisture from 0.8 to 19.7 per cent, and in total sulphur from 0.40 to 4.44 per cent; therefore the entire gamut of bituminous coals is represented. The petrographic nature of the individual coals is not considered in the following analysis, although both "normal" bright coals and splint coals are included in the samples studied. For information on the petrography of the coals and for further information characterizing the coals the original papers should be consulted. Although the coals that are included extend over the whole range of bituminous coals, they do not cover this range entirely adequately. In particular, only 13 of the 90 coals have moisture contents greater than 3 per cent. This concentration at low moisture values means that the effect of moisture, which is an important factor, cannot be determined with as much certainty as would be desirable. All the coals were not tested at every temperature and in both retort sizes. Only the first 30 coals were tested at 1100°, and only about 50 at the other temperatures, except at 900°, where nearly all of them were included. In the accompanying tables the actual number of observations entering into each correlation is given. In this study equations are given for calculating analyses, yields, and properties of coke and by-products from the coal analyses. To decide whether these equations are satisfactory it is necessary to know the accuracy with which these quantities were measured in the assay tests.

Jan 1, 1942

By Leah L. Naugle, H. H. Lowry, H. G. Landua

Evidence has been accumulating in recent years, in part from the work of the Coal Research Laboratory, that coals belong to a family of natural polymers and that even in complex reactions the differences between coals are quantitative and not qualitative. This point of view leads to the expectation that if a series of coals were subjected to a closely controlled set of experimental conditions the results obtained should be related to the chemical analyses of the individual coals. The data accumulated over the past 10 years by the Bureau of Mines in its ('Survey of Coke-, Gas-, and By-Product-Making Properties of American Coals," in what has come to be recognized as the Bureau of Mines-American Gas Association (BM-AGA) carbonization assay test,l-l2 offer an unusual opportunity to check this conclusion. The present paper reports an analysis of the data on the first go coals and coal blends— including coals numbered I to 55B, inclusive —which have been carbonized according to a standard procedure at intervals of 100°C. from 500° to 1100° in either or both 13 or 18-in. cylindrical retorts.13 In Table I are given the name of the seam from which the sample was obtained, the analytical data used, and the reference to the original publication of the Bureau of Mines. The coals range in fixed carbon from 46.2 to 79.0 per cent, in volatile matter from 15.4 to 41.3 per cent, in ash from 2.1 to 15.9 per cent, in moisture from 0.8 to 19.7 per cent, and in total sulphur from 0.40 to 4.44 per cent; therefore the entire gamut of bituminous coals is represented. The petrographic nature of the individual coals is not considered in the following analysis, although both "normal" bright coals and splint coals are included in the samples studied. For information on the petrography of the coals and for further information characterizing the coals the original papers should be consulted. Although the coals that are included extend over the whole range of bituminous coals, they do not cover this range entirely adequately. In particular, only 13 of the 90 coals have moisture contents greater than 3 per cent. This concentration at low moisture values means that the effect of moisture, which is an important factor, cannot be determined with as much certainty as would be desirable. All the coals were not tested at every temperature and in both retort sizes. Only the first 30 coals were tested at 1100°, and only about 50 at the other temperatures, except at 900°, where nearly all of them were included. In the accompanying tables the actual number of observations entering into each correlation is given. In this study equations are given for calculating analyses, yields, and properties of coke and by-products from the coal analyses. To decide whether these equations are satisfactory it is necessary to know the accuracy with which these quantities were measured in the assay tests.

Jan 1, 1942

By A. S. Emanuel

A correlation has been developed for calculating the phase behavior of, gas-condensate systems at reservoir conditions. The correlation is based on the principle of corresponding states and has been coded for an IBM 7094. Experimental K-values were determined for several gas-condensate systems at reservoir conditions to evaluate various semi-empirical parameters of the correlation. The approximate range of application of the correlation is 150 to 300F and 1,500 to 6,000 psi. INTRODUCTION The rapid development of digital computers during the past several years has made feasible the calculation of hydrocarbon phase behavior by methods based on rigorous thermodynamic principles. Good correlationsl have been developed for low to moderate pressures, but these techniques have not yet been extended successfully to reservoir fluids at high pressures. Consequently, the determination of phase behavior of oil and gas systems at reservoir conditions is still based almost entirely on generalized data correlations or on experimental studies of the fluid in question. While these methods have been used successfully many times, they do have inherent limitations that restrict their applicability. Generalized correlations, such as the NGShlA K-charts, are limited to the range of pressure, temperature and components for which the data were determined. The accuracy of these correlations is often questionable because the effect of total system composition is not well defined. Experimental studies offer a reliable method for determining phase behavior, but usually the studies are costly and time consuming. Recently, Leland and co-workers presented a new approach to calculating phase behavior from the principles of corresponding states.6-8 Corresponding states methods determine the thermodynamics properties of a given system by comparison with a reference substance whose properties are known. The accuracy of this approach depends on close chemical and structural similarity between the reference substance and the system in question and between components within the system itself. For high accuracy, it is usually necessary to correct for chemical and structural dissimilarities. In principle, however, the corresponding states method should be no less accurate at high pressures than at low pressures, provided reference substance properties are known. This paper describes an empirical modification of the basic correlation proposed by Leland, et al.6 for the specific purpose of calculating the phase behavior of gas-condensate fluids at reservoir conditions. The modified correlation, which has been programmed for an IBM 7094, may be used for either approximate or precise determination of fluid behavior depending on the amount of analytical and, experimental data available for the system. BASIC THEORY The basic theory of the corresponding states phase equilibria correlation was first published by Leland, Chappelear and Gamson.6 Subsequently, Leland, Chappelear and Leach published methods for improving the accuracy of the original theory.7-9 The aim of the correlation is to calculate the K-value of each component of a given system as a function of pressure, temperature, and over-all composition, where Once the K-values are known, the phase behavior may be determined directly by an appropriate flash calculation. The basic equation for calculating component K-values was taken from the work of Joffe. 4 For any component i of a mixture, the K-value is given by

