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By C. J. Chindgren

A refractory-lined, garage-type automobile incinerator with a natural gas afterburner for air pollution control was cooperatively constructed and tested by the Bureau of Mines and the Wasatch Metal & Salvage Co. in Salt Lake City, Utah. The incinerator is capable of relatively smokeless burning of 32 to 60 cars per day, dependent on the degree to which the cars are stripped prior to incineration. Preliminary burning campaigns indicate the cost of incineration to be approximately $2.75 per car.

Jan 1, 1970

By L. B. Pankratz

Enthalpies above 298° K were determined for AgCl to 1,400° K and for AgBr to 1,200° K by copper-block calorimetry. Before melting, both compounds showed an anomalous increase in enthalpy, an effect associated with lattice defect formation. Melting points and heats of fusion were determined to be AgCl, 730° K and 2,945 cal/mole; AgBr, 700° K and 2,030 cal/mole. The heat capacity of both melted substances decreased with increasing temperature over the entire liquid ranges investigated. Enthalpies above 298° K were tabulated at even temperatures along with derived entropy increments and heat capacity values. The results were combined with the known heats of formation and entropies at 29.8.15° K to obtain values of the heats and free energies of formation over the range 298.15° to 1,400° K for AgC1 and 298.15° to 1,200° K for AgBr.

Jan 1, 1970

By C. J. Lewis

Considerable amounts of the world's known reserves of elemental sulfur are found near the surface in areas of volcanic activity both active and inactive. Because such deposits cannot in general-be mined by the well-known Frasch process, and because other methods of recovery have not proven to be economically competitive except in isolated instances, at present these reserves remain relatively undeveloped. However, projections of world sulfur demand indicate that new sources of marketable sulfur will be needed in future years 2/, 19/. For this reason, recovery of elemental sulfur from these near-surface deposits is of continuing interest. Solvent extraction as an approach to recovery of elemental sulfur from open pit-mined ores of these non-Frasch deposits has received considerable attention particularly at the research and development level 3 /, 7/, l l /, 16/, 21/,23/, 29/ This method has been and continues to be attractive because it presents the potential of high sulfur recovery and purity of product coupled with a relatively simple process flowsheet in which low energy requirements and reasonable operating costs are thought to be possible. However, the physical and chemical characteristics of the native-sulfur ores, of elemental sulfur, and of the known solvents, have presented difficulties in the development of solvent extraction processes. Up to the present time, viable processes have not been realized within the framework of sulfur marketing conditions.

