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By G. Das, S. V. Radcliffe

The substructural features developed in tungsten as a function of annealing temperature (up to 2200°C) and type of material [undoped and doped powder metallurgy (PM) tungsten and electron beam melted tungsten] have been investigated by transmission electron microscopy. For doped PM tungsten wires, characteristic "par-ticulate" substructural features developed rapidly with increase in annealing temperature above 700°C. The features consisted of parallel rows of elongated or circular shapes (500 to 1000A diam) lying along the direction of the wire axis and were identified as internal voids by diffraction contrast experiments. In recrystallized doped PM rod, larger voids were observed and were identified by precision dark field analysis to be cubic in shape and bounded by (100) planes. In marked contrast with both the doped PM materials, recrystallized undoped PM rod exhibited only very occasional and randomly arranged voids. Furthermore, no voids were observed in either material after electron beam melting. The high concentration of voids in the doped PM materials is attributed primarily to vaporization of doping additions or their pvoducts situated at the original grain boundaries , whereas the few voids in undoped material are considered to be traces of microporosity which were not eliminated during sintering. A tentative mechanism is suggested for the dezlelopment of the voids in relation to the processing sequences (sintering and working) and to the subsequent annealing. In recent years, a characteristic substructural feature consisting of rows of small elongated or circular regions of light contrast lying along the direction of working has been seen in thin foil electron microscopy studies of annealed sheet, wire, and rod tungsten. These features were present in the published micrographs of sheet by Weissmann et al.1 and of wire by Meieran and Thomas2, although the authors did not draw attention to them. Wronski and Fourdeux3 observed similar features in sintered rod tungsten (it was not specified whether or not the material was doped*) and interpreted them on the basis of their ap- particles, based on extraction replica evidence from the fracture surface of the initial hot-rolled slab material from which the sheet was prepared. No diffraction contrast experiments on the features were reported in any of these studies. The present investigation was undertaken with the primary objectives of: a) identifying the nature of these substructural features in tungsten by electron diffraction contrast experiments, since the contrast for voids can be expected to differ from that for crystalline or glassy particles, and b) elucidating the origin of the features and their development. For the latter purpose, doped and undoped powder metallurgy tungsten was obtained as rod and wire to represent different stages of reduction during final processing. These materials were examined both in the as-processed condition and after annealing to successively higher temperatures. In addition, the same doped and undoped materials were examined after vacuum melting in rod form. I) MATERIALS AND PROCEDURE Doped powder metallurgy (PM) tungsten wire (commercial purity 99.9 pct W) was obtained in the as-drawn and surface ground condition (0.030 in. diam "ground seal rod"). Doped and undoped tungsten rod (0.075 in. diam) representing an earlier stage of final processing was obtained from the same commercial source (Refractory Metals Division, General Electric Co.). Lengths of both the doped and undoped rod materials were single-pass melted in an electron-beam zone refiner to examine the effect of vacuum melting on the substructure. Annealing was carried out in a tungsten crucible in a tantalum strip resistance furnace under a vacuum of l0-15 mm Hg. Longitudinal sections of the wire and rod materials were examined by light and electron microscopy. The preparation of thin foils suitable for electron transmission from 0.030 in. diam tungsten wire and the rod specimens was carried out by means of a high-precision microjet technique developed to provide lack of jet stability and precise control of the area thinned. The method is described in detail elsewhere.' The foils were examined in a JEM 6A electron microscope using a goniometer stage (±20 deg tilt, 360 deg rotation) and operated at 100 kV. To minimize contamination problems a 200 µ condenser aperture was used in conjunction with a useful beam current of 50 µA. II) RESULTS AND DISCUSSION A) Diffraction Contrast Analysis. In order to determine the optimum conditions for the development of the substructural feature, a series of isochronal 30 min annealing experiments were carried out on specimens of the doped PM tungsten wire. The transmission electron microscopy analysis showed that the as-drawn wire, Fig. 1(a), consists of 'fibers' whose long axis is closely parallel to the wire axis of (110). The fiber width averages some 0.5 µ. Dense disloca-

Jan 1, 1969

By John J. Henn

Two lime sinter processes for recovering alumina from clay, the double-leach process and the single-leach process, are evaluated in this Bureau of Mines report. In both processes, clay and limestone are mixed and sintered to form calcium aluminate from which alumina is extracted as sodium aluminate by leaching with a dilute solution of sodium carbonate. The pregnant liquor is desilicated, then carbonated to precipitate alumina trihydrate which is recovered and calcined to a,-alumina. The fixed capital costs for plants producing 1,000 tons per day of alumina are $85 million for the double-leach process and $86 million for the single-leach process based on a Marshall and Stevens chemical equipment index of 240.0. Because plant locations are variable with respect to the proximity of clay and limestone deposits, a nomograph is included to determine operating costs at various delivered costs of clay and limestone. For plants at which the delivered cost of clay containing 30 percent A1203 is $2 per ton and the delivered cost of limestone is $1 per ton, the operating costs are $81.04 and $89.87 per ton of alumina for the double-leach process and single-leach pro-cess, respectively.