Jan 1, 1969

By Walter Renton Ingalls

Metallurgical literature has no record of any ore beneficiated for cadmium alone, and the cadmium of commerce is derived from zinc ore, with which cadmium is generally associated. Zinc ores free from cadmium—e.g., the ores of the Franklin and Stirling mines, New Jersey, and of Broken Hill in Rhodesia—are rare. Blende concentrates of 50 to 60 per cent grade have contained (in production of important tonnage) as much as I per cent Cd, which is unusually high. The concentrates from the Tri-State district average from 0.3 to 0.4 per cent Cd, which is high. The concentrates from mines west of the Rocky Mountains seldom are higher than 0.2 per cent. In the periodic system of the elements, cadmium is in the same group with zinc. Its properties and compounds are similar. Its metallurgy is also similar. Cadmium has a melting point of 320°C. and a boiling point of 778"C., while the melting point of zinc is 415'C. and the boiling point gos°C. These conditions, together with the lower reduction temperature of cadmium oxide, indicate means for. separating cadmium from zinc. Cadmium in spelter is viewed, if not as an impurity, at least as an alloying element that may be objectionable, its special effect being hardening. However, for some purposes, a little cadmium in spelter is desired, and 0.4 per cent may be permissible, even in spelter for rolling. Cadmium in spelter for brassmaking is completely volatilized at the temperature of that process, and in bygone days an immense quantity of cadmium must have been lost in the fumes from these furnaces. Pyrometalltjrgy—Early Cadmium compounds, sulphide and oxide, being more volatile than the corresponding compounds of zinc, loss of cadmium begins to occur from the first furnace operation. In normal roasting, even with Tri-State ore, this loss may not be very high. Raw ore, assaying 0.4 per cent Cd, may be expected to give a roasted product of the same assay, which would imply a cadmium loss of about 15 per cent. Roasted ore, assaying 0.4 per cent Cd when distilled at ordinary furnace temperature, yielded spelter containing about half of that in the ore charged. The first draw of spelter under these conditions may assay 0.8 per cent Cd (accounting for 22 per cent of the cadmium recovery) and after the several draws of spelter have been equalized the cadmium content may average 0.35 per cent. If, therefore, 2000 lb. of blende averaging 0.35 to 0.4 per cent Cd is roasted and distilled, there may be obtained 1000 lb. of spelter, assaying 0.35 per cent Cd or 3.5 lb. content, which entering into Prime Western spelter will be sold at the spelter price. It will be observed from the outline hereinbefore (summarizing conditions prior to the introduction of sintering) that the main loss of cadmium occurred in the distillation process and by failure to condense, which could be ameliorated by attaching a prolong to the condenser, thus collecting

Jan 1, 1944

By Alfred H. Bell, Virginia Kline

In 1944, Illinois produced 77,413,000 bbl. of oil, or 4.6 per cent of the total for the United States, and continued to rank sixth in the nation in oil production. This represents a decrease of 6 per cent from 1943, when- the total Illinois production was 82,256,000 bbl. This decrease was much less than the 23 per cent decrease in 1943 from production of the previous year. The principal factor in arresting the production declinc, which had been going on since 1941, seems to be the increased drilling that followed the relaxing of the Federal Government's rules in regard to well spacing. The daily average production for 1944 was approximately 212,000 bbl. Daily averages by months were as follows: Jan......... 219,000 July........ 206,000 Feb......... 220,000 Aug......... 211,000 Mar........ 216,000 Sept......... 209,000 Apr......... 211,000 Oct......... 210,000 May........ 213,000 Nov........ 209,000 June........ 209,000 Dec......... 205,000 During the year, 1991 wells were drilled for oil and gas in Illinois as compared with 1791 in 1943, an increase of II per cent. Of the 1991 wells, 430 are classified as "wildcat" as compared with 461 in 1943. Twenty-eight new pools (Table 2 A) were discovered in 1944 as compared with 29 in 1943. Changes in federal drilling regulations, permitting closer spacing of wells, resulted in a drilling program that emphasized development of proved acreage rather than wildcatting. Data on production and drilling by fields are given in Table I; data on annual production and drilling for Illinois, in Table 3. Discoveries Twenty-eight new fields (Table 2 A), 42 extensions (Table 2 B), and 39 additional producing zones in existing fields (Table 2 C) were discovered in 16 counties in Illinois during 1944. Of the 28 new fields, one was abandoned during the year, 14 were one-well fields, eight others had not more than 6 wells, one had 8, one had 9, one had 11, one had 15, and the largest new field, Roaches North, had 28 producing wells at the end of the year. In all, 109 wells were producing in these new fields on Jan. 2, 1945, as compared with 111 wells producing from 29 new fields at the end of 1943. . The average initial production of the discovery wells of the 28 new fields was 129 bbl. of oil and II bbl. of water, a notable decline from the average initial production of 194 bbl, of oil and 15 bbl. of salt water for the 1943 discovery wells. In fields discovered since 1936, the total number of oil wells producing at the end of 1944 was 12,335. Productive Acreage The area of proved production in the new fields (discovered since 1936) increased from 144,335 acres at the end of 1943 to 173,485 acres at the end of 1944 (Table I), an increase of 29,150 acres. Of this increased area, 1720 acres are in fields discovered during 1944 and 27,430 acres are in extensions of fields discovered earlier.