Jan 1, 1970

By Richard A. Queeney, Lance G. Peterson

ESTIMATES of the stacking fault free energy of copper reported in the literature show an extensive divergence of results. Based on measurements of dislocation node radii, Thornton et al.7 find the lower limit of stacking fault energy to be 60 ergs per sq cm: Jossang and coworkers4 estimate the same value should be less than 40 ergs per sq cm. Assuming stacking fault free energy to be twice the coherent twin boundary free energy, Valenzuela8 reports 72 ergs per cm, while Inman and Khan2 cite a value of 24 ergs per sq cm. which can no doubt be accounted for by almost complete absence of interstitials in solution. However, the minute concentration was sufficient to permit observable recovery of dislocation damping. Assuming a dislocation density of 1010 CM -2 and an average loop length of 0.5 , a concentration of interstitials as low as 0.01 at. ppm is sufficient to reduce dislocation damping by more than a factor of ten. The concentration of interstitial solute atoms in Ferrovac E-0.15 pct Ti was thus estimated at 0.01 at. ppm < (C + N) < 2 at. ppm. The absence at elevated temperature of strengthening due to interstitials, Fig. 1, was therefore anticipated in the titanium alloy. The temperature dependence of the flow stress below 300°K was unaffected by addition of either titanium&apos; or zirconium.&apos; Observed, however, was an initial difference in the absolute value of the flow stress below 320oK, Fig. 1. Grain size may account for the difference; the grain diameter of Ferrovac E was 30 to 45 µ and that of Ferrovac E-0.15 pct Ti 65 to 90 µ. Although second phase particles in the form of titanium carbides and nitrides precipitated in the Ferrovac E-0.15 pct Ti alloy, the spacing was too large to produce any strengthening effect. The mechanical properties measured, therefore, were inherent to the bcc lattice. 1W. C. Leslie and R. J. Sober: Trans. ASm, 1967, vol. 60, pp. 99-111. 2 H. Conrad: Journal of Metals, 1964, vol. 16, pp. 582-88. 3 A. S. Keh and W. C. Leslie: Materials Science Research. H. H. Stadelmaier and W.W.Austin, eds., vol. 1.pp. 208.50, Plenum Press, New York, 1963. 4A. S. Keh, Y. Nakada, and W. C. Leslie: Dislocation Dymmics, Rosenfield, Hahn, Bement, Jr., and Jaffe, eds., pp. 381-406, McCraw-Hill Book Co., New York, 1968. &apos;W. J. Bratina, J. T. McCrath, and H. E. Rosinger: Can. Met. Quart., in press. 6 W. J. Bratina, J. T. McGrath, and D. Mills: Suppl. Trans. Japan Inst. Metals. 1968, vol. 9, pp. 436-43. &apos;H. E. Rosinger and C. B. Craig: Can. Met. Quart., In press. %. Mills. J. T. McGrath. and W. J. Bratina: ScriptaMet,, 1968, vol. 2, pp. 311-13. The purpose of this note is to present the results of a direct measurement of the stacking fault free energy in copper. The present method avoids both the question of interaction forces of nodal dislocations and the assumption that the coherent twin boundary free energy is one-half that of a stacking fault. Fig. 1 shows a transmission electron micrograph of a stacking fault intersecting a high angle grain boundary in copper: Fig. 2 is a schematic representation of the intersecting interfaces. To produce the specimen, pure copper was rolled to 0.002 in. thickness and annealed for several hours at 875°C. These foils were strained in tension to l04 µ in. per in., and rean-nealed to 8 min. Recrystallization and/or grain growth were not observed during the second anneal, indicating that intersections such as Fig. 1 are equilibrium configurations. Many such stacking faults were observed, but few were noted as intersecting grain boundaries in well-illuminated areas. The intersection of Fig. 1 was well away from the specimen edge. Since similar defects have not been observed in fully recrystal-lized and annealed copper, it is felt that this defect is due to the tensile straining. Electron transmission

Jan 1, 1970

By E. S. Tankins

The main purpose of this work was to study the effect of gold on the activity coefficient of oxygen in the liquid Fe-Au alloy and to determine how copper and silver change the activity coefficient of oxygen. A preliminary investigation has been made of equilibrium in the reaction of hydrogen with oxygen in some of the liquid gold alloys. The experimental method, which has been described in detail elsewhere,&apos; consisted of bubbling accurately known H-A-water vapor mixtures through the Fe-Au alloys contained in alumina crucibles within a vertical closed furnace. When equilibrium was reached, the samples were quenched by rapidly lowering the crucible under an atmosphere of argon to a water cooled brass fixture at the bottom of the furnace tube. The melts were found to freeze from the top in less than 4 sec. The heats were carefully prepared for oxygen analysis. The oxygen content was determined by vacuum fusion analysis.&apos; Only high purity electrolytic materials were used in this investigation. The activity and free energy of oxygen in the liquid iron alloys were studied by means of the reaction; The data for the 80 Fe-Au alloys, obtained as a function of temperature, are summarized in Table I and presented in Fig. 1, where log is plotted against . The results can be expressed by: The data were obtained using water vapor-hydrogen ratios between 0.04 and 0.30, and a 25 pct H2-75 pct A mixture. An oxygen content between 0.030 and 0.060