Jan 1, 1969

By J. W. Spretnak, D. A. Chatfield, G. W. Powell, J. R. Eifert

In nzost cases, the driving force for a lattice transformation is produced by supercooling below the equilibriunz transformation temperature. The interfnce reaction in isothermally annealed, multiphase diffusion couples may involve a luttice transformation which also requires a driving force. Direct experinzental evidence has been obtained for the existence of the driring force in the form of a supersaturated phase at the aocc)-0@cc) interface in Cu:Cu-12.5 ult pct A1 couples; the super saturation is equivalent to an excess free energy of approximately 3 cal per mol at 905. A tentatiue interpretation of the dynanzic situation a1 the interface based on the free energy-composition diagram is proposed. THE presently accepted theory of diffusion in multiphase couples1 states that there will be a phase layer in the diffusion zone for every region which has three degrees of freedom and which is crossed by the diffusion path in the equilibrium phase diagram. For binary systems, this restriction excludes all but single-phase fields and, for ternary systems, only one- and two-phase fields are included. In addition, Rhines"~ as well as other investigators3 6 have reported that the compositions of the various phases adjacent to the interfaces are, for all practical purposes, the compositions given by the intersections of the diffusion path with the solubility limits of the single-phase fields of the equilibrium phase diagram. Some studies of the rate of thickening of these intermediate diffusion layers indicate that the thickness of the layer changes para-bolically with time, or: where x is the position of the interface relative to an origin xo, t is the diffusion time, and k is a temperature-dependent factor. crank7 shows mathematically that, if the compositions at an interface are independent of time and the motion of the interface is controlled by the diffusion of the elements to and from the interface, then the segments of the concentration penetration curve for a semi-infinite step-function couple will be described by an equation of the form: hence, Eq. [l] follows from Eq. (21 if the interface compositions are fixed and if the motion of the interface is diffusion-controlled. Although the concept of local equilibrium being attained at interfaces has assumed a prominent role in the theory of diffusion in multiphase couples, experimental evidence and theoretical discussions which challenge the general validity of this concept have been reported in the literature. arkeen' has stated that strict obedience to the conditions set by the equilibrium phase diagram cannot be expected in any system in which diffusion is occurring because diffusion takes place only in the presence of an activity gradient. Darken also noted that it is usually assumed that equilibrium is attained locally at the interface although the system as a whole is not at equilibrium, the implication being that the transformation at the interface is rapid in comparison with the rate of supply of the elements by diffusion. ISirkaldy3 indicates agreement with Darken in that he believes the concept of local equilibrium is at best an approximation because the motion of the phase boundary requires that there be a free-energy difference and, hence, a departure from the equilibrium composition at the interface. Seebold and Birks9 have stated that diffusion couples cannot be in true equilibrium, but the results obtained are often in good agreement with the phase diagram. The initial deviation from equilibrium in a diffusion couple will be quite large because alloys of significantly different compositions are usually joined together. Kirkaldy feels that the transition time for the attainment of constant interface compositions (essentially the equilibrium values) will be small, although in some cases finite. Castleman and sieglelo observed such transition times in multiphase A1-Ni couples, but at low annealing temperatures these times were quite long. Similarly, ~asing" found departures, which persisted for more than 20 hr, at phase interfaces in Au-Ni and Fe-Mo diffusion couples. Braun and Powell's12 measurements of the solubility limits of the intermediate phases in the Au-In system as determined by microprobe analysis of diffusion couples do not agree with the limits reported by Hiscocks and Hume-Rothery13 who used equilibrated samples. Finally, Borovskii and ~archukova'~ have stated that the determination of the solubility limits of phase diagrams using high-resolution micro-analyzer measurements at the interfaces of multiphase couples is not an accurate technique because of deviations from the equilibrium compositions at a moving interface; diffusion couples may be used to map out the phase boundaries in the equilibrium diagram, but the final determination of the solubility iimits should be made with equilibrated samples. The purpose of this work was to investigate the conditions prevailing at an interface in a multiphase diffusion couple and to compare the interface compositions with those associated with true thermodynamic equilibrium between the two phases. Microanalyzer techniques were used to measure interface compositions in two-phase Cu-A1 diffusion couples annealed at 80@, 905", and 1000°C for various times.

Jan 1, 1969

By P. T. Brooks

This Bureau of Mines study describes a process for recovering nickel, cobalt, molybdenum, and chromium contained in complex waste superalloy grindings that, for lack of an economical domestic recovery process, are being largely marketed abroad. The process, devised by laboratory scale operations, includes scrap preparation, dissolution of metallics in hot chlorinated acidic liquor, carbon adsorption, three successive solvent extraction separations, and selective chemical precipitations. Nearly 90 percent of the nickel, cobalt, molybdenum, and chromium were separated and recovered as oxides, carbonates, and basic sulfate products.

Jan 1, 1969

By J. J. Fischer

COMPOSITES containing cold-drawn, high-strength steel wires have shown promise for normal and slightly elevated temperature applications, particularly where strength-to-weight ratios or corrosion resistance are important.'-3 Although tensile strengths up to 500,000 psi may be obtained by cold drawing these wires, processing the composite at elevated temperatures will result in a rapid decrease of the wires' strength. In wrought maraging steels, high-strength levels can be obtained by aging at 900' . Because these alloys do not rely on heavy cold working to achieve their strength, and because they do not overage readily, they are of potential interest for use in composites. In view of this, the tensile strengths of composites containing The total heat effect thus represents the heat of formation, AHf of the compound at 273' . Since the heat of solution of tin in the tin solvent bath is zero, AHz = 3( - H273)Sn and Hf is given by: For LaSn3, AH3 had a measured value of 11,285 i 380 cal per g-atom while for La2Sn, the corresponding value was 33,658 870 cal per g-atom. Using the measured data for the compounds and pure lanthanum, a value of -15,150 200 cal per g-atom was calculated for the heat of formation of LaSn, at 273°K, while Hf for La2Sn3 was found to be -28,090 400 cal per g-i&om. The authors would like to acknowledge the financial support of the Army Research Office, Durham, North Carolina. under contract No. DA-31-124-ARO-D-384.