Jan 1, 1945

By R. Maddin, A. Lawley

Single crystal Mo-Re alloys (99.99+ purity), grown by electron bombardment floating zone heating, were deformed in tension at temperatures from -196° to +200°C. At -196oC, Mo-6 pet Re and Mo-20 pct Re alloys deform by slip on systems of the type (101) [1ll]. Above-78oC, the operative slip system is of the type (112) [111], (101) [1ll], or (211) [1ll], depending upon orientation. Mo-39 pct Re alloys deform by twinning and slip at all test temperatures with a (112) [111] type twinning system. Critical resolved shear stress for slip and twinning is calculated as a function of composition and temperature, and the mechanical properties compared with those of less Pure polycrystalline alloys. HEXAGONAL close-packed rhenium, c/a = 1.615, is highly soluble in molybdenum. The bee molybdenum-rich solid solution extends to approximately 42 at. pet Re* at 2500°C,' Fig. 1. Recent work on polycrystalline alloys has shown conclusively that the addition of rhenium to molybdenum improves both the fabricability and the low-temperature ductility.2"5 Similar behavior is observed for W-Re and Cr-Re alloys.5 Initially, Geach and Hughes2 found that the Mo-30 pct Re alloy could be cold rolled to approximately 90 pct reduction before the onset of cracking. The remarkable effect of the rhenium was later confirmed by Jaffee et al. 3-5 with an optimum condition of maximum strength combined with maximum ductility at the Mo-35 pet composition. At higher rhenium contents, the ductility was severely impaired due apparently to the presence of brittle tetragonal s phase, Fig. 1. In the Mo-35 pet Re alloy, at least 110 ppm (parts per million) oxygen could be tolerated before cold workability was reduced. By comparison, the corresponding tolerance figure in unalloyed molybdenum is ~ 10 ppm. The effect of rhenium was considered in terms of: 1) a reduction in oxygen solubility in the lattice; 2) a redistribution of intergranular oxide from grain boundary films to isolated spheres; and 3) the promotion of twinning as a further mode of plastic deformation. Paradoxically, twinning is often associated with brittle fracture in iron and the silicon irons.6'7 Work to date has been restricted to are-melted and powder metallurgy polycrystalline material of ~ 99.9 pet purity. The present investigation was initiated for the purpose of determining the mode and crystallography of plastic deformation of a series of bee Mo-Re alloy single crystals over a wide temperature range from -196o to +200°C. Using high-purity zone-melted material (~ 99.99 + pet purity), the specific role of rhenium in the molybdenum lattice may be understood more fully since effects due to grain boundaries and oxide redistribution will be absent. At the same time, the study provides a comparison of single and polycrystalline deformation behavior. EXPERIMENTAL TECHNIQUES A) Preparation and Purity of Single Crystals. Alloys in the form of either are-cast and swaged or sintered and ground bar, 0.120 in. diam, were obtained from the Chase Brass and Copper Co. Alloy single crystals ~ 8-in. long were grown from the

Jan 1, 1962

By Wilbur H. Somerton

In order to evaluate the quantitative determination of porosity by various neutron logging systems, four test wells were constructed to simulate some of the possible variab1e.r found in field logging conditions. All of the test holes contain sections of limestone with one section of sandstone included in one well. Each well has a representative section of high, medium, and low porosity. Three borehole sizes are represented by three of the test wells, all containing fresh water. One test well contains saturated brine. Statistical and tune constant checks are made for each system evaluated. Runs and repeat runs are made with the sonde centered and eccentric. Factors evaluated are the effect of borehole size, sonde position, salinity, chemical composition of rock, and statistical variation. A semi-quantitative method of evaluation of these effects is used giving the average maximum per cent error possible for each. Drift and calibration procedures are also discussed. The effect of the various factors appears to be largely a function of the phenomena detected as well as the means of detection. Graphic illustrations of some of these effects are presented. It is concluded, that for accurate log interpretation, the hole size and sonde position should be known. INTRODUCTION The use of neutron logs for the derivation of porosity has become an accepted practice in many areas. In recent years, many different neutron logging systems have been offered to the industry. The neutron sources presently available are of the radium-beryllium or polonium -beryllium type. Detector types used are ionization chambers, Geiger-Mueller-type counters, proportional counters, or scintillation detectors used to detect or measure gamma rays, thermal neutrons, epithermal neutrons, fast neutrons or combinations of these. It is well-known that all systems do not respond alike in all environments. As a result, testing facilities and an evaluation method were developed for use in evaluating the porosity discriminating ability of neutron logging systems using conditions simulating those normally encountered in the field. With such an evaluation, the suitability of a logging system can be determined lor selected field conditions. TEST FACILITIES The testing facilities consist of wells containing rocks of various porosities, constructed to include as many parameters as practicable. Three pits were drilled to a depth of 20 ft and the fourth to a depth of 9 ft, all having 48-in. diameters. Rat holes were dug to a depth of 6 ft in the center of each pit and fitted with sections of pipe having appropriate diameters. The top of this pipe was located approximately 8 in. above the pit bottom. A 6-in, layer of cement was then poured on the bottom and while still wet, 42-in. OD corrugated, galvanized culvert pipe was set on bottom and centered in place. This pipe extends approximately 1 ft above the surface of the ground. The annulus around the culvert pipe was then filled with cement to the top. A 1- or 2-in. layer of sand was placed on the cement bottom to provide an adjustable bed on which to place the series of rocks set in each hole. A cross section of a typical test well containing the porous rocks is shown in Fig. 1.

