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By D. N. Seidman

In the course of a study of the electronic and thermodynamic properties of Pb-Se alloys it was found necessary to have an accurate knowledge of the phase diagram. However, the literature is in disagreement as to whether or not a monotectic reaction occurs in the lead rich portion of the phase diagram. Pelabonl reported only a two-phase region consisting of lead-rich liquid and solid PbSe extending from almost pure lead to the compound PbSe, and gave the melting point of PbSe as 1065°C. The data of Friedrich and Leroux2 are in general agreement with this type of diagram, with the melting point of the compound being 1088°C. However, Nozato and Igaki by inverse rate thermal analysis observed a monotectic reaction isotherm exlacing at 860°C with a monotectic composition of 20.5 at. pct Se. The miscibility gap in the liquid state extends from 7.5 to 20.5 at. pct Se. Hansen and Anderko4 accepted Nozato and Igaki's phase diagram in the region of the lead-rich monotectic. To reinvestigate this portion of the phase diagram, both thermal analysis and metallographic examination of various compositions were performed. The thermal analysis apparatus was constructed according to the specifications of the National Bureau of Standards. A t/t-l pct Rh thermocouple was calibrated against the melting point of copper (NBS), zinc (NBS), and antimony (A. D. Mackay), the emf being measured with a Rubicon Type B potentiometer sensitive to lpv. The absolute accuracy of the thermal analysis obtainable with this system is ± 0.5oC. Starting materials were semiconductor grade lead and selenium purchased from the American Smelting and Refining Co. Both elements were 99.999 pct pure with only trace impurities detected upon spectroscopic examination. One hundred galloys were sealed in quartz crucibles with a central thermocouple well under a vacuum of less than 1 p. This procedure prevented any composition change due to vaporization during the run. Cooling curves were obtained on the alloys listed in Table I. Data was taken by the direct method at cooling rates ranging between 1/2 to 2°C per min. The alloys were heated well above the liquidus and shaken vigorously to insure homogeneity. No evidence of an arrest indicative of the monotectic reaction was observed, and the two-phase region reported by Pelabonl and Friedrich and Leroux? was confirmed in general, although our data give higher liquidus temperatures than Friedrich and Leroux. The melting point of stoichiomet-ric PbSe determined for two different samples was 1080.7 0.5oC. The results of this investigation are compared with Nozato and Igaki's data in Fig. 1. To Complement the thermal analysis data, an 86 at. pct Pb specimen was examined microscopically. This composition was in the center of the miscibility gap reported by Nozato and Igaki.3 The alloy was heated to 1000°C, held for 1/2 hr, and water quenched. The specimen was polished using standard metallographic techniques for lead. The alloy was etched with an acetic-nitric acid etchant for 10 min at 45°C. Microscopic examination did not indicate the existence of two separate layers or solidified droplets imbedded in a matrix, as would be expected if a miscibility gap were present. The mi-crostructure shown in Fig. 2 consists of uniformly dispersed, dendritic PbSe in a lead-rich matrix.

Jan 1, 1962

By R. E. Hurst, D. E. Ramsey, J. M. Moore

The "frac" method of well stimulation has been applied successfully to all producing formations in the Permian Basin area. During the five years since its development, many changes and improvements have been made in treating materials. procedures, and equipie11t. A number of fluid carrying agents, having different physica1 and chemical properties, have been developed to meet variorus well requirements. The current trend is toward larger gallonage treatments, employing higher injection rates. The use of "down-the-casing" techniques has greatly reduced high surface working pressures, attributable to friction losses resulting from injection throrugh tubing. Petrographic studies of various Permian Basin formations, coordinated with laboratory and well log data, have been found a valuable guide in planning frac treat111o1t.s. A knowledge of the extent (and orientation of naturally occurring fractures and planes of weakness in the formation, aid in predicting the ultimate drainage pattern resulting from the frac treatment. INTRODUCTION The South Permian Basin covers an area in Wcst Texas and New Mexico about onc-half the size of the state of Texas, This vast region has been called the "Permian Basin" for so long that the term will he used here. It includes an area south of the Matador Arch. approximately 250 miles wide and 300 miles long. Structural features of importance within the basin are the Northwest Shelf, Eastern Platform, Midland Basin, Central Basin Platform, and Delaware Basin. The principal producing formations include sand, limestone and dolo-mite, with lesser amounts of shale, anhydrite. chert. and various silicates. All of the producing formations in the Permian Basin have responded to some type of frac treatment. Essentially, a frac treatment may be defined as the injection, into a formation. of a fluid carrying agent containing a particulated solid (usually sand), for the purpose of increasing production. The application of this method of well stimulation to many differing Permian Basin reservoirs has necessitated numerous changes and improvements in carrying agents, solids, service equipment. well equipment. and treating techniques. CARRYING AGENTS A number of different types of fluid carrying agents have been developed since the introduction of the frac method of well stimulation. These agents have different physical and chemical properties, and in many cases the extent of production increase derived from the frac treatment depends on the choice of fluid carrier. Unfortunately, due to many different systems of nomenclature used in the oil field, these differences are not always recognized by the oil Operator. In general, carving agents may he divided into the following broad classi-