Jan 1, 1969

By M. Yoshinuga, S. Watanabe

Some iron ores, sinters and pellets occasionally show abnormal behavior during reduction which makes them undesirable as blast furnace burden. These may be divided into the following three types: (1) decrepitation of iron ore, (2) swelling of iron ore and pellet, (3) size degradation of sinter. In this paper reduction experiments and microscopic examinations were made to clarify the mechanisms and causes of these abnormal phenomena. Decrepitation occurs mainly when compact hematite ores containing small amounts of limonite are heated to about 500°C. Abnormal swelling of ores and pellets is caused by the rapid growth of fibrous metallic iron from the surface of wustite grains during rapid reduction and is fundamentally related to their original microstructure. Size degradation of sinter occurs through the development of cracks in the reduction stage from hematite to magnetite. About 80% of the iron ore used in Japan's blast furnaces comes from abroad, and the iron and steel industry must import this raw material from distant overseas places at high freight rates. The blast furnace operators, therefore, have made strong efforts to cut costs under these restrictive raw materials conditions by increasing productivity and simultaneously decreasing coke consumption. If, however, a high proportion of the ore burden consists of unsuitable materials furnace irregularities often result, establishing the need for detailed investigations of the basic natures of the ore constituents and their reactions during the reduction process. Recent investigations '-' of various ore burdens suggest that some iron ores, sinters and pellets are occasionally abnormal in appearance and behavior during reduction studies and may prove to be undesirable for use in the blast furnace. In the present study reduction experiments and microscopic observations were made to clarify the causes and the mechanisms of the abnormal behavior observed in some constituents of the burden and their effect on blast furnace performance. REDUCING APPARATUS The four kinds of reducing apparatus used in this investigation were the following: 1. The JIS* (Modified Gakushin') apparatus shown in Fig. la is most commonly used in Japan to evaluate the reducibility of ores under static conditions. It consists of a stainless steel tube of 60 mm inside diam suspended from a balance. 2. Linder's Reduction Test apparatus (Fig. lc) has a reducing barrel 130 mm diam and 200 mm long which rotates at 30 rpm. Some modifications were made in test procedures. 3. Gakushin Standard Test apparatus for determining the reducibility of granular ores (Fig. Id) consists of a horizontal silica tube 32 mm diam, 370 mm long and a movable electric furnace which enables rapid heating and cooling of the specimens. 4. The test apparatus for reduction under load (Fig. lb) gives a comprehensive evaluation of the behavior of ores under conditions simulating the static loading and the chemical reduction conditions encountered in. a blast furnace stack. A stainless steel tube of 50 mm diam and a carbon rod of 35 mm diam were used as the sample container and the support for the weight, respectively. In each investigation care was taken to select the most suitable method and apparatus to distinguish the abnormal nature of the ore in question. SIZE DEGRADATION OF SINTER DURING REDUCTION Sinter makes up the major portion of the blast furnace burden and its behavior during reduction should bear a close relationship to the iron productivity. Recently, some of the sinter was found to show serious size degradation during reduction at a relatively low temperature range. Because this phenomenon was thought to be a possible source of furnace irregularities, tests were made to clarify the phenom-

Jan 1, 1969

By E. G. King

Heats of formation of three crystalline oxides of rhenium (Re02, ReO3 and Re207) have been determined by the method of solution calorimetry, using an aqueous perchloric acid--ceric perchlorate solvent. Copper metal and cupric oxide were utilized as auxiliary substances. Heats were determined at 298' K for the reactions Re + 2CuO = Re02 + 2Cu, Re + 3CuO = ReO3 + 3Cu, and 2Re + 7CuO = Re207 + 7Cu. Standard heats of formation were derived using the value of -37.23 ±0,15 kcal/mole as the heat of formation of CuO. The standard molal heats of formation of the rhenium oxides were determined: Re02, -107.3 ±0.8 kcal; ReO3, -140.8 ±0.9 kcal; and Re207, -301.9 ±1.8 kcal.

Jan 1, 1969

By L. F. Haven

"The desirable shovel speed-torque curves are described, along with the characteristics of the more important electrical components used to approximate these curves. A particular shovel regulator system combining these components is discussed in detail and some of the advantages and disadvantages of the system are given.INTRODUCTIONIN 1959, STATIC CONTROL was for the first time successfully applied, installed and operated on a mining machine in North America. Since that time, a great deal has been learned about this control by the people maintaining these machines as well as by the de-signers.In 1961, the first SCR (Silicon Controlled Rectifier) or thyristor control system was installed on an excavator. This control differed from the earlier static control in that thyristor excitors supplied the generator fields directly. The development of thyristors of a sufficient rating to supply amounts of phase-controlled power to the generator fields eliminated the bulky Mag. Amp. -Rectifier combination previously used."

Jan 1, 1969

By Wilson Blake

A mathematical model based on the finite element method of stress analysis has been used to describe the behavior of the western wall of the Kimbley Pit as its slope was steepened from 45° to 57°. Theoretical stress changes because of slope modification are slight except at the toe of the modified slope. Magnitudes of stress created are small when compared with the strength of a competent rock. Resulting displacement patterns point out the need for determining the in-situ state of stress at a site prior to excavation or modification. A comparison of model results with field measurements shows that, in general, the model has described the measured behavior of the west wall of the Kimbley Pit remarkably well. The Bureau of Mines and the Kennecott Copper Corp. began joint research on open-pit slope stability at the Kimbley Pit, Ely, Nev., in 1961. The initial or planning phase of this research dealt with a detailed geologic study of the Kimbley Pit, determination of in-situ stresses in the district, laboratory and field tests to determine rock properties, and the design of a full-scale experiment to study the behavior of this pit as its western wall was steepened from 45° to 57°. Fig. 1 shows a cross-section of the original pit outline, the steepened pit outline, major geologic features, and the two instrumentation adits. After the final or slope modification phase of the research began, a laboratory research program was initiated to develop a mathematical model that would analytically describe the behavior of the pit as its western slope was steepened. This theoretical model study of the slope modification at the Kimbley Pit was conducted with the finite element method of stress analysis. The results are described in this report.