By Donald Jaffe, Michael B. Bever

The solidification of Al-Zn alloys (2 to 70 pct Zn was investigated at different rates of solidification. The resulting structures were studied; the amounts of nonequilibrium eutectic were measured and compared with the amounts calculated on the assumption of no diffusion in the solid. The compositions of the cored primary constituent were investigated by quantitative autoradiography after activation of the zinc by neutron irradiation. These compositions were also determined from microhardness values. IN a recent investigation of the soltdification of aluminum-rich AI-Cu alloys,' the amounts of non-equilibrium eutectic were measured and compared with the amounts calculated on the assumption of no diffusion in the solid. The compositions of the cored primary constituent were investigated by quantitative autoradiography. The work reported here extends the investigation of nonequilibrium solidification to the Al-Zn system in the range from 2 to 70 pct Zn. In addition to autoradiography, microhard-ness values were used to determine compositions on a micro scale. Solidification Experiments The alloys contained approximately 2. 6, 12, 20, 30, 50, and 70 wt pct Zn and the balance aluminum. According to published diagrams the eutectic reaction occurs at 382°C between the eutectic liquid (95 pct Zn), a (82.8 pet Zn), and $ 498.9 pct Zn). Solid-state reactions at lower temperatures (due to the miscibility gap between 350" and 275"C, the eutectoid at 275'C, and the precipitation from supcrsaturated a) did not affect this investigation. Even if they occurred to any appreciable extent, they did not alter the evidence pertaining to the solidification structures. The alloys had to be of high purity to avoid radioact~ve contamination during activation. The aluminum analyzed 0.015 pct Si, 0.009 pct Fe, less than 0.004 pct Cu, and less than 0.006 pct Mg with traces of sodium and titanium; the zinc was reported to be at least 99.99 pct pure with traces of iron and magnesium. The alloys were prepared under argon in an induction-heated, bottom-pouring furnace, and poured into a coated steel mold, which could be preheated to temperatures up to 700°C in order to control the rate of solidification. The pouring temperatures ranged from about 40" above the liquidus for 2 pct Zn alloys to about 130°C above the liquidus for 70 pct Zn alloys. As soon as the melt entered the mold, the readings of a thermocouple placed % in. above the bottom of the mold were recorded by a recording potentiometer. Cooling at the rate induced by the initial temperature of the mold was continued to a temperature 100°C below the liquidus; the mold with its contents was then quenched in icy brine. Quenching from a fixed interval below the liquidus was used to provide a standardized procedure, since the solidus and liquidus temperatures and the interval between them vary greatly over the composition range investigated. The temperatures from which the samples were quenched were below the equilibrium solidus, but under nonequilibrium conditions some liquid was still present. This residual liquid solidified during the quench. The samples measured 314 in. diam and 11, in. height. Drillings for chemical analysis were taken

Jan 1, 1957

By R. Taggart, R. H. Ericksen, D. H. Polonis

Transmission electron microscopy techniques hare been used to study the spontaneous marfensite phase that forms during the thinning of Ti-Cr alloys. The structure of this phase has been found to differ. from the hcp martensite and has been identified as a clisforted fcc lattice. The spordaneous marlensile in this system is interpreted as a metastable isomorph of the equilibriunz TiCr, phase. WHEN thin-foil specimens for transmission electron microscopy were prepared from metastable alloys of the Ti-Cr system, a spontaneous transformation occurred' when the foils contained the untrans-formed 0 phase or two-phase mixtures of the 0 and w phases. The purpose of this paper is to examine the relationship that exists between the crystal structure of the spontaneous product and that of the matrix. The differences between the martensite transformation that occurs in the bulk material and the spontaneous reaction that occurs during the preparation of thin foils are compared with the observations that have been reported for similar phenomena in a commercial titanium alloy.' A spontaneous reaction that exhibits characteristics similar to a martensite transformation has been reported to occur in thin foils prepared from the retained metastable structures of several alloy systems.1'3"7 ~ull~ observed such a spontaneous reaction in 0 brass and attributed the apparent increase in the martensite transformation temperature to a decrease in the non-chemical free energy associated with bulk strain energy. He also showed that the spontaneous product did not have a specific habit plane, but that its orientation relationships to the parent matrix were dependen on the thickness of the transforming region. It has also been pointed out by Breedis6 that in thin films the absence of the constraints imposed by a bulk matrix can cause different requirements for the martensite plate interface and lattice distortion which is reflected bv a dependence of the transformation mechanism on the specimen geometry. In the case of the spontaneous reaction reported for Au-Zn alloys7 a definite habit plane was determined and shown to correspond with the habit plane calculated on the basis of the Bowles and Mackenzie crystallographic theory of the martensite transformation.'- lo EXPERIMENTAL PROCEDURE A series of titanium alloys containing 5.5, 5.9, 6.4: 7.6, 8.0, 11.3, and 18.7 at. pct Cr were prepared from high-purity (iochrome) chromium and iodide-grade titanium by levitation melting. The experimental procedure used for sectioning the alloys and for thin-foil preparation has been reported in an earlier paper.' X-ray diffraction patterns were obtained using a 114-mm Debye-Scherrer camera and Cu-Ka radiation. In order to minimize fluorescent radiation from the specimen, a strip of aluminum foil 0.002 in. thick was placed in contact with the X-ray film. After a specimen was removed from the camera: an additional X-ray experiment was performed, to insure that no spurious lines were obtained due to the presence of the aluminum foil. The interstitial impurity analysis for the alloys used in this study was as follows: oxygen, 100 ppm: hydrogen, 30 ppm: nitrogen, 28 ppm. EXPERIMENTAL RESULTS Electron diffraction patterns were obtained from several individual crystals of the spontaneous marten-

