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Jan 1, 1888

New Products Equipment

Jan 6, 1953

C. A. HANSEN (communicated appendix*).-Since the above paper was written, tests have been conducted with a view to securing a sounder basis for discussing the effects of temperature on the behavior of the zinc cell. The following data, while making no pretense to great accuracy, are still reasonably close. Cells were operated with the same feed solutions, but at varying temperatures, the latter being controlled by means of immersed steam coils. Current efficiencies obtained indicate that the corrosion rate

Jan 11, 1918

Executive SIDNEY .J. JENNINGS, Chairman GEORGE D. BAR HON .I. E. JOHNSON, JR. EDWIN LUDLOW ROBERT M. RAYMOND Membership KARL EILERS, chairman LEWIS W. FRANCIS .1. E. JOHNSON, JR. LOUIS D. HUNTOON ARTHUR. L. WALKER Finance GEORGE D. BARRON. Chairman. CHARLES F. RAND BENJAMIN B. THAYER Library E. GYBBON SPILSBURY1 Chairman ALEX C. HUMIPHREYS3 GEORGE C. STONE .J. H. JANEWAY4 BRADLEY STOUGHTON Papers and Publications BRADLEY STOUGHTON, Chairman

Jan 10, 1918

Jan 1, 1931

By M. B. Bever, A. B. Michael

THE structure of cast A1-Si alloys is altered profoundly by modifying agents. Sodium, in particular, reduces the size of the silicon particles in the eutectic and tends to change their shapes from plates to nearly rounded grains. This refinement is accompanied by a shift of the eutectic to higher silicon concentrations and lower temperatures. Similar effects can be attained by rapid solidification. Hypotheses advanced to explain modification have involved the formation of a ternary eutectic,1 the removal of oxides by fluxing,' and even a presumed allotropic transformation of silicon. Other hypotheses assume that the modifying agent causes an envelopment of the silicon particles by the aluminum-rich solid solution, but attribute this envelopment to different mechanisms. According to various explanations, the growth of the silicon particles is obstructed by an immiscible sodium-rich liquid," an adsorbed layer of sodium,' or a ternary compound;5 his obstruction has been conceived as purely mechanical or as a colloidal action.' It has also been proposed that sodium reduces the surface tension on the Al-Si interface, thus permitting the aluminum-rich solid to grow faster and to envelop the silicon particles.? Still other hypotheses stress undercooling and the attendant change in the rate of nucleation of silicon, but fail to ascribe any definite function to the sodium addition." '" Procedure High-purity alloys of aluminum and 3 or 7 pct Si were treated with modifying agents containing radioactive sodium tracers. The experiments were intended to investigate the partition of sodium between the primary aluminum-rich solution and the eutectic, and, if possible, to determine whether sodium is concentrated in or around the silicon particles in the eutectic. Radioactive sodium fluoride, alone or mixed with stable sodium chloride, was allowed to react with the alloy for 5 min immediately before solidification in the crucible. Modification could not be attained with additions of less than the equivalent of approximately 0.1 pct Na. Some alloys were not completely modified, but comparison of the structures of treated and untreated specimens indicated a very considerable reduction in particle size of the silicon in all of the former. A treated alloy is shown in Fig. 1. Radioactive sodium fluoride was prepared by bombardment with deuterons having an energy of 14 mev. This bombardment (totaling, for example, 6 microampere-hours in one run) produced radioactive Na24 (half-life 14.8 hr) by the reaction 11Na23 (d,p) 11Na24. The radioisotopes of fluorine also produced have short half-lives and were not detected. A half-life determination by counting confirmed that the measured activity was due to Na24. The distribution of the sodium in the solidified alloys was determined by an autoradiographic technique by which a suitable stripping film is attached to a very thin metallographic specimen. After exposure and development, this emulsion remains superimposed on the specimen and may be examined microscopically or photographed by reflected light. The emulsion of the autoradiograph can be correlated directly with the underlying surface by simple adjustment in focus. The details of this technique have been described elsewhere." Results Fig. 2 is a micrograph of the autoradiographic emulsion ("autoradiograph") lying directly above the area of eutectic in Fig. 1. Fig. 3 shows a similar autoradiograph of a region consisting of primary solid solution. The small black dots (tracks) in these autoradiographs are developed grains in the emul-