Jan 1, 1969

By J. C. Williams, M. J. Blackburn

Several of the decomposition processes that can occur in supersaturated phases in a Ti:11.6 wt pct Mo and a Ti:20 wt pct V alloy have been studied by transmission electron microscopy. The deformation induced "marternsitic phase" in the Ti:Mo alloy has been found to have a bcc or bct structure rather than the previously reported hexagonal structure. The morphology of&apos; the transformed region is a rather complex asserrlblage of twins, twinning occurring in one or more systems; this internal twinning has been found to occur on (112). The w phase is formed in both alloys on aging and is present in the Ti:Mo alloy after quenching. The structure of this phase has been confirmed as hexagonal in both systems, however, differences in morphology and stability are found between the two alloys. Thus in the Ti-Mo alloy the w phase has an ellipsoidal morphology with the major axis lying parallel to <111>ß or [0001]w while in the Ti-V alloy the phase forms as cubes, the cube faces lying parallel to {100}ß or {2021}w Some observations on the particle sizes, volume fraction, and composition of the w phase in the Ti-Mo alloy are listed. The mode of formation of The a phase from the (ß + w) structures is also different in the two alloys. In the Ti-Mo alloy the a phase is formed by either a cellular reaction or by the growth of isolated needles, whereas in the Ti-V alloy the a phase is nucleated at an w:ß interface and grow to consume the w phase. Some of the difjerences in behavior of the w phase are attributed to the mismatch between it and the solute enriched ß matrix in which it forms. MaNY transition elements tend to stabilize the bcc or ß-phase when added to titanium. In general two types of phase diagrams are produced, either a ß-stabilized (ß-isomorphous) system, e.g., Ti:Mo, -Ti:V, Ti:Nb, or a ß-eutectoid system, e.g., Ti:Cr, Ti:Fe, Ti:Mn. In previous papers&apos;-4 the phase transformations in the a-phase and (a + ß)-phase alloys have been described and this work has been extended to ß-stabilized systems. Specifically, transformations in the alloys Ti:20 wt pct V and Ti:11.6 wt pct Mo have been studied; in both of these alloys the ß phase is retained at room temperature when quenched from the ß-phase field. A number of phase transformations can occur in such metastable ß phases and the two alloys were chosen to include most of the transformations reported for ß-stabilized systems. We list these possible phase transformations below. Ti:11.6 Mo quenched from >780°C to retain the ß phase: a) The w phase can form on quenching.5 b) Martensite can be produced by subzero cooling or deformation. Two martensite habit planes have been reported in Ti:Mo alloys; (334)ß and (344)ß=6 c) On aging at temperatures <-550° C the w phase is formed before the a-phase.5,7 d) On aging at temperatures >550°C the a phase is formed.7 e) The martensite can be tempered. It has been reported that the a phase rather than the ß phase is precipitated during tempering.&apos; Ti:20V quenched from >660°C to retain the ß phase:9 a) At aging temperatures <260°C separation into two bcc phases occurs. b) The w-phase is produced prior to the a phase on aging at temperatures <-400°C. c) At temperatures 2400°C the a phase is formed directly. T-T-T diagrams describing the temperature and time regimes for the formation of these phases have been published7,9 for a Ti:12 pct Mo and a Ti:20 pct V alloy. We have attempted to investigate these transformations using transmission electron microscopy, however thin foils undergo a spontaneous transformation in all conditions except the equilibrium (a + ß) structure. This transformation has been reported previ0usly10,11 and we will comment on its morphology and nature in the various sections of experimental results. EXPERIMENTAL The compositions in wt pct of the two alloys investigated were: Ti:11.6 Mo, 0.100 02, 0.006 N2, 0.0015 H2 Ti:20V, 0.0574 O2, 0.0111 N2, 0.005 H2 These alloys were cold-rolled to 0.020 in. thick sheet. Specimens were heat treated in vacuum or in inert gas at temperatures >500°C and in a circulating air furnace at temperatures <500°C. Thin foils were prepared using standard techniques, described in detail previously." Dark field micrographs were obtained using high resolution technique. RESULTS Martensitic Transformation in Ti:11.6 pct Mo. Detailed study of the deformation induced martensite is not possible due to a spontaneous transformation which occurs near the edge of thin foils as shown in Fig. 1. Similar transformations have been observed in iron-" and copper-base13 alloys as well as other titanium alloys, but some observations specific to the Ti:1l.6 Mo alloy are listed below. a) The boundaries of these transformed regions are glissile and move under the influence of the electron beam during examination. b) Selected area diffraction indicates the transformed regions have the same structure as the matrix, being separated by tilt boundaries. The misori-

Jan 1, 1969

By W. H. Eddy

Laboratory batch and small-scale continuous flotation tests were con-ducted by the Bureau of Mines on a mica waste tailing from Kings Mountain, N.C., to determine the feasibility of producing high-quality mica, feldspar, and glass sand. Mica was recovered by two methods; one was by flotation in an alkaline circuit, which produced a mica concentrate assaying 92.0 percent mica with a recovery of 87.l percent, and the other by flotation in an acid circuit, which produced a mica concentrate assaying 91.0 percent mica with a recovery of 79.4 percent. Continuous flotation processing yielded a feldspar concentrate assaying 1.10 percent Na20 and 13.50 percent K20, with recoveries of 66.4 and 80.6 percent, respectively. The feldspar tailing was high-quality quartz glass sand analyzing 98.6 percent Si02 and 0.02 percent Fe203.