Jan 1, 1970

By D. G. Swarthout, J. W. Savage, R. W. Guard

The Nb-N constitution diagvam has been examined from 1100° to 1450°C at 1 atm N2 pressure. On the basis of- our work plus that of Brauer and coworkers the stable nitvide Phases are: a) a solid solutlion, basic niobium (bcc) with nitrogen contained interstitially; NbN,, x = <0.40; b) ß NhNx,x = 0.39 to 0.45; hexagonal (W2C type) (NbzN); a =3.058A,c = 4.961 + 0.001A c) y NbNx x = 0.75 to 0.80; tetragonal (distorted NaCl type) (Nb4N3); a = 4.386A,c = 4.332 + 0.001A; d) 6 NbN,, x = 0.88 to 0.91; cubic (NaCl type); a = 4.3885 + 0.0007A; e) E NbNx x = 0.92 to 1.00; hexagonal (Tip type); a = 2.958A, c = 11.272 * 0.0015A. In addition, a metastuble transition phase 6&apos; has been observed and occurs only during the transition 6 — E. 6&apos; NbN has these distinguishing parameters: NbNx,x = 0.96; hexagonal (anti-NiAs type); a = 2.94A, c = 5 .46A. The high-temperature phase fields in the system are governed by two reactions: a) 6 + Y + E, a entectoid reaction occurring at 1270" ± 20° C; b) o + N2 = E, a 2 012 1 reaction occurring at 1370" ± 20° C. As part of a study of the electronic low-temperature. properties of transition metal nitrides, a number of specimens of niobium nitride were prepared. Preliminary observations on these specimens showed several points of disagreement with data already in the literature. It was, therefore, decided to determine the constitution diagram for the Nb-N system between 1100" and 1450°C. The objective of this research was to define the temperature and composition regions of stability of the various phases and to explain the differences among previously proposed diagrams. Review of Previous Literature. The research on the Nb-N system to 1964 has been summarized by storms.&apos; Although he does not present a phase diagram, his review covers the research on the system thoroughly. One of the earliest works on NbN is that of Ascher-mann and coworkers2 who studied the superconductivity of the cubic 6 NbN. Subsequent work by Horn and ziegler,3 Cook, Zemansky, and Boorse,1 Rögener:5 Schroder6 and sellmaier7 has qualitatively confirmed the first results on superconductivity, although their methods of preparation differed considerably. The constitution diagrams proposed for the system by Brauer and Esselborn8 and Elliott9 are shown in Fig. l(a)and (b). The diagram in l(a) has been modified by more recent results in Brauer&apos;s laboratory (private communication). Although 6&apos; is shown on this diagram, Brauer has indicated that he now believes 6&apos; to be a metastable phase in the temperature range shown. The diagram of Elliott, Fig. l(b), is based primarily on the results of Elliott and Komjathy10 on ni-trided niobium strip or rod specimens examined by X-ray diffraction and metallography. It will be noted that these proposed diagrams are in conflict with respect to the temperature and composition ranges of

Jan 1, 1968

By J. P. Heller

The purpose of this discussion is to comment briefly on one of the points raised in the paper. The topic is that referred to in the Conclusion 2, in which the authors note a "disproportionate increase in mixing rate" as they proceed from a displacement performed at viscosity ratio 0.998 to one at 1.002. The recovery curve of this displacement, Fig.2A, shows a quite noticeable difference between the two runs in which displaced and displacing liquids were interchanged. This difference is ascribed by the authors to the change in viscosity ratio between the two experiments. This interpretation of the experimental results must certainly be based on rather precise measurements of the fluid viscosities or, at least, of the ratio of their viscosities. The ordinary Ostwald viscometer, employed in the usual way, is only just able to distinguish between liquids whose viscosities differ by two or three parts per thousand. The experimental refinements which then must have been necessary to measure with any precision a viscosity ratio of 1.002 would be worthy of mention. Indeed, one would have expected the authors to devote at least a paragraph to the display of this technique. For the same reason - to emphasize that the details of such unusually critical experimental work should be reported and discussed in the literature — I would have liked to see some comment by the authors on the requirements for temperature control during both the viscosity measurements and the displacement experiments. The temperature coefficient of viscosity of Soltrol C at room temperature has been measured in this laboratory at about - 1.9%/1°C. How much did the coefficients for the fluid mixtures used in the experiment differ from this and from each other Even if the two fluids were identical in this respect, it would appear that a temperature difference of .l°C between them in the flow system would produce a viscosity con- trast equal to that imposed by their composition. Reference to the experimental solutions of these problems would render Conclusion 2 more credible. Published theoretical work on the stability problem contains no indication of such extreme sensitivity to the viscosity ratio in the immediate neighborhood of unity. On the contrary, perturbation calculations such as those made by Chuoke1 and Perrine2 lead to initial finger growth rates proportional to the first power of the viscosity difference. The later instability growth calculated by Scheidegger,3 using the assumption of zero pressure gradient perpendicular to the average flow, is also simply proportional to the viscosity difference. The conflict regarding the sensitivity of the dependence of instability growth or mixing rate on the viscosity contrast needs explicit recognition in the literature. In particular, it would seem that the experimental work reported here should be supported by a more detailed description of the viscosity controls. Further discussion of possible alternative interpretations of the data would also be in order. For instance, is it possible that the unconsolidstted bead pack used changed its characteristics between the runs (due, perhaps, to the handling and inverting involved in the injection of the front) Or, are the data points of Fig. 2A averages from several runs performed in a series in which the two liquids alternated as displaced and displacing fluids? To summarize, it seems to me that the relationship asserted by Conclusion 2 in the paper needs the support of more detailed experimental evidence. REFERENCES 1. Chouke, R. L., van Mews, P. and van der Poel, C.: "The Instability of Slow Immiscible Viscous Liquid-Liquid Displacements in Porous Media", Trans., AIME (1959) Vol. 216, 188.