Jan 1, 1954

By R. M. Waterstrat, B. N. Das, Paul A. Beck

The central region of the Ti-Mn system was studied by means of x-ray diffraction and metallography. The following intermediate phases were found: an MgZn2-type Laves phase having a wide range of homogeneity, the p-phase of unknozvn structure, and the + -phase with a large tetragonal unit cell, stable at 930°C and lower temperatuves. MaYKUTH, Ogden, and jaffee1 determined the soh-inh bility limits of manganese in and titanium. They also confirmed the structure of the intermediate phase TiMn2 which was previously identified as a Laves phase of the MgZn2 type.2 In the equiatomic region they found an additional intermediate phase, y, which presumably formed by a peritectic reaction at approximately 1200°C. This last observation was disputed by Rostoker, Elliott, and McPhers0n,3 who reported the formation of TiMn by a peritectoid reaction between 900" and 1000° C, but found no evidence of any intermediate phase other than the Laves phase at higher temperatures. Elliott and Rostoker4 reported furthermore that the X-ray diffraction pattern of TiMn could be identified as that of a o phase, although their data were not consistent with this inter~retation. Margolin and Ence6 presented X-ray diffraction data for the and TiMn, phases, and obtained metallographic indications for the existence of additional intermediate phases. They concluded from metallographic observations that two Laves phases are formed, separated by another phase, designated as &. A phase diagram for the Mn-Ti system has recently been published by Savitskii and Kopetskii,' which shows considerable disagreement with the work of Hellawell and Hume-Rothery,' in particular with regard to the terminal solid solutions based on the allotropes of manganese. The present investigation was undertaken primarily to clarify the phase relationships in the equiatomic region of the Ti-Mn system. The metals used in preparing the alloy specimens Were iodide titanium and electrolytic manganese, the latter having a nominal purity of approximately 99.9 pet. The electrolytic manganese was covered with a thick coating of a brown manganese oxide which was reduced by heating the manganese flakes for several hours at a temperature of 1100°C in an atmosphere of dry hydrogen. Three alloys, see Table I, were made using sponge titanium and manganese not treated in hydrogen. The alloys were prepared by arc-melting in an atmosphere of helium or argon. The composition of each alloy was calculated by assuming that the entire weight loss during melting was due to evaporation of manganese. Subsequent chemical analysis of certain alloys indicated that the compositions calculated in this manner were usually correct within 1.4 pct, as shown in Table I. All alloy specimens were wrapped in molybdenum foil before sealing them in silica tubes containing argon at a pressure of 1 atm at the annealing temperature. After quenching in cold water, the alloy specimens were bright and clean, with no evidence of any surface reaction. The alloys listed in Table I were examined metallographically, using an etchant consisting of 20 pet HNO3, 20 pet HF, and 60 pet Glycerine. powder for X-ray diffraction examination was prepared by crushing a portion of each annealed alloy

Jan 1, 1962

By Charles R. Cavanaugh, John F. Elliott

The activity of nickel in liquid Pb-iVi alloys which are rich in lead was measured in the temperature region of 700° to 1100°C by means of the galvanic cell: The electrolyte used was stabilized zirconia. Tlze data were correlated using the a function, and a plot of the temperature coefficient aE/aT All subsequent calculations of the thermodynamic properties are based on these two functions. The activity, activity coefficient, and molar properties of mixing of nickel are reported. Nicke1 shows extreme positive deviations frorn ideality while lead shows a very slight positive deviation in the composition range studied The study of the activity of nickel in liquid Pb-Ni alloys reported herein was undertaken to explore the use of stabilized zirconia, an oxygen-ion electrolyte, with liquid-metal electrodes, and to obtain further information on the thermodynamic properties of the liquid binary Pb-Ni system. The cell The reversible electromotive force of the cell results from the difference in the chemical potential of the oxygen at the two electrodes: po, (left) - p~ (right) = -4E5 [I] The chemical potential of oxygen on the right is fixed by the activity of nickel in the solution and pure solid nickel oxide. That on the left is set by pure solid nickel in equilibrium with pure solid NiO. By definition: Since the chemical potential of nickel is related to the chemical potential of oxygen through the equilibrium constant for the formation of NiO from nickel and oxygen gas, the electromotive force of the cell is also expressed In this case, n is 2, E is the reversible potential of the cell, and 5 is Faraday's constant. The work of Kuikkola and wagnerl and Schmalz-reid2 has shown that the stabilized zirconia electrolyte is essentially an ionic conductor at the oxygen levels encountered in the experimental arrangement of the work, i .e., PG > 10-l7 atm. THE EXPERIMENTS The advantage of this type of reversible cell over those using a liquid electrolyte is the simplicity arising because the electrolyte also functions as one of the containing crucibles. A further simplification was the choice of the Ni (sat.)-NiO electrode as the standard. This permitted a ready check on the behavior of the electrolyte, as the potential of the cell must become zero when the right electrode becomes saturated with nickel, either because of a change of temperature or because of the addition of nickel to the electrode. It also permitted the potentials being measured to lie in the most satisfactory experimental range of 0 to 100 mv. Although it was not theoretically necessary, lead was included in the standard electrode as it assured good contact between the electrode and electrolyte. Cell Design. The general arrangement of the experimental cell assembly is shown in Fig. l(a) and the details of the cell itself are contained in Fig. l(b). The anode lead wire on the interior of the cell was connected to a coil of perforated sheet nickel. Within this coil were nickel oxide pellets which were held beneath the surface of the liquid Pb-Ni alloy. A disc of nickel oxide was held at the bottom of the external crucible (alumina) by means of the thermocouple protection tube. The nickel oxide disc and pellets were compressed dry at 10,000 psi and sintered at approximately 1000°C for an hour in air. A major experimental difficulty of reversible electromotive force cells with liquid electrodes is the selection of suitable materials for connecting