Jan 1, 1969

By J. R. Cahoon, W. V. Youdelis

In a recent publication by Flemings and Nereo, equations for the calculation of the solute distribution in castings were developed, and the solute distributions for unidirectionally solidified A1-4.5 pct Cu ingots cast under various thermal conditions were calculated. The equations derived by Flemings and Nereo for the dendrite "expansion" and "steady-state" zones are essentially equivalent to those previously published by Kirkaldy and Youdelis, 16 for, although the flow velocity cooling rate, and temperature gradients appear in the fundamental differential equations, calculation of the solute distribution requires that the above be explicitly related to the assumed or measured solid-liquid mass distributions during solidification. In the treatment of Kirkaldy and Y-oudelis the mass distributions are simply assumed or measured without any prior and explicit association of the mass distributions to a velocity parameter. The treatment of Flemings and Nereo permits solidification conditions more complicated than the simple unidirectional case to be considered (although in principle the treatment of Kirkaldy and Youdelis could also be extended to include the more general solidification case); however, we note some limitations in the treatment of Flemings and Nereo, and the purpose of this discussion is to point these out and also to indicate those points of similarity in the mass distribution models used which make the two treatments equivalent. Both the Kirkaldy-Youdelis and Flemings-Nereo treatments consider a zone of dendrite "expansion" followed by a "steady-state" zone. However, Flemings and Nereo have failed to consider a zone of "collapse" which begins at the base of the first dendrites to reach the top of the ingot. The omission of this zone of "collapse" results in too high a value for the solute concentration in the latter portion of the ingot to solidify and the conservation of total solute is not possible. In the zone of "collapse" the solute concentration rapidly decreases, which may be accounted for as follows: consider a mushy zone of length X,, shown schematically in Fig. 11 (a), which develops at the chill face and then moves as a steady-state configuration along the length of a solidifying ingot. The solute distribution in this zone, when it first attains the steady state, is shown qualitatively in Fig. 11(b). The segregation is positive (above Co) in the region ab because this region contains primary dendritic solid, ranging from kco to kcE in composition (where k is the partition coefficient and CE is the composition of the eutectic liquid), and liquid metal near eutectic composition. The segregation is negative (below Co) in the region bc because it contains primary dendritic solid only slightly above kco in average composition and liquid metal only slightly above Co in composition. As the zone X, moves as a steady state

Jan 1, 1969

By N. A. D. Parlee, M. T. Utine

ThE kinetics of absorption of oxygen by induction-stirred liquid silver (at constant Po2 and T) has received some study here.&apos;&apos;2 This paper describes a study of the kinetics of effusion (non-bubble-forming), and some additional work on absorption. A Sieverts type of apparatus was used. The kind of reaction tube assembly has been described.4 The same 25-kw, 450-kc induction unit was used as in earlier absorption work1&apos;2 but the "coupling" was different. The runs were made under the following conditions: i) saturation at 1 atm, effusion at 0.81 atm;

Jan 1, 1969

By R. V. Mrazek, F. E. Block, S. B. Knapp

The mixed homogeneous and heterogeneous kinetics of the thermal decomposition of tungsten hexacarbonyl were studied by employing a batch reactor. The system was such that a sample of tungsten hexacarbonyl could be injected into the preheated reactor, and the progress of the reaction followed by a simple pressure measurement. Both the homogeneous and heterogeneous reactions were found to be first order, and approximate activation energies were determined for each reaction. It is shown that the dis-proportionation of carbon monoxide to give carbon and carbon dioxide cannot be the source of carbon in tungsten deposits prepared by this reaction. The kinetics of the thermal decomposition of tungsten hexacarbonyl have been investigated as part of a continuing study by the U.S. Bureau of Mines on the decomposition of organometallic compounds. Reactions involving the thermal decomposition of metal carbonyls have a potential application in the preparation of pure metals and fine metal powders. Indeed, it was these applications which provided the impetus for much of the early work involving the carbonyls of nickel1 and iron.&apos; The relative lack of study of other metal carbonyls can be traced to the comparative difficulty in synthesizing these compounds. The most common use for tungsten hexacarbonyl has been as an intermediate in vapor-phase plating.7&apos;8 However, attempts to obtain a carbon-free deposit of tungsten by this method have not been successful, and some investigators have taken advantage of the carbon contamination and used this process to form tungsten carbide deposits.lo Other investigators have studied the thermodynamic properties11"14 and molecular structure of tungsten hexacarbonyl. However, very little is known about the kinetics of this thermal decomposition, the mechanisms involved," or the source of carbon in the resulting plate. In contrast, studies have been made of the kinetics of the thermal decomposition of nickel tetracarbonyl, iron pentacarbonyl, and molybdenum hexacarbonyl.&apos;l It has been found that these thermal decompositions occur by a mechanism which is partially heterogeneous in nature. Information available on the equilibrium constants for the decomposition of tungsten hexacarbonyl was used to determine a temperature range, 500" to 560°K, in which the reaction could be expected to be essentially complete. APPARATUS The apparatus used allowed the injection of a sample of tungsten hexacarbonyl into a preheated batch reactor and the use of a simple pressure measurement to follow the progress of the reaction in the sealed reactor. The pressure was sensed by means of a pressure transducer (Consolidated Electrodynamics Corp., 0.3 pct)* capable of operating at the *Reference to specific products is made to facilitate understanding and does not imply endorsement of such brands by the Bureau of Mines._______ reaction temperature. This type of sensing element was chosen to avoid the problem of condensation of the sublimed carbonyl in the capillary tubing leading to any type of remote pressure-sensing device. stirring was provided by rotating the entire apparatus. Glass beads placed in the reactor provided a pulsating agitation. To minimize thermal gradients in the reactor walls, the reactor was constructed of aluminum. The support tube which held the reactor in the furnace was thin-walled stainless steel to minimize heat conduction out of the reactor. As a result of these measures, a nearly uniform temperature (°C) was maintained throughout the reactor. Fig. 1 is a schematic diagram of the apparatus. The small gear motor rotated the entire apparatus at about 200 rpm. The bearings shown at the ends of the air cylinder were perforated to allow air to be fed to the charging piston and to allow inert gas to be fed to the reactor during the preheating period. The sample was simultaneously injected and sealed inside the reactor by operation of the air piston. Fig. 2 shows a cross section of the air cylinder and the adjoining portion of the support tube leading to the reactor. The sample carrier is shown in place at the right-hand end of the injection rod extending from the air piston. The piston is shown in the retracted position, as it would be prior to the start of an experiment. The small Teflon gasket which encircled the sample carrier at the end of the injection rod sealed the reactor when the sample was injected. This seal was maintained throughout the test by maintaining air pressure on the piston. The sample carrier was a 2-in. section of thin-walled, -in.-diam nickel tubing with an internal blank about 1 in. from the base and with the base end sealed.