Jan 1, 1970

By G. L. Fisher, R. H. Geils

The effect of small amounts of columbium (<0.01 to 0.10 pct) on the ?-a transformation occurring during the continuous cooling of a low carbon Ni-Cu steel was investigated. Dilatometer specimens were aus-tenitized at 950" and 1068?C and cooled at 17? and 375 C° per min. Columbium caused a marked depression in the ?-a transformation temperature except when cooling at the slower rate from 950°C. The effec of columbium on the transformation temperature was greater the higher the austenitizing temperature and rate of cooling. A maximum depression of 92 C" was observed. Metallographic examination of specimens of <0.01 and 0.07pct Cb steels heated at 1200°C for 1 hr and cooled at various rates showed that columbium had a major effect on the ferrite morphology. The fer rite in the columbium -free steel remained equiaxed at cooling rates as high as 440 C? per min while the columbium-bearing steel exhibited mixed structures o equiaxed and bainitic ferrite at cooling rates as low as 130 C° per min. The ? grain boundaries in the columbium -free steel provided the ferrite nucleation sites in rapidly cooled specimens. There was a complete absence of nucleation at these sites in the colum bium-bearing steel. It is concluded that columbium depresses the transformation temperature by suppressing ferrite nucleation at the austenite grain bound-aries. In this respect the effects of columbium are analogous to those of boron in low C-Mo steels. It is well known that small columbium additions can substantially strengthen plain carbon steels. As little as 0.02 pct Cb can increase the yield strength of mild steels by 10,000 psi.1 A fine precipitate of CbC has been observed in columbium-bearing steels2 and is generally thought to be responsible for the strengthening. Little attention has been devoted to the effect of columbium on the ?-a transformation. Webster and woodhead3 have studied the effect of columbium on the isothermal proeutectoid ferrite reaction in mild steels. They found similar transformation behavior in steels both with and without columbium additions. However, as the austenitizing temperature increased, the incubation time for the start of the ferrite transformation became longer in the columbium-containing steel. Morrison1 found that the addition of 0.03 pct Cb to a C-Mn steel lowered the transformation temperature by 50 C° during cooling from 1200°C at a rate of 80 C" per min. The strengthening effect of columbium has recently been utilized in an age-hardenable, low-alloy steel containing copper and nickel.4 A small amount of columbium has a substantial effect on the as-rolled strength of this steel. By increasing the columbium level from <0.01 to 0.13 pct the as-rolled yield strength is increased by 15,000 psi. Columbium also significantly lowers the ?-to-a transformation temperature of this steel during continuous cooling from the austenitizing temperature. Because of the low carbon level in this steel (0.05 pct max), it is almost entirely ferritic. Thus, it offers the opportunity of studying the effect of small columbium additions on the proeutectoid ferrite reaction. Of particular interest in this study was the reason for the marked lowering of the transformation temperature by columbium during continuous cooling. EXPERIMENTAL PROCEDURE Materials. The compositions of the steels used in this investigation are shown in Table I. The steels were 30-lb air induction melts. They were forged to 4 by 8 by 1 in. plate at 1230°C, air cooled, and then reheated to 1230°C and cross-rolled in two passes to in. plates. Dilatometry. A Leitz Bollenrath dilatometer was used to record the transformation during continuous cooling from two different austenitizing temperatures. The dilatometer specimens were + in. in diam and 2 in. long. Oxidation and decarburization of the specimens was prevented by maintaining a small positive pressure of dry argon in the dilatometer furnace and by plating the specimens with 1 mil of Cu. For the lowest cooling rate, 17 C" per min, the temperature of the specimen was measured with a Pt-Pt 10 pct Rh thermocouple placed in a & in. diam well in the center of the specimen. During air cooling, 375 C° per min, this method of measuring the temperature interfered with the operation of the dilatometer. However, it was found that the temperature of the specimen could be measured accurately by placing a thermocouple in an identical specimen in a holder adjacent to the one being used to operate the dilatometer mechanism. The dilation-temperature curves were recorded on photographic film and then converted to volume percent ferrite-vs-temper-ature curves. The cooling rates obtained with the dilatometer are shown in Table 11. Cooling rates of

Jan 1, 1970

By W. R. K. Wu

This Bureau of Mines report presents a statistical study of the repeat abilities of coal-plasticity parameters obtained in the tests with the Gieseler plastometer and the Audibert-Arnu and Hoffmann dilatometers. Repeatability is expressed in terms of one or two standard deviations for the differences between duplicates. The statistical method employed here is summarized. Results are tabulated for the temperature and nontemperature parameters of the three tests.