Jan 1, 1964

By G. V. Jere, V. Krishnan, C. C. Patel

Standard free energy and standard enthalpy changes as a function of temperature have been calculated for the chlorination reactions of different oxides constituting columbite and tantalite. The tallies of standard lee-energy change (F) indicate the possibility of pvefeential chlorination of different oxides but the ease 0.f chlorination of columbium pentoxide at about 250°C and the chlorinating tendency of columbium pentachloride in promoting the chlorination of tantalum and other metal oxides, p7-evetzt the separation of columbiu?n and tantalum from other oxides and pom each othel.. It is likely that low temperatuves of chlorination and continuous 1err2oval of columbium pentachloride from the ..eaction zone may help partial separation of columbium from tantalum as well as from titanium. The standavd enthaply change (AH?) values shotr that 1ou.-temperature chlorination around 300" to 500°C is likely to sustain the chlorination , without external heating. COLUMBIUM (niobium) and tantalum metals, their alloys and interstitial compounds are finding extensive uses in nuclear reactors and high-temperature equipment.la-3 These metals also find uses in chemical process plants, electrical rectifiers and capacitors and as "getters" in electronic tubes.la With the development of Kroll process of reduction of volatilized titanium tetrachloride by magnesium for the production of titanium metal, chlorine metallurgy is receiving greater attention. Chlorine metallurgy has several advantages, the foremost amongst them are: the ease of chloride formation, separation of the different constituents of minerals by selective chlorination, and the reduction of the chlorides in vapor phase to the respective metals. Recently, Si-bert, Kolk, and Steinberg4 have considered a number of methods for the preparation of columbium metal and the most promising is found to be the halide reduction. Since the minerals columbite and tantalite are comparatively abundant in nature, the future of the metallurgical processes depends on the utilization of these minerals for the production of columbium and tantalum chlorides by chlorination. In this paper, an attempt has been made to interpret thermodynamically the chlorination of individual oxides constituting columbite and tantalite, with the help of the recent thermodynamic data.5-8 For this purpose, standard free energy and standard enthalpy changes of the chlorination reactions of the oxides with chlorine, both in absence and presence of carbon as the reductant, have been calculated as a function of temperature and represented graphically. Similar calculations for the reactions employing carbon tetrachloride and carbonyl chloride as chlorinating agents have also been incorporated in this paper. REPORTED WORK ON CHLORINATION Cuvelliezg has patented a process for the separation of columbium and tantalum from their concentrate, wherein 75 pct Cb05 is claimed to be chlorinated at 1050°C in the course of 7 hr using chlorine or chlorine containing nonreducing gases, the products of reaction being CbC1, or CbOC1,. At this temperature, Ta,05 is claimed to remain unaffected. It is further claimed1° that at higher temperatures, the proportion of Ta205 chlorinated increases while that of Cb205 diminishes. During the studies on the action of chlorine on individual metal oxides, Kangro and Jahn" have observed that Ta,05 is not chlorinated even at 1200" in the stream of chlorine, while 75 pct of Cb,05 is converted into CbOC1, around 900 to 1100°C. The chlorination of Cb205 by chlorine in the presence of carbon, investigated by Lind and Ingle,' and

Jan 1, 1962

By R. D. Young, E. A. Harre

Nitrogen exists in two broad categories commonly designated as elemental nitrogen and fixed nitrogen. Elemental nitrogen is found in nature as a diatomic molecule and constitutes about 78%, by volume, of the earth's atmosphere. Fixed nitrogen is a common term used for nitrogen that is chemically bound to other elements. Although elemental nitrogen is very abundant, nonleguminous plants cannot utilize nitrogen unless it is in the chemically combined form. The content of this chapter is confined to fixed nitrogen since the uses and properties of elemental nitrogen and the fixed nitrogen compounds are different. Certain bacteria associated with legumes are able to fix atmospheric nitrogen, but not to the extent required by succeeding nonleguminous crops. The need to use fertilizers containing fixed nitrogen compounds to grow food crops has been recognized for hundreds of years, and from antiquity farmers have used organic wastes such as animal manures, vegetable wastes, sewage sludge, fish scraps, etc., containing these compounds for fertilizers. These organic materials have a low nitrogen content, however, and cannot support large-scale food production. Known commercial-size deposits of natural nitrates containing much higher nitrogen content exist only in Chile, and the possibility of the discovery of other significant deposits is remote. The Chilean deposits were the major source of nitrogenous fertilizers until the Haber-Bosch process for the production of synthetic ammonia was developed. In the Haber-Bosch process, nitrogen reacts with hydrogen at high temperatures and pressures and in the presence of a catalyst to form ammonia. Modern plants use air, water, and natural gas or other hydrogen sources to produce the ammonia that is now the key building block of the fixed nitrogen industry. Several major problems that developed in the 1970s continue with the nitrogen industry into the 1980s. These are (1) the continuing sharp escalation in the cost of feedstocks for ammonia production as well as all energy sources, and (2) the very steep increase in the investment cost of production facilities. More than 75% of the fixed nitrogen produced domestically is consumed as fertilizers. The types of materials used as fertilizers have changed significantly during the past years. There has been a trend from the use of low-analysis fertilizers to types which contain high percentages of plant nutrients. The average plant nutrient content (N + P2O5 + K2O) of fertilizers used in the United States has increased from 18% in 1930 to 32% in 1960 and today approaches an average of 44%. In the case of nitrogen fertilizers, the low analysis natural nitrates (16% N) gave way to ammonium sulfate (20% N) after about 1920. After World War II, ammonium nitrate (33.5% N) previously used in munitions, became established as the leading nitrogen fertilizer. Urea use as a fertilizer (46% N) began in the 1960s, and in the past 10 years has become the world's leading solid nitrogen fertilizer. Nitrogen Materials Anhydrous Ammonia-Anhydrous ammonia is a colorless gas at ambient temperatures and pressures and has a sharp pungent odor. Anhydrous ammonia is stored and transported as a liquid in high-pressure cylinders and tanks at ambient temperature, and in low-pressure tanks, barges, and ships at -28°F. Anhydrous ammonia is applied directly at 4 to 7-in. depths in the soil as a high-pressure liquid by special applicators, after which it expands to a gas that dissolves in the soil moisture or is absorbed on soil colloids. In other systems ammonia is metered into irrigation water and is thereby introduced into the soil.