Jan 1, 1969

By H. I. Aaronson, W. L. Winterbottom, G. M. Pound

On the basis of a statistical thermodynamic treatment of the data of smithz2 on the activity of carbon in austenite, a Darken and smith23 deduced that the interaction energy, wy, between carbon atoms occupying nearest-neighboring interstitial sites is repulsive. Aaronson, Domian, and pound 24 (ADP) have applied two different statistical thermodynamic analyses to the same data. One analysis, a composite of the treatments of Darken and Smith,23 Speiser and Spret-nak," and Kaufman, Radcliffe, and Cohen,26 primarily takes account of the positional entropic effects of wy in dilute solutions. The other, due to Lacher 27 and Fowler and Guggenheim," is also applicable to more concentrated solid solutions. The equations which both analyses produce for a,, can be rearranged so that, when In a,, is plotted against the appropriate function of the carbon content of the austenite, the plot will have a slope of unity when the correct value of wy is employed. Since no other constant need be simultaneously evaluated in order to make this determination, ascertaining the most probable value of wy from Smith&apos;s data on the bases of these analyses was an elementary problem in least-squares statistics. ADP demonstrated that the wy&apos;s obtained from both analyses vary with temperature in a statistically significant manner. McLellan, Gerrard, Horowitz, and sprague 29 (MGHS), on the other hand, have recently made a new statistical thermodynamic study of a,, and have concluded from this study that wy is independent of temperature. The equation which they derived for a,, is: where 0 = ratio of the mole fraction of carbon atoms to that of iron atoms, z = number of sites from which occupancy is excluded by the presence of a carbon atom and the repulsive character of its interaction with nearest-neighboring carbon atoms (z = zb in Ref. 24), and x = a geometric parameter taking account of overlapping of the exclusion shells of nearby carbon atoms. z is 1 when wy = 0 and 13 when wy = Q. For a given value of z there is a definite value of X . In the absence of an equation connecting z and X, MGHS computed geometrically the value of x at several integral values of z; x increases from 0.47 to 8.67 as z is increased from 2 to 5. MGHS fitted Eq. [I] to the a,, data of Ellis, Davidson, and Bodsworth30 at 925° and 1050°C and to the data of smithz2 at 1000°C. Confining z to integral values in the range 4 to 6, and also somewhat restricting AG, the values of z, X, and AG were sought which would minimize the average root mean square percent deviation, D, of the calculated a,, values from those obtained experimentally. Finding that D was almost always smallest when z = 5, they concluded that z is independent of temperature. Since:23, 26 where R = gas constant and T = absolute temperature, and w,, was considered to be similarly invariant, this statement cannot be strictly true. The temperature range employed, however, was small and the interval between the values of z tested was sufficiently large so that the results could still be consistent with a constant The statistical treatment of the a,, data applied by MGHS is clearly quite approximate. Since more than three values of a,, are available at each temperature, z, and X, and AG have actually been over deter mined, rather than underdetermined as their treatment implies. In order to make more complete and exact use of the a,, data, we shall employ the Legendre Method of Least Squares, as described by Whittaker and Robinson. This technique permits conversion of the overdetermined system of equations produced by the substitution into Eq. [I] of the available pairs of a,, and 0 data at a given temperature into an even determined system. Solution of the latter system yields the most probable value of each of the three constants. This procedure will allow a statistically rigorous test to be made of the conclusion drawn by MGHS in respect of the temperature dependence of In order to obtain linear iiequations of conditions" from Eq. [I], the exact values of the three unknown constants are replaced by G/RT = =/RT + y, where z, i, and aG are estimated values of the constants. This allows the conditional equations to be written in the form:&apos;l where fi -f6, i, =/RT) = the right-hand side of Eq. [I] for a given pair of ayi and values. When applied to Eq. [I], these relationships become: The i equations of condition are reduced to three "normal equations" in the manner discussed by Whittaker and Robinson. The normal equations are then solved for a, ß, and y. Both of these operations are most conveniently performed by means of the computer technique of Winterbottom and Gjostein.32 This technique was used iteratively until the value of 0 (the most sensitive of the three correction factors) became 10.01. (Until they became small, a, 8, and y