Jan 1, 1956

November 21st, 1871. THE first session of this meeting was held Tuesday evening, in the chamber of the Common Council, the President, Mr. David Thomas, in the chair. Mayor Carroll, of Troy, gave a cordial welcome to the Institute, which was responded to, on behalf of the Institute, by the first Vice-President, Mr. R. W. Raymond. The Council reported the names proposed for membership with recommendation for election. The following named gentlemen were duly elected Anthony, J., - Williamstown, Pa. Babcock, George, - Troy, N. Y. Blake, Theo. A., - San Francisco, Cal. Blossom, T. M., - New York. Boalt, James A., - San Francisco, Cal. Bowman, Amos, - San Francisco, Cal. Chester, Prof. A. H., - Clinton, N. Y. Dewey, C., - Pittsfield, Mass. Dock, Gilliard, - Shamokin, Pa. Emerson, G. D., - New York. Endres, John J., - Pittsburgh, Pa. Firmstone, Frank, - Easton, Pa. Fowle, W. B., - Philadelphia, Pa. Frazier, Prof. B. W., - Bethlehem, Pa. Gardner, George A., - New York. Goodyear, Watson A., - San Francisco, Cal. Griswold, Chester, - Troy, N. Y. Griswold, J. A.,* - Troy, N. Y. Hague, J. D., - San Francisco, Cal. Hahn, O. H., - Eureka, Nev. Harkness, T. C., - Wilkes-Barre, Pa. Harris, Samuel, - Hudson, N. Y. Henry, E. T., - Oxford, N. J. Holley, A. L., - Brooklyn, N. Y. Howe, H. W., - Troy, N. Y. Hunt, Dr. T. Sterry, - Boston, Mass. Jannet, J., - Troy, N. Y. Knapp, John A., - New York. Laughlin, Henry A., - Pittsburgh, Pa. * Since deceased.

Jan 1, 1873

By Michel Dupuy, Daniel Calais

The study of self-diffusion of plutonium in E phase has been carried out by the welded couples method. The tracer used was puZ4O which is detected by its X-ray emission (conversion lines of uranium which are computed between 13 and 21 kev). Intensities were measured with a scintillation counter. Each layer was removed in a direction parallel to the original interface with a grinding machine and a thickness measured with a pneumatic comparator. The concentration-penetration curves obtained were corrected for the effect of heating time from room temperature to annealing temperature and for the expansion due to phase transformations of plutonium. They were analyzed by the generalized Gruzin method. Self-diffusion of plutonium in E Phase is very fast cm per sec between 500" and 620°C) and the diffusion zones are 2 to 3 mm wide for annealing times ranging from 30 min up to 10 hr. The Arrhenius law gives the temperature dependence in the form: From the point of view of self-dqfusion, PUE phase falls into the anomalous bcc metals category (Tip , Hfp, Zrp, Uy) with a low-frequency factor and an activation energy lower than those provided by standard correlations. No theory proposed hitherto to explain these anomalies (influence of dislocations, of extrinsic vacancies bonded to inlpurities, of bi-vacancies) can clearly explain the self-diffusion coeffzcients of plutonium. DIFFUSION in bcc metals is a present-day problem. A recent symposium (Gatlinburg, 1964), followed by a book,' has been devoted to it. A great many experiments seem to show that diffusion in certain bcc metals obeys unexpected laws. The activation energies measured are sometimes strangely low (B hafnium, y uranium). For certain metals (0 zirconium, p titanium) the curves of log D (D = diffusion coefficient) as a function of 1/T (T = absolute temperature) are not linear. The frequency factors Do, which are of the order of 1 sq cm sec-' in fcc metals, vary from 1 to 10~6 sq cm sec-'. Various theories have been put forward to explain these anomalies; none is yet satisfactory. We wished to introduce a new experimental result by studying the self-diffusion in c plutonium. This allotropic phase, stable from 475°C up to the melting point (640°C), is in fact bcc. Unfortunately, nothing is known of the characteristics of the point defects in this phase, which limits the scope of the hypothesis which can be made about the mechanism(s) of self-diffusion in plutonium. 1) EXPERIMENTAL METHODS 1) Principle. We used the welded couple method. The two pellets of the couple initially have different 240 isotope contents (X emitter). After diffusion, the concentration/penetration curves are drawn up by the generalized Gruzin method. 2) Gamma Spectrography. The metal used in our study is plutonium, either low in puZ4O (isotopic content 1 pct) or high in puZ4O (8 pct). The latter also contains plutonium 241 (-1 pct) and 300 ppm of ameri-cium produced by the reaction Pu2U-AmM1 + 8-. The emission spectra of these two plutoniums placed in leak-tight vinyl bags have been studied by y spectrograph~. The detector is a thin crystal of thallium-doped sodium iodide. The activity of the plutonium rich in 240 is about twice that of the plutonium low in 240 in the energy band of 17 kev (L conversion lines of uranium); this band was used in these measurements. 3) Preparation and Examination of the Diffusion Couples. Diffusion couples were made from plutonium with a high and low PU"' content. Pellets (6 6 mm. thickness 3 mm) mounted on a polishing disc with ground parallel faces were polished mechanically on both sides. In this way, pellets with two parallel faces were easily obtained. The polished pellets were joined by a 6 phase anneal (420°C, 1 hr) in a small screw press (pressure of 20 kg per sq mm cold); a centering ring enabled the two pellets to be pressed coaxially. The couples then were subjected to the diffusion treatment by annealing in the E phase in sealed silica ampules in argon at atmospheric pressure. The annealing temperatures and times are given in Table I. The couples were encased in a mild steel ring, the joint interface being thus parallel to the ground face of the ring. The diffusion couple/ring assembly underwent successive abrasions by means of a magnetic plate grinder. The thickness of the abraded layer was measured with a Solex pneumatic comparator when it was less than 0.1 mm (accuracy 0.2 p) or with a mechanical micrometer (accuracy 3 p) for passes of the order of 0.2 mm. All these operations were done in glove boxes, as plutonium is particularly toxic. After each abrasion we determined the emission spectrum of the ground face. The emissive surface is defined by means of a diaphragm 3 mm in diam. We noted more particularly the X activity in the 17-kev