Jan 1, 1983

By John G. Simmons

A tutorial account of the tunnel effect between metal electrodes separated by a thin insulating film is presented. Energy diagrams of metal-insulator -metal sandwiches are briefly discussed, and the isothermal and thermal J-V characteristics for symmetric and asymmetric tunnel junctions are derived from a generalized expression. Experimental data from tunnel junctions are presented, and it is shown how, correlation between theory and experiment permits a determination of some of the oxide properties. Finally, the barrier heights in AT-Al2O3-A1 junctions determined by various inr3estigators are discussed. The object of this paper is to give a tutorial account of the electric-tunnel effect between metal electrodes separated by a thin insulating film and to illustrate its utility in the study of metal-oxide interfaces. This paper will emphasize the theoretical aspects of the electric-tunnel effect: however, a brief account of the more recent experimental work will be presented. A more comprehensive experimental study of the tunnel effect will be presented in the following paper by Drs. Pollack and Morris, see p. 497. We will open with a discussion of the energy diagrams for metal-insulator-metal junctions and what we mean by the electric-tunnel effect. Following this is an account of the theoretical studies of Sommerfeld and Bethe, and Holm, and the recently reported calculations on symmetric and asymmetric junctions using the generalized formula. The theoretical presentation is concluded with calculations on the temperature dependence of the tunnel J-V characteristic. In the experimental section, it is shown how barrier heights and thicknesses are determined by comparing the experimental data with the theory. Finally, the results of various investigators on the determination of the barrier heights in Al-Al2O,-A1 systems are discussed. I) POTENTIAL BARRIERS BETWEEN CLOSELY SPACED ELECTRODES Since it is necessary to supply energy to a metal in order to observe electron emission from its surface, it is evident that the potential energy of an electron within a metal is lower than that of an electron at rest outside the metal. It follows, then, that the electron must undergo a change in potential as it crosses the metal-vacuum interface. In the Sommerfeld1 free-electron theory of metals it is assumed that the free electrons, the electrons responsible for the electrical characteristics of metals, move in a constant potential environment in the metal, and are contained within the metal by a potential barrier at the metal-vacuum interface. It will be evident that the idea of a constant potential environment is a very idealized model, since the potential energy of an electron is influenced by all of the atoms and the other electrons within the metal; however, its use is justified by the many excellent results it gives.2 Fig. l (a) is the energy diagram of the model envisaged by Sommerfeld; the metal is represented by a potential-energy well of depth V,; the vacuum level represents the energy of an electron at rest outside the metal. At 0°K the electrons, which exist in pairs in discrete energy levels, fill up the well to an energy ?, the Fermi level. The distance, Vo - ?, from the Fermi level to the vacuum level is known as the work function of the metal, and represents the minimum energy required to free electrons from the interior of the metal at 0°K.