Jan 1, 1969

By W. F. Hosford, E. W. Kelley

By testing polycrystalline specimens from textured plates which had Previously been used to provide materials for growing single crystals, it has been possible to relate the plastic anisotropy of textured materials to the deformation behavior of single crystals. The deformation studies have been conducted at room temperature on textured polycrystalline magnesium and binary Mg-Th and Mg-Li alloys. Variously oriented specimens of the textured materials were deformed in plane-strain compression and in uniaxial tension and compression. The stress-strain curves are similar in their general jorm of anisotropy and stress levels to those obtained on single crystals of the same alloys. The degree of anisotropy is lower, however, in the polycrystalline materials and correlates with the intensity of the basal texture. Yield loci for the textured materials appear reasonable in terms of the deformation mechanisms, and deviate sharply from the form predicted by the Hill analysis for aniso-tropic material. A N earlier study1 of single crystals has shown that magnesium and magnesium alloys with thorium and with lithium deform at room temperature primarily by basal slip, {10i2) twinning, and (1011) banding. The (10i1) banding mode is a combination of {10ll) twinning followed by (1012) twinning and basal slip within the doubly twinned material.2, 3 Magnesium with lithium can also deform by {1010)(1210) prism slip.1&apos;4&apos;5 Still other deformation modes have been reported for magnesium6-11 but these are considered to play a minor role in room-temperature deformation. In a polycrystalline material, plastic deformation must occur in the individual grains through the operation of one or more of the various deformation modes. Because the critical shear stress for basal slip is very low compared to the activation stresses for the other deformation modes,&apos; basal slip accounts for much of the deformation in the polycrystalline aggregate. However, since there are only two mutually independent basal slip systems, and because five independent systems must be active for an arbitrary shape change in any material,&apos;&apos; modes other than basal slip must account for some of the strain. The deformation of textured magnesium, like that of other hcp metals, must be controlled by the same mechanisms observed in single crystals. In strongly textured material, the form of the anisotropy should be similar to that of single crystals, and the degree of anisotropy should depend on the intensity of the texture. EXPERIMENTAL PROCEDURE The anisotropy of deformation was investigated through the use of plane-strain compression tests, as well as uniaxial tension and compression tests. Materials. Test specimens were cut from the three textured plates of magnesium which had previously been used to provide material for single crystals.&apos; These plates, furnished by Dow Chemical Co., had been reduced about 80 pct during the process of being hot-rolled to their final 1/4-in. thicknesses. The plates had the three respective compositions, pure magnesium, Mg-0.5 wt pct Th (0.49 pct Th by spectro-graphic analysis), and Mg-4 wt pct Li (3.84 pct Li by chemical analysis). Impurities other than iron were less than 0.0005 pct Al, 0.01 pct Ca, 0.001 pct Cu, 0.0006 pct Mn, 0.001 pct Ni, 0.003 pct Pb, 0.001 pct Si, 0.001 pct Sn, and 0.01 pct Zn. Iron was 0.001 pct in the pure magnesium, 0.002 pct in the Mg-0.5 pct Th, and 0.014 pct in the Mg-4 pct Li. The textures of the three plates were determined by X-ray diffraction utilizing only the reflection technique out to an angle of 50 deg from the sheet normal. The resulting basal pole figures are presented in Figs. 1, 3, and 5. Grain sizes in the plates were ASTM number 4 in the pure magnesium and number 7 in each of the alloys. Plane-Strain Compression Tests. Plane-strain compression specimens approximately $ in. thick by 4 in. wide by $ in. long were prepared for each of the three compositions. These specimens were prepared in a manner similar to that used for the single-crystal specimens of the earlier study.&apos; All polycrystalline specimens were stress-relieved at 500°F for hr as the final step in their preparation for testing. The testing procedure was identical to that used for the single crystals, involving compression in a channel and using 2-mil Teflon film as a lubricant. The specimens were tested in six orientations of interest, these being the six combinations of the rolling, transverse, and thickness directions of the material serving as loading, extension, and constraint directions in the plane-strain compression test. Each of the six orientations was assigned a two-letter identifying code. These are combinations of the letters (thickness direction), R (rolling direction), and T (transverse direction) with the first letter signifying the loading direction and the second letter the extension direction. For example, ZR specimens were compressed in the thickness direction while extension was permitted to operate in the rolling direction of the textured material. To facilitate comparison of the present work with that of the single-crystal study1 the orientations used for single crystals are given in Table I along with the polycrystalline orientations that most nearly correspond. To insure reproducibility, at least three duplicate

Jan 1, 1969

By William Cochran

The mineral waste disposal system at the Grace Mine, Morgantown, Pa., was designed to minimize environmental effects while allowing much of the waste from the iron mine, mill, and concentrator to be utilized. Standard cost estimating procedures were used by the Bureau of Mines to determine waste disposal costs. Mill tailings and rock waste disposal costs were estimated at $0.151 and $0.276 per ton, respectively, for the 1965-67 production period. Total waste disposal cost was reduced about $0.015 per ton by utilizing part of the waste as aggregate. The net average cost for disposal of all mineral waste was $0.189 per ton.

Jan 1, 1969

By L. Cichowicz, K. K. Millheim

The constant-rate drawdown test performance for a low-permeability, verticany fractured gas well was investigated. A series of gar wells were tested by flowing each well at constant rate until the data could be analyzed using con-ventional radial flow theory. Each well was then shut in to build up. After a sufficient buildup was obtained, another flow Iest commenced but at a higher flow rate than Ihe first test. Again, the well was shut in when radial fiow was obtained. his procedure was repeated for three to four different flow rates. Two wells in the San Juan basin were tested using this procedure. Both wellere fractured after completion, cleaned up and then shut in until flow testing commenced. Test designs of both wells permitted investigation of the most realistic values of egective permeability, wellbore radius and turbulence factor. Also, being able to determine the eflective fracture flow area and vertical fraclure efficiency was inherent with this testing approach. It was observed that fractures in both wells influenced the Pressure behavior for approximately Is to 40 hours (depending on the flow rate) before radial flow was evident. After this time, drawdown data were analyzed using radial pow theory. When a low-permeability gas well has vertitally oriented, induced fractures, the early flow geometry ic. essentially linear. It will be shown how to determine when a flow test has been conducted long enough so lha&apos; the most representative values of effective permeahiiity. wellbore radius and turbulence factw can be calculated. From the linear pressure data, valuable information about The fracture treatment, such as the effective flow area and vertical fracture efficiency, can be determined for vertically froctured wells. Introduction During tests on gas wells in the Sari Juan basin7 initial transient behavior lasted for many days because of the low permeability of some porous media. As a result, stabilized flow performance could not be obtained. If these wells received some type of stimulation treatment, early pressure behavior deviated from conventional theoretical radial Row. When conventional radial flow theory was used to analyze these low-permeability fractured gas wells, larger values of flow capacity and absolute open flow potentials (AOF) sometimes resulted. Wells were assigned open flow poten- tials that proved to be 3 to 10 times higher than the well would sustain over a longer period of production. In some cases where the wells had flowed for longer periods of time during a constant-rate drawdown test, it was noticed that the effective flow capacity appeared to be decreasing with time until a certain value was reached. The early nonradial pressure behavior can be explained If linear flow is assumed. Rusell and Truitt mathematic. ally investigated the vertically fractured well in a bounded area. They showed that early flow behavior was essentially linear and, for x,/x. approximately less than 0.10 radial flow was obtained after short periods of time. Then realistic values of effective permeability and skin could be determined. Scotta experimentaliy studied the vertically fractured well with a heat flow analog. He showed that earb flow was linear, Both studies indicate that, for small values of x,/x,, linear flow approaches radial flow if the well is tested long enough, To help prove this concept of early linear flow caused by induced vertical fractures, two low-permeability gas wells were tested. Both wells received large fracture treatments prior to testing. A vertical fracture was indicated from the analysis of fracture treatments, As anticipated, tests of both wells indicated early linear flow that was later followed by a period of radial flow, Data collected from each well were analyzed. From the well tests, plus other information on each well, the effective permeability, wellbore radius and turbulence factor were calculated. Effective fracture flow areas calculated from test analyses for each well proved to be approximately one-fourth the created area calculated from classic hydraulic fracturing theory: other fractured wells that were tested but not presented in this paper also indicated that the effective fracture flow area was one-fourth to one-third the created area predicted from hydraulic fracturing theory. The vertical fracturing efficiency was estimated from the calculated values of effective wellbore radius and fracture flow area. For the two wells tested, calculated fracture lengths x, were 112 and 105 ft, and the vertical fracturing efficiencies E, were 122 and 183 percent. Development of Flow Model Agnew&apos; showed that most induced fractures below 1,500 ft are vertical. Anderson and Stah15 indicated that most of the fractures they studied were vertical. Thc model proposed for early flow in most vertically fractured gas wells is shown by Fig. 1. This model should approximate early flow behavior until radial flow is reached, at which time a radial model with an effective wellbore radius of 0.5 they will