Jan 1, 1970

By R. T. O’Brien, J. M. W. Mackenzie

A microelectrophoresis technique has been used to measure the zeta potential of quartz over a range of pH and Ni (11) and Co (Ilj concentrations. Results have been discussed in terms of adsorption of Ni (11) and Co (11) cations and hydroxide precipitates. Possible relationships between the experimental results and the formation of lateritic nickel deposits have been discussed. The adsorption of metallic cations to the surface of silicate minerals is of significance in many industrial and natural processes. In an earlier publication,&apos; the adsorption of Fe (111) to the quartz surface, a phenomenon of importance in flotation, was studied qualitatively using microelectrophoresis techniques. This paper reports the extension of this work to an investigation of the adsorption from aqueous solution of Co (11) and Ni (11) to the quartz surface. The adsorption of these metals was of interest for two reasons; firstly, the importance of such an adsorption process in the formation of nickel deposits by the lateritization of nickeliferous rocks, and secondly, the comparison of electrophoresis data for these metals, whose hydroxides precipitate in the pH range 7-8, with similar data for Fe (111) where the hydroxide first precipitates at pH 2.8. The development of laterites is essentially a near-surface geological process involving vertical and, in part, horizontal redistribution of elements derived from rock-forming minerals. This redistribution of elements leads to the formation of layers within the lateritic profile which are enriched in one or more of these elements and, depending on the nature of the original rocks, continued lateritization may give rise to iron ores, bauxites or nickeliferous laterites. The mechanisms discussed in this paper deal with the last mentioned type of deposit although the considered factors are applicable to laterites in general. Nickeliferous laterites are derived from basic and ultrabasic rocks containing ferro-magnesian silicates. These rocks may be partly or wholly converted to serpentinites. Besides their high Mg, Si and Fe contents, they also contain small amounts of Mn, Al, Cr, Ni, Co, Cu and Zn. The nickel content is usually near to 0.2-0.3%, but for economic use this must be increased during lateritization to over 1% and preferably over 2%. The zone of nickel enrichment is usually at some depth within the lateritic profile. Unpublished work by Mr. O&apos;Brien on nickel-bearing laterites in eastern Australia indicated four visually different types of material which were separated from crushed samples under a stereo-microscope. Although chemical analyses indicated that all four types of fragments contained 2-4% nickel and smaller amounts of cobalt, X-ray diffraction and optical studies revealed only quartz, hematite and chromite as well as, in one of the types, a serpentine mineral. No distinct, nickeliferous minerals were detected. Furthermore, it was possible to extract some 60% of the nickel content of the laterites with cold 0.5N hydrochloric acid. It was therefore postulated that much of the contained nickel was present as amorphous, adsorbed material. In considering this fact, as well as the problem of the actual method of transfer and fixation of elements within the lateritic profile, it was further postulated that the transfer of these elements probably took place partly as solutions and partly as colloids and that the fixation of these was caused by adsorption and flocculation. The existence of nickel in solution in water draining from serpentinites has been confirmed by Smurov.2 Although we have no evidence for the transportation of nickel in the colloidal state, it is well accepted that colloids are important in the formation of laterites. Previous work by Mr. Mackenzie&apos; has already indicated that iron may be adsorbed on quartz under conditions which could be expected in a lateritic profile, but no information was available for nickel or cobalt. Although adsorption possibly also takes place on minerals other than quartz, the latter is significant because silica is an important constituent of the silicate parent rocks. During lateritization, it is released to form free quartz and it is likely that it is initially extremely fine-grained. This would provide abundant opportunities for adsorption and it was de-

Jan 1, 1970

By J. R. Johanson, A. W. Jenike

"A solid flows out of a bin provided that the outlet is sufficiently large so that stable obstructions to flow do not develop. The geometry and surface finish of a bin and the construction of the feeder determine the type of flow pattern which then develops within the bin. The pattern, in turn, affects the uniformity and consistency of the stream, segregation, caking, degradation, live capacity and the action of level measuring devices.In most bins now in operation, material flows toward the feeder through a channel which forms within the stationary solid. This is referred to as funnel flow. If the hopper of the bin is sufficiently steep and smooth and the feeder capable of drawing material across the whole area of the outlet, all the solid flows whenever the feeder is in operation; this is referred to as mass flow. Mass-flow bins are usually far superior to funnel-flow bins; their initial cost is also usually higher.The paper describes the design criteria used in deter-mining the minimum bin outlet needed for flow and the bin geometry needed for mass flow."