Jan 1, 1965

By James Kemp

PostScript to a paper presented at the New York meeting, February, 1915, and printed in Bulletin No. 98, February, 1915, pp. 129 to 154. The writer looked over the quarry with care in the search for fossils, having in mind shells or corals of fairly large size. In the brilliant summer sunshine, none were observed on the glaring white ledges. The impression was gained that none were present and the statement to this effect was made in the edition of this paper published in the Bulletin' of the Institute for February, 1915, p. 136. On closer examination in the laboratory it has been discovered that the limestone itself is made up of minute organisms, which are clearly revealed by microscopic examination of thin sections. The principal component of the rock is a small foraminifer, 0.1 to 0.3 in. (2.5 to 7 mm.), of the genus Orbitoides, presumably an Oligocenic form. Figs. 1 and 2. illustrate it. The accompanying description has been kindly summarized by Marjorie O'Connell, M. A., Curator in Paleontology in Columbia University, who first detected the evidences of organisms in the rock. Orbitoides kempi O'CONNELL N. SP.1 The foraminiferan which makes up the Seboruco limestone is an Orbitoides of a Species new to North America. The only Orbitoides heretofore described from this country is 0. mantelli from the lower Oligocenic of the Gulf States. This form from Cuba, then, so different in all of its characteristics from the 0. mantelli, is of great interest as perhaps forming a basis of correlation over wide areas. The most closely related Species is 0. dispansa Sowerby, which occurs in the Nummulite limestone of the Eocenic of the Bavarian . Alps, in the Priabona beds of the lower Oligocenic of Massano, and elsewhere in Italy, as described by Gümbel.2 The age of the limestone in Cuba would thus Seem to be of upper Eocenic or lower Oligocenic age, probably the latter. The fossil has the form of a sphere Surrounded by a wavy rim of horizontal extent, the whole resembling two flat-brimmed, round-crowned hats placed base to base. The total extent of the Shell ranges up to 7+ mm., while the thickness of the central sphere is 2.5 mm. in one of the largest individuals. Like all of the other Species of Orbitoides, this form begins with a Single layer of chambers which multiply in one plane and assume a circular outline; but it is in the subsequent growth that the distinguishing specific characters appear, for the chambers at the central portion of the shell increase more rapidly than do those near the periphery and in consequence a Swelling is produced which finally gives the Spherical form which is so characteristic. The rim, on the other hand, shows little chamber-increase and remains thin. This is clearly Shown in the sections figured, where the central row of larger chambers forms the equatorial zone. Radiating from this row, in section, there appear, a number of solid cones alternating with broad reticulated ones. The solid cones mark the more dense structure forming the walls surrounding the reticulated or chambered cones. These appear upon the Surface as distinct pits, whereas the solid part appears as raised walls.

Jan 7, 1915

By M. A. Cook

Sutherland used an ion-pair adsorption model to derive the author's hy-drolytic pee-acid) adsorption equation for the contact bubble curves of Wark and Cox. To do so it was necessary to postulate that the sum of coverages of surface anion sites by the collector and depressant anions is practically unity. It is here shown that the free energy of Sutherland's postulated collector ion (x-)-depressant ion (OH-) exchange reaction (for no other than the OH- to compete with X-), namely EX + (OH-) Z SOH- + X-, is in some cases positive and X- should not even adsorb. Also, in many cases the (OH-) adsorption must be quite negligible even though the collector covers only about a sixth of the mineral surface at the threshold of air bubble contact. This, however, contradicts the postulate that permits one to derive the correct bubble contact eqwztion for the ion-pair model. Furthermore, the requirement for charge neutrality leads in the ion-pair model to the (impossible) constancy of the ratio @+)/(OH-) along a contact bubble curve in which pH may change by more than seven units. HYDROLYTIC ADSORPTION EQUATION Hydrolytic (free-acid or free-base) and ion-pair (H', X-, or R', OH-) adsorption models of the collector in metal sulfide and similar flotation systems are superficially alike and somewhat difficult to differentiate. This is because they yield, under seemingly valid assumptions, equivalent forms of the equations describing the distribution of the collector between the aqueous solution and the mineral surface. This has been discussed by the author and associates1-4 and more recently by Sutherland,' both for simple collector-mineral and for more complicated collector-depressant-mineral systems. In the hydrolytic adsorption model the equations describing the contact bubble curves of Wark and coxeJ7 are as follows :2 Here X is the collector anion, D- the depressant anion, 9, and On are the fractions of the free-acid sites S on the surface of the mineral covered by collector and depressant free acids, respectively, and @ is the fraction of uncovered sites. Kx is the free-acid collector dissociation equilibrium con- stant, K1 that for the free-acid collector adsorption, KD that for the free-acid depressant dissociation, and K2 the equilibrium constant for the free-acid depressant adsorption. Eqs. 1 to 5 yield upon simultaneous solution the result is the critical free-acid concentration for bubble contact in the absence of depressant-free acid. Eq. 8 expresses the conditions along a simple collector-mineral contact bubble curve for the case HD = 0, or V = 0. Last and Cook showed that Eq. 6 applies generally and with good accuracy in the collector-depressant-metal sulfide mineral systems. Inci-dentally, it has been shown by infrared absorption studies that in some cases the free-acid adsorption process splits out water.' In this case, Eq. 2 might be written SHOH + HX Z SHX + H20, with a similar equation replacing Eq. 4 for depressant-free acid-water exchange. This possibility does not change, however, the basic equations or considerations of the hydrolytic adsorption model. Indeed, this type of free acid-water exchange reaction was predicted for fluorite and iron ore flotation by oleic acid in the dry grinding and boiling processes.410