Jan 1, 1969

By R. Lagneborg

WhEN mechanical twins initiate cracking it has been proposed1 that the friction stress for dislocation motion, in the Cottrell criterion for brittle fracture2 should be replaced by the stress required to propagate a twin, ttp. TF is the fracture stress, d the grain diameter, ß a geometric constant, u shear modulus, and y the effective surface energy. Since TTp is likely to vary with grain size, it cannot be substituted by a constant in Eq. [I]. If an expression for the energy change caused by a twin in a stressed material could be obtained, it is in principle possible to compute the critical size of the twin, i.e., the size at which the system can decrease its energy spontaneously, as a function of applied stress, thus giving the stress required to just barely propagate the twin, i.e., TTP. Consider a circular twin disc with a radius r and having a lenticular cross section, Fig. 1. Twin dislocations3 of strength b exist in the twin boundary parallel to the twin plane, one loop on each atomic plane. Assume that the total numbers of loops, n, can be replaced by one circular loop of a multiple dislocation, nb with a radius r. The energy change of the system, AW, due to such a twin in an applied stress field can then be calculated: The first term is the total twin surface energy, the second the elastic energy due to the twin dislocations, and the third the energy released by the twin in the applied stress field. yt is the twin boundary energy, r, the radius of the dislocation core, and T the applied

Jan 1, 1968

By Arnulf Muan, R. E. Johnson

Equilibrium CO2 /CO ratios of a gas phase coexisting with selected oxide phase assemblages of the system CaO-"Fe0"-SiOz and vnetallic iron have been determined at 1080°C. The data obtained are used to calculate activity-conzposition relations for metasili-cute, orthosilicate, and CaO- "FeO" solid solutions, and to determine a new value for the free energy of formation of C&S&0,. The metasilicate solution is practically ideal, whereas large deviations from ideality exist in the othe,r two solid solutions. BECAUSE of the geochemical and metallurgical importance of the oxides CaO, "FeO", and SiOz, the system CaO-"FeO"-SiO2 has been the subject of several experimental studies during the past 30 years. Following the delineation of phase relations at liquidus temperatures by a group of investigators at the Geophysical Laboratory of the Carnegie Institution of Washington in 1933,1 Chipman and associates in the early forties2,3 determined activities of FeO in liquids of this system. Since that time, many attempts have been made to interpret the data of Chipman et al. in terms of the constitution of the silicate liquids and the interaction parameters among the various constituents of the system (see for instance papers by Richardson4 and by Flood and coworkers5). One of the assumptions made in some of these interpretations4 is that the binary silicate systems CaSiO3-FeSiO3 and CazSi04-Fe2SiO4 mix ideally in the solid state. The objective of the present study is to provide experimental data on activity-com position relations in solid solutions of the system CaO-"FeO"-SiO2. Such data will contribute toward an understanding of the thermodynamics of silicate solid-solution phases in general, and will serve specifically to confirm or refute some of the assumptions made in interpreting liquid slag behavior. PREVIOUS WORK Phase relations in the system CaO-"FeO"-SiO2 in contact with metallic iron were determined by Bowen, Schairer, and Posnjak,1 and additional phase-equilibrium data for this system have been presented by Allen and snow.' A reproduction of the most up-to-date phase diagram for this system is shown in Fig. 1.7'8 Of particular interest in the present investigation are the relations among the various crystalline phases slightly below the lowest solidus temperature in the system, as shown in Fig. 2. The present work will be concerned primarily with some of the composition

Jan 1, 1968

There are no data available of shipments until 1858, and then estimated, when railroad service became available. By reason of the iron made in the county, and the large amounts of salt, the tonnage used locally was quite large, and until 1860 these are estimated from the probable salt and iron production. After 1859 the tonnages shipped by rail are partly estimated from the total shipments of the Allegheny Valley Railroad from four counties. It is believed that the totals are below, rather than above, what the actual production was. While considerably larger for the same years than figures given by the Secretary of Internal Affairs and census reports, these data were always too low in those days, partly because of lack of facilities for gathering them, but more largely because of the strong prejudice existing in those days against furnishing such data to any governmental agencies.