Jan 1, 1969

Jan 1, 1969

By R. K. Buhr, H. Thresh, M. Bergeron, F. Weinberg

The microsegregation of nickel and chromium in directionally solidified AISI 4340 steel castings has been measured using electron probe microanalysis. Minimum concentrations were observed to occur at the center of the dendrite stalks, as reported previously. However, the position of the maximum concentrations could not be determined from the dendrite configuration. An etching technique has been developed which shows the position of maximum concentration. Measurements were made of the distribution of nickel and chromium in the dendritic structure. The ratio of maximum to minimum concentration was determined as a function of primary dendrite arm spacing for both as-cast and partially homogenized materials. The results are compared with observations reported in the literatuve. A S part of an investigation of solute segregation in directionally solidified AISI 4340 steel casting, electron probe microanalysis was used to measure the distribution of nickel and chromium in the dendritically segregated material. This complemented the observations on the segregation of radioactive phosphorus obtained by autoradiographic techniques in the same castings.&apos; Kattamis and I?lemings2 have reported similar measurements, using electron probe microanalysis, on dendritically segregated AISI 4340 steels. They found minimum solute concentrations occurred at the center of dendrites, maximum concentrations occurred in the center of interdendritic regions, for symmetrically oriented dendrites, and a regular variation of concentration within dendrite arms. The ratio of maximum to minimum concentration was found to be essentially independent of position in the castings, except near the chill surface where it was somewhat higher. Assuming complete diffusion in the liquid and no diffusion in the solid during freezing, they considered that isoconcentration curves in the steel were homothetic. As a result, isoconcentration curves of the various elements, contour surfaces of dendrites produced by isothermal-transformation studies, and the contour of the solid-liquid interface would all be similar, and could be superimposed by a uniform expansion or contraction of the contours. Preliminary results of the present investigation suggested that isoconcentration curves were not homothetic. It was also evident that points of maximum concentration could not be predicted from the dendrite configuration. Since the ratio of maximum to minimum concentration appeared to be an important parameter in defining the overall segregation in a casting, other techniques for determining the point of maximum concentration were investigated. In addition the overall solute distribution associated with the dendritic structure was examined for both nickel and chromium, and the consistency of the distribution for neighboring dendrites was determined. METHOD Fifty-pound heats of AISI 4340 steel were cast in a manner similar to that used by Flemings et al3 with a water-cooled copper base plate and exothermic sides and top. The nominal composition of the material was C, 0.41 pct; Mn, 0.66; Si, 0.35; S, 0.012; P, 0.010; Ni, 1.88; Cr, 0.95; Mo, 0.28. The steel solidified directionally from the chill surface, with a dendritic structure which increased in dendrite arm spacing with increased distance from the chill. Results of the general investigation of the cast structure and segregation of radioactive phosphorus in these castings have been reported elsewhere.&apos; For the present measurements, sections were cut from the casting at several distances from the chill surface. The sections were subsequently heat-treated, mounted, and then polished on a plane perpendicular to the general freezing direction of the casting. Electron probe microanalysis was carried out with the JEOL-JXA3 microprobe using a voltage of 25 kev and beam current of 0.15 µa. The take-off angle is 22 deg. Quartz crystals were used in the spectrometers and measurements made for Ka radiation from both nickel and chromium simultaneously. A thin layer of carbon was deposited on all specimen surfaces prior to examination in the microprobe. Early measurements were made on polished surfaces, with indentation marks produced by a hardness tester to indicate the area of interest. It was found desirable to use etched surfaces, as opposed to polished surfaces, to reduce sample preparation time and more readily relate the microprobe scan to the structure. To determine if this could be done, without introducing significant errors, a series of measurements were made on polished and etched surfaces of the same specimen. Both polished and etched surfaces produced similar results within normal scatter as shown in the observations. Subsequent measurements were then made on etched surfaces. Measurements with the microprobe analyzer were made by point counting, for periods of 100 sec, at 10-µ intervals. Ten-second counts were made on pure nickel and chromium standards, incorporated in the specimen mount before and after each set of measurements. The results were adjusted for background, then corrected for dead time using the expression:

Jan 1, 1969