Jan 1, 1961

By R. D. Nelson, F. E. Bowman

Evidence has been found for a (010)a?(111)B[102]a /,11[341]/B crystallographic relationship between the monoclinic a and B phases of plutonium during the a?B transformation. The results of an X-ray diffraction study, where [010] fiber textured a samples were used in the absence of suitable single crystals indicate that the (OIO)a planes become (111)B planes upon transformation under near-equilibrium conditions. The transformation strain along the fiber axis, which was the [010] direction, was measured dila-tomekically; the measured 8.5 pct expansion compares favorably with the 8.44 pct expansion in the in-terplanar spacing represented by the (010)a?(111)B relationship. From plots of the atom positions in each of the related planes, a correspondence was deduced between the [102]a, direction and the [341]B direction. Further analysis of the two lattice structures in the light of this relationship revealed a rotation about the [102] direction of 1 deg 43 min and a slight shearing in this same direction of about 30 min. THIS paper discusses the (B crystal structure of plutonium and the orientation relationship existing between the monoclinic a and B phases during the a?ß transformation. The kinetics of the a?ß and (3 — a transformations have received extensive consideration, and because of the crystallographic complexity of these phases, the question of the mechanisms by which these transformations occur is especially intriguing. Nelson and Shyne1 evaluated the existing experimental evidence and concluded, from the indirect evidence available, that both the ß ? a and a ? ß transformations occur by a martensitic process. Their data reveal the anisotropic nature of these transformations which suggests the existence of specific crystallographic relationships between the parent and product phases. In this paper, we are concerned with the confirmation of the existence of such a relationship resulting from the a ? ß transformation and the derivation of the crystallographic details necessary to specify it. EXPERIMENTAL RESULTS X-ray diffraction and dilatometric data were obtained from samples of a plutonium having a [010] fiber texture. These cylindrical specimens, approximately 1 cm in diam, were prepared by transforming the ß phase to a under the influence of a uniaxially applied compressive load.' The [0l0] direction is parallel to the direction of applied stress; it is also perpendicular to the (010) planes. This correspondence between the plane normal and the direction having the same indices is, in the monoclinic a plutonium structure, restricted solely to this (010)[010] combination. Such a specimen was mounted in an evacuated, elevated temperature specimen holder on an X-ray dif-fractometer so that the diffracting surface was perpendicular to the fiber axis. The a diffraction pattern, Fig. 1, taken at about 115ºC, revealed the predominance of the (020) reflection. This monoclinic, P 21/rn space group yields no (0k0) reflections when k is odd. The temperature was raised slowly to 160°C to effect the complete transformation to the phase; then it was lowered to 120°C so that a diffraction pattern of the ß could be obtained near the a = ß equilibrium temperature for direct comparison with the a at the same temperature. The (3 diffraction pattern, Fig. 2, obtained under these conditions showed a (222) reflection relatively much more intense than in the random pattern. The other reflections appearing with sig-

Jan 1, 1970

By P. B. Leavenworth

Twenty-six fields were found in the Texas Gulf Coast in 1940 as compared to 17 fields in 1939. Of these, 14 were oil fields and 12 were gas and distillate. About 150 wells were drilling at the end of the year. Production for the year 1940 amounted to 104,127,247 bbl. as compared to 100,-253,937 bbl. for 1939. Considerable wildcatting for Wilcox production featured the exploration, but discoveries were few and the type of fields found mainly gas and distillate. On the whole, the program was discouraging. New Fields Alta Lomu. Galveston County.—The Alta Loma field was discovered on May 20, 1940, by the Stanolind Oil and Gas Company's No. I John A. Hulen, which blew out at a depth of 9166 it. and ran wild for several days, with an estimated production of 400 bbl. per hour of 36" gravity oil from a sand in the top of the Frio. Water soon appeared but the well produced more than I3o,ooo bbl. of oil between May 20 and June 10, together with a large amount of salt water. Later the well was killed and recompleted on Nov. 23, for 276 bbl. of 34" gravity oil per day. Probably this was the most sensational discovery of the year, although development to the end of the year was disappointing. The discovery was the result of reflection seismograph work of the Stano-End Oil and Gas Co., the principal leaseholders. Bailey's Prairie, Brazoria County.— Glenn H. McCarthy9s No. I W. B. Munson was completed in a lower Frio sand from perforations 11,345 to II,349 ft. for 8 bbl. of fluid (50 per cent black oil, 27" gravity, and 50 per cent B. S. and W.) on Sept. 24, 1940. It was finally recompleted as a gas well from perforations 11,631 to 11,651 ft., on Oct. 9, 1940. The well had been drilled to a total depth of 11,860 ft. This well produced for only a short time and the area is at present inactive. Blessing, Matagorda County.—The Texas Company's No. I A. B. Pierce was completed from a Frio sand from 8265 to 8300 ft. on July 8, 1940, for an initial production of 29 bbl. of distillate, I 1/2 million cu. ft. of gas. One other gas and distillate well was completed in 1940. Borden, Wharlon County.—J. F. Hutch-ins' No. 2 A. P. Borden Estate was completed on Feb. 11, 1940, for 108 bbl. of 35,6° gravity oil, from a Frio sand at 4758 to 4771 ft. This is the second well drilled in the area by Hutchins. Two other wells in 1940 were failures and there was no activity at the end of the year. Dyersdale, Harris County.-The Dyers-dale field was opened by the completion, on Sept. 15, 1940, of H. C. Cockburn's No. I G. Burkitt from a sand in the top of the Frio, through perforations from 4067-4072 ft., for 240 bbl. of low-gravity oil. By the end of the year the field had been fairly well outlined and did not appear to be a major discovery. Duck Bay, Calhoun County.—Coronado Oil Company's No. I Welder, alter having drilled to 10,002 ft., perforated casing from 5654 1/2 to 5659 it. and was completed for 60 bbl. of 36.8° gravity oil On July 27, 1940, from a Miocene sand.