Jan 1, 1942

By E. A. Gulbransen, K. F. Andrew

In a recent communication14 we have reported on the kinetics of the reactions of zirconium with O2, N2 and H2 as a function of the time, temperature and pressure variables. A systematic study was made and the results correlated with fundamental theories of gas-metal reactions. This paper will present a similar study for titanium. Titanium and zirconium are members of the IV group of the periodic table and possess many similar physical and chemical properties as a result of their similar electronic configuration for the outer electrons. The two metals are relatively inert to both gas and liquid phase corrosion at room temperature. However, at moderate temperatures the metals become active and react readily with the common gases including O2, N2 and H2 which are of interest in this study. A study of the kinetics of these gas-metal reactions is of interest for three reasons: (1) to understand the rate of reaction of titanium and its role in the behavior of high temperature alloys; (2) to understand the practical difficulties of the reduction, refining and working of titanium; and (3) to correlate the data with fundamental theories of gas-metal reactions and crystal structure predictions. Literature Survey Several review papers8 and books4243 exist on the preparation and properties of titanium and its alloys. THE METAL Titanium has, at room temperature, a hexagonal lattice of the zinc type. Hagg19 gives a value of 2.953A for the (a) axis, a value of 4.729 for the (c) axis and a density of 4.427 at 20°C. Burgers and Jacobs6 have observed the transformation of the hexagonal to the body-centered cubic structure at 880°C and have established a value of 3.31 for the cube edge and a density of 4.31. TITANIUM-OXYGEN Carpenter and Reavell6 using a pressure change method have studied the reaction at temperatures of 742° and 1000°C and for a pressure of one-fifth of an atmosphere. The probabilities for reaction are calculated from kinetic theory and they report a value of 10-5 for O2 at 1000°C and 10-6 at 740°C. The titanium-oxygen system has been investigated by Ehrlich.10,11 Five phases are observed. Between (TiO2 and TiO1.90) an alpha-phase, consisting ofarutile lattice, is found. A beta-phase is observed between (TiO1.80 and TiO1.70). A gamma-phase is homogeneous between (TiO1.56 and TiO1.46) and has a structure of the corundum type. The delta-phase exists between TiO1.25 and TiO0.6 and has a sodium chloride structure. From TiO0.42 to Ti the metal structure is observed. The surface oxide films have been studied by Hickman and Gulbransen.20 The rutile structure is observed in the temperature range studied, 300 to 700°C. Three crystalline modifications of TiO2 exist: rutile and anatase which are tetragonal and brookite which has an orthorhombic structure. Anatase is reported36 to exist in two forms: I and II. Anatase II changes to anatase I at 642°C. Anatase I is stable up to 915°C where rutile becomes the stable modification. At 1300°C rutile transforms to brookite which melts at 1900°C. The monoxide, TiO, may be prepared from the dioxide by high temperature reduction with carbon or magnesium. Its melting point is 1750°C. TITANIUM-NITROGEN Carpenter and Reavell6 report that at 1000°C a linear rate law is observed. The probability of reaction is given as 10-8 at 1000°C. Fast12 has studied the solubility of nitrogen and its effect on the mechanical properties of the metal. The crystal structure of TiN has been shown by several workers2'21'44 to follow the sodium chloride structure. However, the calculated density is found to differ from the pycnometric value. This is studied by Brager3,4 in detail. He has suggested that the titanium sites in the lattice are only partially filled at low temperatures. As the temperature of preparation is raised the vacant sites become occupied which expands the lattice and increases the hardness and density. An (a) value of 4.22Å is given for room temperature. TITANIUM-HYDROGEN The solubility and the crystal structures observed in this system have been reviewed in a recent book by Smith.40