By Philip E. LaMoreaux

Fluoride, generally less than 0.5 ppm, is present in ground water from rocks of Paleozoic age and older, in northern and eastern Alabama. Some of the water-bearing formations in the Coastal Plain area of the State yield water with as much as 6.8 ppm fluoride.

Jan 1, 1950

By D. Weinstein

Yieldilzg in annealed arc-cast molybdenunz in torsion was studied as a function of strain rate and tem-perature. The temperature dependence of the yield point for different strain rates was used to calculate a heat of activation for the yield point. The heat of activation was not a constant but was approximately a linear function of the stress at yield. It is proposed that the rate effect in yielding is determined in part by a site place-change of C (or other interstitial atom) in the metal. THE low-temperature embrittlement phenomenon in metals and alloys has been known to exist for a long time. Although a transition from ductile to brit-tle behavior has been observed in some close-packed hexagonal metals1 and a face-centered cubic alloy, the most common class of metals exhibiting this be-havior has a body-centered cubic lattice structure. For example, a ductile to brittle transition has been observed in iron,3 molybdenum,4 chromium,5 colum-bium,6 and tungsten.7 In the present investigation, molybdenum specimens were tested in torsion over a wide range of temperatures at three widely separated strain rates, and the temperature for onset of embrittlement was determined. Characteristic of body-centered cubic metals and closely associated with plastic deformation is the appearance of a sharp upper and lower yield point. Theoretical explanation of the yield point in iron and low-carbon steel is due to Cottrell,8 who attributes the phenomenon to the pinning of dislocations by the formation of impurity atmospheres around the dislocations. These atmospheres tend to lock the dislocations and make them more difficult to move. The stress required to move a dislocation and thereby cause plastic deformation is greatly increased, and thus an upper yield point is observed. In addition, theoretical analysis,9 as well as experimental observations, show that the upper yield point is strongly a function of temperature. The upper yield point is observed to decrease with an increase in testing temperature, and above a certain temperature (-700° K in iron) it no longer appears. This is consistent with the concept that thermal vibrations will help free a dislocation from its atmosphere, so that the external stress required to free a dislocation from its pinning atmosphere decreases with increasing temperature. Furthermore, with increasing temperature the equilibrium concentration of impurity atoms around a dislocation decreases exponentially with the result that the dislocation is less firmly pinned. In Cottrell&apos;s theory of yield point a static model is visualized in which the pinning atmospheres, particularly interstitial atoms, are immobile, and the dislocations are anchored to stationary positions in the lattice. However, experiments1,7 show the upper yield point to be time-dependent or a function of the rate of straining, a high strain rate causing a high upper yield point. Present theory does not adequately account for the rate dependence of the yield point, and the exact function of the interstitial atom is not under stood. Nevertheless, observation of the temperature dependence and rate dependence strongly suggests that the upper yield point phenomenon is due to the interaction between dislocations and pinning atoms, and that a diffusion mechanism is important in determining the yield point.

Jan 1, 1962

By E. C. Carris

THE particular field of application of machines utilizing air cur¬rents as the primary separating medium is in the cleaning of the fine sizes of bituminous coal. Approximately 12,000,000 tons of bituminous coal were cleaned by air machines during 1940. They have not found any application for cleaning anthracite. Since the development and introduction of the first successful com¬mercial pneumatic oscillating machine for cleaning bituminous coal in 1916, by the Sutton, Steele and Steele Co., Dallas, Texas, and the Ameri¬can Coal Cleaning Corporation, formerly of Welch, W. Va., four other successful pneumatic coal-cleaning machines have been developed and introduced to the American coal-mining industry: 1. Peale Davis: "Pneumo-Gravity" machine, 1924. 2. Arms "Concentrator," oscillating table, 1924. 3. Heyl and Patterson oscillating table, 199.7. 4. "Stump Air-Flow," pulsating air jig, 19391. Out of these five developments only the Sutton, Steele and Steele, or American Oscillating, and the Stump Air-Flow Jig remain on the market. They are the predominating pneumatic coal-cleaning machines in use in the United States. HISTORY OF AMERICAN TYPE SEPARATOR The first successful American machine, the CJ table (Fig. 1) was developed by the Sutton, Steele and Steele Co. The SJ table was the first standard model designed specifically for the cleaning of coal. It was installed in the original Crane Creek plant, owned and operated by the American Coal Co. at McComas, West Virginia. This plant was designed by The Roberts and Schaefer Co., Chicago, Ill., working in cooperation with the American Coal Cleaning Corpora¬tion, which had taken over the patent rights and sale of the pneumatic separators. Eight machines were installed in this plant. They were known as the type SJ. They were 60 by 84 in., the short dimension being the width of