Jan 1, 1941

By P. B. Leavenworth

Twenty-six fields were found in the Texas Gulf Coast in 1940 as compared to 17 fields in 1939. Of these, 14 were oil fields and 12 were gas and distillate. About 150 wells were drilling at the end of the year. Production for the year 1940 amounted to 104,127,247 bbl. as compared to 100,-253,937 bbl. for 1939. Considerable wildcatting for Wilcox production featured the exploration, but discoveries were few and the type of fields found mainly gas and distillate. On the whole, the program was discouraging. New Fields Alta Lomu. Galveston County.—The Alta Loma field was discovered on May 20, 1940, by the Stanolind Oil and Gas Company's No. I John A. Hulen, which blew out at a depth of 9166 it. and ran wild for several days, with an estimated production of 400 bbl. per hour of 36" gravity oil from a sand in the top of the Frio. Water soon appeared but the well produced more than I3o,ooo bbl. of oil between May 20 and June 10, together with a large amount of salt water. Later the well was killed and recompleted on Nov. 23, for 276 bbl. of 34" gravity oil per day. Probably this was the most sensational discovery of the year, although development to the end of the year was disappointing. The discovery was the result of reflection seismograph work of the Stano-End Oil and Gas Co., the principal leaseholders. Bailey's Prairie, Brazoria County.— Glenn H. McCarthy9s No. I W. B. Munson was completed in a lower Frio sand from perforations 11,345 to II,349 ft. for 8 bbl. of fluid (50 per cent black oil, 27" gravity, and 50 per cent B. S. and W.) on Sept. 24, 1940. It was finally recompleted as a gas well from perforations 11,631 to 11,651 ft., on Oct. 9, 1940. The well had been drilled to a total depth of 11,860 ft. This well produced for only a short time and the area is at present inactive. Blessing, Matagorda County.—The Texas Company's No. I A. B. Pierce was completed from a Frio sand from 8265 to 8300 ft. on July 8, 1940, for an initial production of 29 bbl. of distillate, I 1/2 million cu. ft. of gas. One other gas and distillate well was completed in 1940. Borden, Wharlon County.—J. F. Hutch-ins' No. 2 A. P. Borden Estate was completed on Feb. 11, 1940, for 108 bbl. of 35,6° gravity oil, from a Frio sand at 4758 to 4771 ft. This is the second well drilled in the area by Hutchins. Two other wells in 1940 were failures and there was no activity at the end of the year. Dyersdale, Harris County.-The Dyers-dale field was opened by the completion, on Sept. 15, 1940, of H. C. Cockburn's No. I G. Burkitt from a sand in the top of the Frio, through perforations from 4067-4072 ft., for 240 bbl. of low-gravity oil. By the end of the year the field had been fairly well outlined and did not appear to be a major discovery. Duck Bay, Calhoun County.—Coronado Oil Company's No. I Welder, alter having drilled to 10,002 ft., perforated casing from 5654 1/2 to 5659 it. and was completed for 60 bbl. of 36.8° gravity oil On July 27, 1940, from a Miocene sand.

Jan 1, 1941

By L. S. Darken

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By D. S. Tannhauser, I. Bransky