Jan 1, 1950

By Morris E. Fine, Richard A. Kloske

The stress-strain beha1,ior in tension of Au-Ag alloy single crystals containing nominally 1,3, 5, 95, 97, and 9.9 at. pct Ag was studied uS strain role and lektlperalure down lo 4.2K. A slrain aging yield hob lc,rrs observed on aging under stress in the temperature range 30° lo 75°C. The species diffusing to the dislocation is thought to be a divacancy-solute complex wilh /he. solute then pinning the dislocation by short-Range ovdering and possibly Suzuki locking. At room tempevullcve the critical reso1ved shear stress .follo~c.s an empirical equation of the form tc = A +Bc' where A and B are 90 and 420 ,g per sy mm tor gold base alloys and 60 and 510 g p~r sq )11ttz .tor si1ver base alloys. This strengthening was attributed to a long-range size ejtect. The alloy slrenglliening at i.2'K is greafer than at room temperature. The additional atrloutzf was altribuled lo a uwak skovl-range i?~levacIion between the solute and dislocallon cove. The activation energy .tor deformation a/ 4.Z0h7 decreases on alloying. 11 increases irr other fee systetns. hi the 5 at. pcl Air-Ag- alloy in pmvlicular there is very extensive easy glide and lavge overshooting- of the synmetry line at 4.Z°K. There is also u sharp decrease in the vale of. strain hardenitlg near the widdle of stage II with the new rate bezng abold the sarne as tlzal In easy glide. This uws attributed to a sudden reduction of activity on the pvitrrarg sgstertr. In Au-Ag alloys the critical resolved shear stress Tc. at room temperature is essentially a parabolic function of atomic concentration:' the 50 at. pct Ag-50 at. pct Au alloy is about 10 times stronger than the pure metals. This strengthening occurs in spite of the similarity in valence and atomic size. Solid-solution strengthening in fcc metals is characteristically greater at low temperatures than at room temperature. In Ag-10 at. pct Au and Au-10 at. pet Ag; r, (20.4K)/Tc (300°K) is 2.3 and 2.5. respectively.- compared to 1.2 in pure silver.3 Suzuki' and Flinn5 explained the alloy strengthening at room temperature as a combination of Suzuki locking and short-range order hardening. The agreement between the computed and measured strengthening was very good: however, in Ag base-A1 alloys Hendrickson and Fine6 concluded that Suzuki locking resulted mainly in a yield drop effect. Recent reviews of the solid-solution strengthening in fcc metals by Fleischer2 and Haasen8, 9attributed the strengthening at room tenl-perature to the combined effect of atom nlisfit and change in shear modulus 011 the long-range stress field surrounding a dislocation. The parameter used by Fleischer was The shear tnoduli of Ag-0 to 6 at. pct Au alloys were measured by Pur-wins. Labusch. and Haasen.In While addition of 4 at. pct Au caused an appreciable increase in the C,, elastic constant. there was a decrease on increasing the solute to 6 at. pct Au: C,, and C :: were not measured in the 6 at. pct alloy. The greater solution hardening at low temperatures implies the presence of short-range interactions between the solute atoms and dislocations These include size and electronegativity effects. Whether the extra alloy strengthening at low temperatures is due to locking or friction hardening is still a controversy."".' In the present research the stress-strain behavior of Au-Ag single crystals containing 1 to 5 at. pct Ag and 1 to 5 at. pct Au was measured vs strain rate and temperature down to 4.2' K. Particular attention was paid to yield drop effects. These have not been previously reported. PROCEDURES The alloys were supplied by the Engelhard Industries. Inc.. as strips 0.050 by 0.250 by 12 in. The compositions are given in Table I. Single crystals were grown under static vacuum using a traveling molten zone technique. Crucibles shaped to the size of the strips were made of high-purity graphite prebaked for 24 hr at 1100°C in vacuum. The crucible and its charge were placed in

Jan 1, 1970

By P. K. Foster, C. M. Payne, A. McNabb

Some measurements of the rate of loss of hydrogen from cylinders of iron and steel are analyzed in terrns of a trapping theory. The apeement is encozcraging and gives rise to estimates for the density of traps in the metal. Furthermore, the results appear to be consistent with the assumption that the diffusion constant D for the steady flux of hydrogen through iron lies on the extrapolation of the linear curve (log D us 1/T) obtained at higher temperatures. IT has been shown in a previous paper1 that the literature relating to hydrogen diffusion in steels contains sufficient evidence to invalidate the application of Fick's laws to hydrogen diffusion in steel at low temperatures. To account for the deviations from simple diffusion behavior a trapping theory was developed, and the fundamental laws modified accordingly. In the present paper, new data on the evolution of hydrogen from long cylinders are presented, and together with some published data are examined in terms of the requirements of the theory.' Properties of solutions of the basic equations derived previously1 and appropriate to the present experimental conditions are outlined in the first section as they determine the form in which the experimental data must be presented for a comparison of theory and experiment. Two new solutions not previously reported have been derived as described in the Appendix. The experiments and treatment of data are then given in Sections 2 and 3 and the results are discussed in Section 4. 1) THEORETICAL CONSIDERATIONS The hydrogen-diffusion theory1 applied in this paper postulated that lattice-dissolved hydrogen at a concentration C diffuses randomly in accordance with Fick's first law, but that the lattice contains a uniform density N of traps which can capture and delay hydrogen atoms. kC atoms are trapped per second in a region containing unit concentration of vacant traps while p are released per second in a region containing unit concentration of occupied traps. On this basis it was shown (Eq. [30] of Ref. 1) that, when local changes in the lattice-dissolved concentration C are slow enough for equilibrium to be established with the traps, the system is represented in dimensionless form by the equation:

Jan 1, 1965

By P. M. Robinson, M. B. Bever

THE heats of formation at 273°K of the compounds InBi, In2Bi, and TIBi2 have been determined by metal solution calorimetry with bismuth as solvent. The published information on the thermody-namic properties of these compounds is limited. The structure of the compound InBi (mp, 383°K) is tetragonal of the PbO (B10) type.1 The compounds In2Bi (mp, 362°K) and TIBi2 (mp of highest-melting composition, 486°K) are now believed to have structures of the NizIn (B8) type273 and not the A1B2 (C32) structures reported earlier.4, 5 The compounds In2Bi and TIBi2 have limited homogeneity ranges at room temperature, while the compound InBi has no detectable homogeneity range.' Samples of the compounds were prepared from 99.99 pet Bi (Mallinckrodt Chemical Works), 99.999 pet in (American Smelting and Refining Co.), and 99.99 pet Tl (Amend Drug and Chemical Co.) by melting the components in sealed, evacuated Vycor tubes. The compounds InBi and in2Bi were of the stoichiometric compositions. The compound TIBi2 contained 40 pet T1; this composition was chosen because at room temperature the alloy of stoichiometric composition does not lie within the homogeneity range.' The melts were held approximately 50°C above the liquidus for 8 hr and then quenched into iced brine. The samples were homogenized for 48 hr at temperatures 20°C below the temperature of complete solidification. Metallographic examination of sections taken from the center and the ends of the ingots did not reveal second phases or segregation . The heats of formation were determined as the difference in the heat effects on solution of a compound and of a mechanical mixture of its components added from the reference temperature of 273°K to liquid bismuth at 623°K. The details of the calori-metric procedure and method of calculation have been described elsewhere? The calorimeter was calibrated by adding bismuth at 273°K to the bismuth bath at 623°K. The calculated values of the heats of formation of the compounds, listed in Table I, are based on a value of 4.96 keal per g-atom for the difference between the heat contents of bismuth at 273" and 623oK7 No published values are available for the heats of formation of the compounds InBi and In2Bi. Hultgren et a1.7 have calculated a value of -0.50 i 0.10 keal per g-atom for the heat of formation at 423°K of the compound TIBi2 containing 40 at. pet T1 from heat-content measurements in the range from 398" to 700°K and the heats of formation of the liquid alloy. The difference between this value and the value of -0.66 * 0.01 keal per g-atom at 273°K is too large to be attributed to a difference between the heat capacities of the compound and the components over the temperature range 273o to 423oK7 However, the direct determination of the heat of formation by a calorimetric method should give a more accurate value. The heats of formation at 273°K of the compounds InBi and In2Bi lie on a straight line when plotted as a function of composition, Fig. 1. The compound In2Bi, therefore, appears to be barely stable with respect to its neighboring phases. In order for the free energy vs composition curve to be concave towards the composition axis, the entropy change on formation of In2Bi must be more positive than that on formation of InBi. As the compounds are ordered,2, 3, 8 there is no configurational entropy change on formation. The difference between the entropy changes on formation of the two compounds, therefore, is probably associated with the vibrational entropies. In view of the low heats of formation, the changes in vibrational entropy, due to changes in bond strength on formation of the two compounds, are likely to be small. Owing to the volume contractions on formation of the two compounds,5 the vibrational entropies probably decrease slightly but the decrease of the vibrational entropy of InBi is expected to be larger than that of In2Bi.

Jan 1, 1965

Jan 1, 1887

I would like to congratulate the authors on an interesting paper and, in particular, on their justification of the use of superposition in treating gas wells. They state, however, that no theory has previously been developed lor treating the variable rate drawdown case. In a paper published a few years ago by my colleagues and myself, a method is described which allows a constant rate drawdown curve to be derived for any well. regardless of real rate variations. This method has the great advantage that it is not necessary to make any assumptions regarding the form or uniformity of the reservoir, and the derivation suggested by the present authors is simply an idealized case of our more general treatment. In the light of several years' experience in the derivation of constant rate drawdown curves: I would like to point out that the method proposed by Odeh and Jones may lead to confusing answers, particularly if applied over an appreciable time interval. The reason is that, if pressures are measured when a well is flowing, non-linearities in plots like Figs. 1 and 2 can arise due to either (1) changes in the skin factor with time and/or flow rate, or (2) an inhomogeneous reservoir. Separation of these two effects is only possible if some of the pressures used in the analysis are measured when the well flow rate is 0 or, in other words. during brief shut-in periods. REFERENCES 1. Arthur, K. B.. Metunomski, Z. G. and Ruche, Ms "Intetet ct methode d'utilisa tion des mesures de pression [)our Petude des gisemonts" Revue de T'I.F.P. (Nov., 1962) XVII, 1299. 2. Thomere, R. and Arthur, K. R.: "Analysis of the Pressure Bet~avior of a Production Well Subject to Interterence and Its Application to Reservoir Models", Paper SPE 1189 presented at SPE :Amund Fall Mecting Ireld in Denwer, Colo. (Oct. 3-6, 1965).

Jan 1, 1966

By Stanley Rajnak, John E. Dorn

The saddle-point activation energy for the nu-cleation of a pair of kinks is estimated as a function of the applied stress, the lattice constants, and the height and shape of the Peierls' hill by employing the line-energy model of a dislocation. The kinetics of disloration motion by the Peierls' mechanism are discussed and the microscopic dislocation velocities and macroscopic strain rates are formulated by the Arrkenius type of approach in terms of the activation energy for the formation of pairs of PEIERLS was the first to illustrate that a straight-dislocation line has its lowest energy when it lies in a potential valley parallel to lines of closest packing kinks. The log of the dislocation velocity is found to be approximately proportional to the log of the local applied stress. It is also shown that the low-temperature mechmical properties of several bcc metals might be explained in terms of the Peierls mechanism, good agreement being obtained between theory and experiment for the flow stress us ternperature, activation energy vs stress, and activation volume us stress curves for these metals. of atoms on the slip plane. When such a straight dislocation is moved rigidly from one valley toward the next, the atoms in the vicinity of the core of the dislocation change their positions and bond angles, causing the energy of the dislocation to increase. Midway between two adjacent valleys, the disloca-tion energy reaches a maximum value and any additional small displacement will cause the dislocation to fall down the hill into the next valley. The maximum shear stress necessary to promote such