Jan 1, 1943

By J. P. Heller, H. B. Bradley, A. S. Odeh

A potentiometric model technique is presented for determining the areal sweep efficiency of a five-spot well pattern, at and beyond breakthrough. A sharp interface between displaced and displacing fluids is assumed. Although the prototype svstem is referred to as a waterflood operation, obvious changes in the notation and computations will adapt the results to other displacement processes. The results of the study include the following. 1. Areal sweep efficiencies for a five-spot well pattern, at and beyond breakthrough, for mobility ratios (displacing to displaced fluid) of 4:1, 2:1, 1:1 and 1:4. 2. Extension of potentiometric analysis to the investigation of the areal sweep efficiency beyond breakthrough in a five-spot pattern by the application of conformal mapping and conductive-solid models. 3. The use of layers of conductive fabric in representing mobility ratio changes in potentiometric models. 4. The development of a probe mechanism for probing conductive solids. The results obtained by conductive-cloth models agree with earlier areal sweep efficiencies at breakthrough obtained by Aronofsky and Ramey 1 on the potentiometric analyzer using electrolytic-tank models. Results beyond breakthrough differ from those obtained by the X-Ray Shadowgraph technique. Data from this study show that, for mobility ratios greater than one, water cut rises rapidly as fluid is produced after breakthrough. However, for mobility ratios smaller than one, a large increase in area swept resulted with only a small increase in water cut. INTRODUCTION In calculating reservoir performance of waterflood-ing operations and other fluid-injection programs, it is necesssary to estimate the areal sweep efficiency * before and after injected-fluid breakthrough into production wells. Influence of mobility ratio on oil-production history, before and after breakthrough for a five-spot well pattern, has been studied by X-Ray Shadowgraph techniques 2-5 and by gelatin models.6 In none of these investigations was the transition zone controlled experimentally. Steady-state anaiog techniques assume that a vertical and discrete interface exists between the displacing and displaced phase. Thus, when using a potentiometric analysis, it is assumed that no transition zone exists. To determine the areal sweep efficiency beyond breakthrough for a five-spot well pattern using the potentiometric analyzer, four principal problems had to be resolved. These were the following. 1. The laborious method of representing changes in mobility ratio in electrolytic tanks by means of contoured wooden blocks. 2. Vapcrization of the electrolyte solution during the study causing concentration changes and, thereby, variable conductivity. 3. The scale-limitation problem 7 that is accentuated by abrupt eiectrolyte depth changes. 4. A wellbore geometry problem. EXPERIhlENTAL EQUIPMENT AND PROCEDURES CONDUCTIVE-SOLID MODEL The theory, equipment and procedural techniques of the electrolytic-tank potentiometric model have been treaced excellently by Lee8 and by Muskat.9 By the use of a conductive solid to represent the fluid conductivity of the porous media, the need for contouring wooden blocks to represent mobility ratio was eliminated. It was found that a carbon-black coated fabric, Uskon D-16,** could be employed as a fairly uniform conductive media. This material, when stacked in appropriate layers and pressed together, can be used to represent changes in mo-

By T. Leffers, A. Grum-Jensen

The development of texture in copper and brass (15 pct Zn by weight) rolled at room temperature and in copper rolled at -196°C has been followed by determination of pole figures for various degrees of reduction. The concurrent development in microstructure has been investigated by transmission electron microscopy. For low deformations, the texture in brass, and in copper rolled at -196°C, is the same as the texture in copper rolled at room temperature. The difference in texture does not show until 50 pct reduction. At the same reduction at which the difference in texture appears, mechanical twinning starts in brass and low-temperature rolled copper. Nevertheless, Wassermann&apos;s twinning theory is found to be incompatible with the present resulls. All fcc metals and alloys develop, by heavy rolling, one or the other of two types of texture, classified for convenience as copper type and brass type, or possibly a &apos;(mixed" texture representing an intermediate stage between the two types. The pure fcc metals, except silver, develop copper-type texture by rolling at room temperature. Silver and many alloys, including brass with more than 10 pct Zn, develop brass-type texture.&apos; By rolling at low temperatures a transition in texture from copper type to brass type has been observed for copper of commercial purity.2&apos;3 It is generally accepted that there is a correlation between the type of texture developed and the stacking fault energy. Metals and alloys having fcc structure develop brass-type texture when rolled at room temperature if the stacking fault energy is low, whereas those with higher stacking fault energies have copper-type texture.2 Thus, the difference in stacking fault energy must cause a difference in deformation mechanism responsible for the difference in texture. Of the numerous theories advanced concerning the nature of this difference in deformation mechanism, four seem to be of current interest. Smallman and Greeen,2 Dillamore and Roberts,4 and Dillamore5 refer to the fact that cross slip more easily takes place in a material with a higher stacking fault energy and suggest that the copper-type texture is developed by deformation with extensive cross slip whereas the brass-type texture is developed by deformation without cross slip. Haessner6 has advanced the theory that the copper-tye texture is developed by a combination of normal {111} slip and slip on other planes, mainly 1100). Thus his theory, like the theory above, proposes an additional deformation mode for the formation of the copper-type texture. Contrary to this, wassermann7 and Ahlborn et al.8 believe that the copper-type texture is obtained by normal slip. In their opinion mechanical twins will change a copper texture into a brass texture. For this reason it is suggested that the brass-type texture is developed when, in addition to normal {111}(110) slip, mechanical twinning is present. None of these theories are, however, supported by direct experimental evidence. In a recent experiment Hu et al.9 have followed the development of rolling texture in copper and brass. The texture of copper and brass was found to be es-