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

S. Tandanand, Twin Cities Mining Research Center, U. S. Bureau of Mines As an addition to the fine reviews on drilling presented in the foregoing papers, we feel it would be appropriate to mention briefly some work in this area by the U. S. Bureau of Mines. The Bureau has had under way for several years at its Twin Cities Mining Research Center studies directed toward a better understanding of basic drilling mechanisms. The work includes drillability investigations with diamond rotary, and with percussive drilling systems, as well as fundamental studies of rock behavior under drill bit types of loading. Results of our work to date have contributed the following to the state of the art. MECHANISM OF ROCK FAILURE-Rock fragmentation through use of mechanical energy systems, including drilling systems, consists of two major components-machine and rock. The two components are related to each other by their functional behavior and their resultant motion which the components mutually influence. Forces in the systems are transmitted directly to the bit which in turn induces stresses in the rock. When the induced stresses exceed the strength of the rock, the rock fails resulting in penetration. Rock strength is a function of the forces applied to the rock. Stresses under a drill bit, regardless of bit configurations, are essentially compressive, resulting in a condition where the rock has the highest resistance to failure. The ratio of principal stresses induced under drill bits is an indication of the mode of failure in the rocks. Initially, compressive stresses under the drill bit cause rock to undergo inelastic deformation. The impression observed at the first stage of crater formation under the drill bit shows that rock is no longer elastic. Associated subsurface failure at this stage precedes total rupture which subsequently appears at the rock surface. Thus, explanation of crater formation, by applying theory of elasticity alone, is likely to be over-simplified. ENERGY VERSUS VOLUME OF ROCK REMOVED-Experimental results show that energy per unit volume of rock removed is constant for a particular rock and bit type. Rock offers a definite resistance to penetration, depending on the method of the energy application; this may be defined as the drilling strength of a rock. Energy consumption in a drilling system may be divided into two components: 1) Energy required to move the machine parts; and 2) energy consumption in breaking rock. Component 1 is dependent on the type of the machine. Component 2 is dependent on the strength properties of rock and the efficiency of the bit in rock cutting. The sum of the energy required in both components determines the total energy required in breaking rock. Our work in this area has included consideration of both diamond and percussive drilling systems. PENETRATION RATE-For a drilling rate expression to be useful in predicting field performance, it should include the operating characteristics of the drilling machine. Eq. 37, for example, is simply a statement of the fact that the drilling rate is determined by the power output of the machine (2pNT) and the power requirements to break the rock in the hole (AER). In order to predict the performance of a particular drill and the effect, for example, of the rotary speed, on the drilling rate, R, Eq. 37 must be modified to include the

Jan 1, 1967

By D. K. Bose, C. K. Gupta, K. U. Nair

A new approach to processing an indigenously available low grade molysulfide concentrate by chlorination with elemental chlorine in presence of oxygen is reported. Recovery of nickel and copper values associated with the sulfide concentrate by suitably treating the residue obtained after chlorination is also reported. In the chlorination process, a gaseous mixture of chlorine and oxygen in the volume ratio bf 2:5 has been passed at 1.66 x 10- 5 m3/s for 1800 s over a 0.01 kg batch of molysulfide concentrate at a temperature of 573°K. Most of the molybdenum has been volatilized as molybdenum oxychloride which has subsequently been extracted in water. The molybdenum value from the aqueous solution has been recovered in the form of calcium molybdate (CaO.MoO3) by treatment with calcium chloride (CaCI2). In an alternative processing scheme, the molybdenum rich solution has been treated with an oxidizing agent (K2S20f.J) and allowed to boil to recover a major portion of the molybdenum value in the form of molybdic oxide (MOOS). The spent charge obtained after molysulfide chlorination has been mixed with about 1 wt % sodium chloride and heated at 773K under an oxygen atmosphere. The reacted mass has been water-leached to yield a nickel-copper bearing solution with limited iron. The process liquor appears to be well suited for further processing by known hydrometallurgical recovery processes for nickel and copper. In the conventional process of molybdenum extraction, the molysulfide concentrate (-59% Mo) is first subjected to roasting to produce molybdic oxide. The oxide is then further processed in sequential steps involving vacuum distillation, ammonia leaching, and calcination to higher purity prior to hydrogen reduction to metal. In India there is at present some small tonnage production of molysulfide concentrate from a byproduct recovery plant of the M/s. Uranium Corp. of India Ltd. (M/s UCIL), Bihar. Efforts are being made at this laboratory to process the low grade fraction of the concentrate which contains sulfides of copper, nickel, and iron; quartz; and chlorites. Here, the conventional routes involving roasting and vacuum distillation appear unsuitable to produce an acceptable quality of molybdic oxide at high recoveries. Formation during roasting molybdates of some of the impurities present in the sulfide concentrate make subsequent vacuum distillation less efficient. In view of these problems, in earlier work reported from this laboratory the low grade concentrate has been processed hydrometallurgically to P. produce calcium molybdate. Starting from this molybdenum intermediate, processes have also been developed for the production of molybdenum and ferromolybdenum. Chlorination as an alternative to roasting for metal sulfides has been drawing considerable interest. The high reactivity of chlorine, the relatively low temperature of operation, the suitability of application to low grade resources, the convenience of recovering sulfur in non-polluting form, and the purity of chlorides which are separated by distillation all favor chlorination. In recent years, considerable work has been reported on the chlorination of common metal sulfides. In the field of molybdenum extraction from its sulfide resource, use of chlorination technology has been rather limited. Senderoff and Labrie3 were the first to chlorinate molysulfide concentrate with elemental chlorine at about 823°K to molybdenum pentachloride for use in the electrolytic preparation of molybdenum. The only other reported work, by Haver, Uchida and Wong, involved reaction between molysulfide and chlorine at 673°K to recover sulfur. The reaction products were, however, identified as molybdenum pentachloride and sulfur monochloride.

Jan 1, 1979