Jan 1, 1964

Maryland Geological Survey, Johns Hopkins University, Baltimore, Md Edward B Mathews, State Geologist A list of publications-and maps will be sent upon request. The Survey published 12 general reports between the years 1897 to 1928, inclusive Vols. 1 and 9 are out of print, others may be obtained at the uniform price of $1 each. Separates of many of the papers contained in the volumes may be had; in the following list a few of the available separate papers of most direct interest are cited. Vol. 1, pt 4, Bibliography and cartography of Maryland, by E B. Mathews (1897), 25 cents, vol 5, pt 4, Report on the coals of Maryland, by Clark and others (1905), 25 cents paper bound, vol 6, pt 1, The physical features of Maryland, by E B. Mathews, W. B. Clark and others (1906), 25 cents paper bound, including map, 75 cents, vol 8, pt 2, Maryland mineral industries (1896¬1907), by Clark and Mathews, free, vol 8, pt 3, Report on the limestones of Maryland, by E B Mathews and J. S Grasty (1909), 25 cents paper bound, vol 9, pt. 3, Report on the iron ores of Maryland, by J T. Singewald, Jr. (1911), 25 cents paper bound, vol 10, pt 1, The geography of Maryland, by W B. Clark (1918), 25 cents paper bound Vol 11, pt 1, The coal formations and mines of Maryland, by various authors (1922), 35 cents paper bound, vol 11, pt 2, The fire clays of Maryland, by various authors (1922), 35 cents paper bound Most of a series of Systematic Reports on the geologic formations found within the state are also available: Pliocene and Pleistocene, $1; Upper Cretaceous, $5; Lower Cretaceous, $5, Triassic (in preparation), Carboniferous and Permian (in preparation);

Jan 1, 1933

By Howard Smith

OF late considerable experimental and, theoretical interest has been shown in the rates of transformation from a single phase, usually a supercooled solid solution, into one or more phases. Such reactions may involve both diffusion and transformation of the major constituent, as in iron alloys, or it may simply involve diffusion, as in superstructure forma-tion and in age-hardening systems. Most of the work has been confined to ferrous alloys1-9t although two investigations have been made on copper alloys10,11. That such work may be of considerable, practical importance has been demonstrated by Bain12, by the workers at the Kaiser Wilhelm Institut fur Eisen-forschung13,14, and by the everyday use of precipitation and age-harden-inn principles15. Experiments in this country have generally followed Davenport and Bain's technique of rapid supercooling followed by isothermal treatment. In Germany16,17 the work has been extended to the study of the influence of accurately controlled and measured rates of cooling. The work on steel indicates that there are two subcritical temperature ranges where reaction starts sooner after quenching and proceeds at a more rapid rate than at other temperatures. At subcritical temperatures above Ar" where reaction is dependent upon atomic migration there is a period of time of which the length depends upon the alloy content and the temperature, before which no reaction has been detected. Daven-port and Bain1 find that different sorts of atoms in solid solution in gamma iron affect the length of this "prereaction" period differently, manganese

Jan 1, 1935

By K. R. Grube, D. N. Williams

It is often desirable to perform fatigue studies at relatively high strains and at low strain rates. A low-cost fatigue machine has been constructed for this purpose which has proven quite versatile. This machine is based on the principle of repeated bending of a strip sample over a shaped mandrel. A photograph of a group of fatigue tests in progress is shown in Fig. 1. The test sample is held in place between two shaped mandrels having a flat at their base to grip the sample firmly. A cam-driven loading frame is used to bend the sample alternately over each mandrel. The sample slides freely in this frame and is held in place by a light spring to accommodate increases in sample length. The pivot point for the loading frame is selected so as to minimize movement at the loading point during operation. The number of cycles to failure is recorded by a rachet counter which is kept in operation by a series electrical connection through the sample and is operated by the drive cam. The maximum strain imposed at the sample surface on bending from one mandrel to the other is readily calculated from the relationship, where t is the sample thickness and r is the radius of curvature of the mandrels. The rate of straining can be controlled by control of the cam speed. The device as shown in Fig. 1 is set up to run six samples at ambient temperature. A much larger number of samples can be run at one time without difficulty. ALSO-, by slight realignment of the components the mandrel unit can be enclosed in a separate chamber permitting control of test temperature and environment. This permits a variety of fatigue and corrosion fatigue problems to be studied.