Jan 1, 1969

By P. R. Swann, R. M. Fisher, W. R. Duff

Observations by transmission electron microscoPy of the microstructures in quenched Fe-A1 alloys provide the basis for revision of the Fe-A1 phase diagram. The diagram is characterized by first-order transitions between the disordered ferromagnetic a! solid solution and the two ordered phases FeAl and Fe3Al. However, second-order transitions showing corre-luted fluctuations in the degree of order near the critical temperature occur between the paramagnetic a! and FeAl and the FeAl and FeAl phases. ELUCIDATION of the true nature of the Fe-A1 equilibrium diagram has proven to be an extremely challenging problem as evidenced by the fact that six quite different versions of the iron-rich portions have been published since 1958.&apos;-6 The most recent diagram shown in Fig. 1 was proposed by Rimlinger6 based on X-ray diffraction analysis and dilatometry. He shows the single-phase fields of the ordered phases of the types FeAl(L20) and Fe3A1(D03) and the disordered bcc Fe-A1 solid solution, a, separated from one another in every case by large two-phase regions. Thus, he implies that in Fe-A1 alloys ordering always occurs via a classical phase transition. In contrast to this view, theoretical studies3&apos;" have concluded that the transitions a — FeAl and FeAl — Fe3A1 should be second- or higher-order in character. A further revision of the Fe-A1 diagram of state is presented in Fig. 2 based on our previous8,9 and current observations by transmission electron microscopy of the microstructures found in quenched specimens. The average quenching rate was 50,000°C per sec and although this was sufficiently rapid to prevent Fe3A1-type ordering below -550°C it was not sufficient to suppress ordering of the type FeAl in the temperature range -650" to 800°C. However, ordering during the quench is easily recognized since the FeAl phase formed during holding at temperature rapidly develops large antiphase domains whereas FeAl formed during quenching has a very fine domain size, -50Å diam. Each symbol in Fig. 2 indicates the result of a micro-structural examination of specimens heat-treated (-1 hr) until equilibrium was established. The results will be discussed in the order of the points, A - Dl marked on both diagrams with reference to the phase fields, critical temperature, and "transition" ranges, respectively. The dark-field micrograph corresponding to point A is shown in Fig. 3 and was obtained using a 111 reflection of the Fe3A1 structure which reveals both a&apos;/4<111> and a&apos;/2<100> antiphase domain boundaries.10 The structure observed in this specimen is typical of single-phase Fe3A1 and shows no evidence for FeAl or any other additional phase. The dark-field micrograph shown in Fig. 4 corresponds to point B on the two diagrams. It was taken with a 100 FeAl reflection which reveals a/2(111) domains and exhibits the typical structure of single-

Jan 1, 1970

By W. C. Hagel, J. H. Westbrook

THERE has been a recent revival of interest in the intermetallic compound AgMg as an experimental material for study of the physical and chemical properties of simple ordered structures. Studies of mechanical behaviors,1-4 diffusion,5,6 and thermo-dynamic properties7&apos;8 have been reported. In several of these studies, heat treatments have been carried out in argon-filled silica capsules at temperatures as high as 750°C with no apparent adverse effects. The present authors were, therefore, startled to discover in the course of some yet unpublished work, that gross melting of near-stoichio-metric AgMg compositions occurred in such samples more than 100 deg below their melting point of about 800°C. This note is to report a brief series of experiments carried out to establish the reason for this behavior. Gross errors in sample composition and failure of furnace temperature controls were quickly eliminated as causes of melting. The first tangible lead came from chemical analysis of an AgMg sample which had melted during treatment at 750°C. A silicon content of 3.3 wt pct was found. Since satisfactory analyses had been obtained on the original as-cast ingot, contamination by diffusion and/or reaction with the fused silica capsule seemed a distinct possibility. A perplexing fact, however, was the apparently capricious incidence of the effect. Not only was it previously unknown, even in the experience of the present authors; but, in the early part of the present study, melting sometimes occurred and sometimes not with specimens treated under constant conditions. Indeed, one sample successfully survived a 750°C heat treatment and yet melted completely during the course of a subsequent anneal in an identical capsule at a lower temperature. To obtain evidence that silicon contamination could lower the melting point to the extent observed, the following experiment was performed. A series of ternary alloys was made up with a stoichiometric AgMg base and containing 0.1, 0.2, 0.4, 1, 2, and 4 wt pct Si. Melting was done in MgO crucibles under a cover of argon gas. After holding 10 to 20 min in the temperature range 850° to 900°C, the alloys were allowed to solidify in the crucible and the temperature during cooling automatically recorded with a Pt/Pt-10 Rh thermocouple. Results from the cooling curves are shown in Fig. 1. Checks within 2 to 5C° were obtained upon repeated melting, cooling, and freezing. The whole series of cooling curves as well as metallographic examination of the melted alloys established that the AgMg rich portion of the AgMg-Si quasibinary is an eutectic-type system. The melting point of AgMg is lowered from approximately 820°C in the pure stoichiometric binary9 to about 710°C in the saturated intermetallic phase. Since second phase was observed in all samples on cooling to room temperature, the solid solubility of AgMg for silicon evidently falls rapidly with decreasing temperature as indicated schematically by the dashed solvus in Fig. 1. It is thus established that a silicon content

Jan 1, 1963

Jan 1, 1946

Jan 1, 1936