Jan 1, 1963

By Frank E. Woolley, John F. Elliott

Mathematical models of the transient thermal behavior of a high-temperature solution calorimeter1-3 have been developed. The thermal behavior of the calorimeter is appoxirrzated by linear lumped-parameter models, and hence is described by sets of linear ordinary differential equations with constant coefficients The response of the models to various inputs is shown to agree with the response of the real system. Application of the modeling to experimental design and analysis of data illustrates the usefulness of simple models of complex systems. The early eperiments1,2 with the high-temperature solution calorimeter indicated that the change in the temperature of the bath resulting from the addition of a solute sample to the bath involved not only the direct effect due to the solution process but also possibly a secondary effect arising from the change in coupling between the bath and the induction heating coil. Consequently, an extensive analysis of the calorimeter was carried out, and models of the transient thermal processes of the instrument were developed to aid in improving the design and interpreting the behavior of the system. This paper describes the dynamic modeling; the use of it in treating experimental results has been reported earlier.3 The high-temperature solution calorimeter was constructed to measure directly the partial molar heats of solution of solute elements in a variety of liquid metal solvents.1-3 The calorimeter consists of an induction-heated liquid metal bath into which small samples of a solute element can be dropped. The bath temperature is recorded continuously, and the change in the measured bath temperature with time, dTm = f(t), resulting from the solute addition are the raw data from which the enthalpy change caused by the addition is determined. To extract the rmodynamic results from the data, the temperature change must be compared with that resulting from calibration additions of known enthalpy change. Accordingly, it is necessary to understand the transient thermal processes arising as a result of the addition to the bath. Neither modeling nor experimentation alone could provide the required insight into the working of the calorimeter. The alternate use of both methods in conjunction greatly assisted the design of the equipment and experiments, and the interpretation of the data. THE PHYSICAL CHARACTER OF THE SYSTEM The essential parts of the calorimeter, Fig. 1, for model studies are the thermocouple, the liquid metal bath and the surrounding refractories. The system is the solvent metal bath and those refractories around it which undergo a temperature change as a result of an addition to the bath, and which determine the way the temperature of the bath responds to an input. The inputs are the combined transient thermal effects arising when an addition is made to the bath. They include the thermal effects of the addition itself and the results of changed coupling between the bath and the induction coil. The response is the variation in the measured bath temperature, dTm(t) = Tm(t) - Tm(O), from an initial steady state resulting from the inputs. It was assumed in this study that the physical properties of the various elements of the system are independent of the inputs and time, although these properties may vary as the result of changes in the composition and size of the bath during a series of additions. This separation of inputs and the system is equivalent to assuming that the system is linear, i.e., that its behavior can be described by linear differential equations with constant coefficients. Linear behavior can be expected whenever the departure of each portion of the system from its steady-state condition is small enough to cause negligible changes in the thermal properties of the materials and in the various heat-transfer coefficients. Radiative heat transfer is important in this system, so the assumption of linearity should be valid only for small temperature deviations. Several conclusions were drawn from operation of the calorimeter in earlier experimental studies: 1) Radiative heat transport from the top of the bath is a significant portion of the total heat lost from the bath. However, for small changes in the bath temperature the change in transport by this path could be assumed to be proportional to the change in the bath temperature. 2) A very small portion of the heat input is lost through the thermocouple to its water-cooled holder. The thermal resistance and thermal capacity of the thermocouple protection tube are small, so the temperature of the thermocouple should follow closely that of the bath. 3) The remainder of the total heat lost from the bath will pass by conduction through the crucible to, and through, the other refractories, eventually being absorbed by the water-cooled induction coil or by the water-cooled sides and bottom of the enclosure. 4) The thermal resistance between the bath and crucible is very small. Thus the thermal capacity of the crucible will affect the temperature of the bath very soon after an addition of heat to the bath. 5) The thermal resistance between the crucible and the silica sleeve is large, especially if a radiation shield is placed in the gap. The effect of the thermal capacity of the sleeve thus will be significant only at longer times. The thermal resistance through the packing below the crucible also is large, so the packing and the silica sleeve will have similar effects on the behavior of the system. 6) A large temperature drop exists across the gap containing the water-cooled induction coil. Thus for relatively small changes in the thermal input to the bath, the refractories beyond the sleeve

Jan 1, 1970

By C. K. Leith

THE purpose of these conferences has been to find some basic principles to guide us in the chaos which confronts us, to arrive at elements of a national policy. None such exists, nor, as a matter of fact, have there been any concerted efforts by the public or the mineral industry to evolve one. In the absence of such a policy the administrative agencies of the government can hardly be expected to be consistent or really effective in their handling of mineral problems, domestic or foreign. Basic Facts MINERAL reserves are unequally distributed among the nations. The principal world supplies are grouped around the north Atlantic, and nearly three-fourths of the world's total is controlled politically and commercially by English-speaking people. No one nation has a complete supply of the minerals necessary for modern industry; specialization, reciprocity, and large-scale movements between the nations are inherent in nature's unequal distribution of them. The principal sources of supply are relatively few compared with the nations to be served-a fact which determines broadly certain natural outlines of the world flow. National isolation with regard to minerals can be accomplished only through backward steps in industry and lower standards of living even in the nations possessing the most of the mineral supplies. A certain measure of unified commercial control, international in scope, is a natural consequence of the limited number of the large sources of supply. Mineral supplies for the world as a whole are so large that there is little need for concern about early exhaustion, but every nation has important problems of early exhaustion of particular minerals, which must affect their policies.

Jan 1, 1933

By Charles M. Stone, Dale S. Preece

Introduction The Strategic Petroleum Reserves (SPR) is a national program dedicated to storage of large quantities of crude oil in leached salt caverns in the Texas-Louisiana gulf coast area. The program has required storage in existing caverns at each site and includes plans to leach new ones. The structural stability of each cavern depends on the behavior of the surrounding salt. In the past cavern stability has been predicted based on experience with other caverns in the vicinity. With the development of good non-linear finite element structural computer programs, it is possible to predict stability before the cavern is created. An important step in verifying the applicability of these predictive methods is comparison of analytical and field data. The analytical data come from finite element analyses of a specific cavern where the laboratory determined material properties and an approximation to the cavern geometry are used as input. These comparisons have been made for caverns in the Bayou Choctaw Dome (Louisiana) and Eminence Dome (Mississippi) with reasonably good correlation being obtained between measured and predicted volumetric response of the caverns. This paper discusses 1) the acquisition of material properties, 2) the finite element program SANCHO, and 3) the comparison of analytical and field data for each of the caverns.

Jan 1, 1982