Jan 1, 1970

Copper ores are widespread through the Lachlan Geosyncline in New South Wales, but the size of the orebodies is generally small. The largest deposits occur in the Cobar district where an iron-rich copper ore type has been developed in Silurian sediments. Similar de- . posits to the south in the Nymagee-Mt. Hope-Melrose districts are related to quartz feldspar porphyries of probable Upper Silurian age. Deposits to the east in the Tottenham-Girilambone districts are less complex mineralogically and are possibly related to an ultra-basic source.Copper mineralization in the Highlands further to the east is often developed in Ordovician andesite or MiddleUpper Silurian acid volcanic sequences. The deposits in andesite contain considerably less galena than those in the acid extrusives; a small proportion of the mineralization in the latter has texture, mineralogy, and geologic setting analogous to the Captain&apos;s Flat copper-Iead-zinc deposit, for which both syngenetic and epigenetic origins have been proposed. Very little copper mineralization occurs within granitic material, even though rocks of this type ranging from Silurian to Carboniferous in age crop out through much of the geosyncline, and the extent of the metal contribution from plutons to the deposits in volcanics is open to question. Numerous deposits are known in the contact zone around Mid-Devonian and Mid-Carboniferous granites, however, and the formation of these orebodies has undoubtedly been influenced by plutonic activity. Small occurrences of copper with associated minor nickel sulphides are developed in a narrow serpentinite belt of possible Lower-Middle Devonian age in the southern section of the Highlands.

Jan 1, 1970

By Swan. J. D.

Repairing and replacing equipment damaged by corrosion and abrasion is a major cost throughout industry, especially in the coal mining industry. Careful study of corrosion and abrasion, and their causes and effects, often leads to the selection of alternative materials which can provide economies. What, actually, are corrosion and abrasion and how do they contribute to the cost of operating a coal-preparation plant? Furthermore, what can be done to alleviate corrosion and abrasion problems and thereby reduce operating costs? These questions will be answered in the following discussion, which will describe the destructive action of corrosion and abrasion and give several methods for controlling corrosion and abrasion losses, These methods include the substitution of stainless steel for carbon steel, the use of corrosion inhibitors, and the use of design to eliminate corrosion and abrasion. Examples will be given illustrating the benefits that have resulted in plant tests when these methods of controlling corrosion and abrasion were used.

Jan 1, 1970

By R. Cohen-Alloro

Classical apparatus for granulometric separation generally have limited applications which are found either in the level of the size of separation or in that of the accuracy and the efficiency of the separation or in that of the rate of feed. In industrial practice, the classification of the products of coarse dimensions generally poses no problems. On the contrary, the separation of fine particles presents some difficulties, however the apparatus is used (mechanical classifiers, curved screens and sieves, hydrocyclones, etc...). These difficulties are due to hprfections of separation, rather high cost prices, and sometimes large amounts of recycled materials.

Jan 1, 1970

By Arnulf Muan, Carlos Landolt

Equilibria involving Cu-Pt alloys, copper oxides, and atmospheres of known ox2gen pressures have been determined at 1000&apos; and 1200 C. The data obtained have been used to calculate activity-composition relations in the alloys. A moderate negative deviation from ideality is found. At high copper concentrations, the results of the present study are in good agreement with those of previous investigators, whereas at low copper concentrations the activities obtained in this investigation are slightly higher than those reported previously. The present study is part of a research program dealing with the determination of phase relations and thermodynamic properties of copper-containing systems at high temperatures. The information available for such systems is very scanty, particularly for copper oxides and their combinations with other oxide components. Platinum is commonly used as a container in studies of oxide equilibria. To evaluate quantitatively the extent of reaction between the oxide and the container, a knowledge of activity-composition relations in Cu-Pt alloys is necessary. Such data are not available for Cu-Pt alloys in the temperature range of particular interest in the present research program, and particularly for alloys low in copper. Studies of various aspects of the systems Cu-Pt and Cu-0 have been reported in previous literature. The system Cu-Pt is known1 to form a continuous solid-solution series above 812.C, whereas ordered phases are present in certain composition ranges at lower temperatures. Thermodynamic data for the system have been reviewed by Hultgren et al.,&apos; who presented free energies of mixing at 65Oo C, mainly derived from electromotive force cell measurements by Weibke and Matthes.3 Enthalpies of mixing at 640°C have been obtained by Oriani and Murphy4 with liquid tin calorime-try. Their results differ considerably from those derived from the temperature dependence of the data of Weibke and Matthes. Thermodynamic data for the disordered alloys have been obtained by Assayag,5 and more recently by Schmahl and Minzl,6 by Myles and Darby,7 and by McCormack, Myers, and Saxer.8 The two latter sets of data7&apos;&apos; became available after the present study was completed. In the system Cu-0+ two oxides are stable at high temperatures, CuO and CuzO+ each having only minor deviations from stoichiometry. Equilibria in the liquidus temperature region of the system Cu2O-CuO have been studied by Roberts and systemsmyth,9&apos;10CuzO-CuO by Vogel and ocher,I1 by Osterwald,12 and recently the the present authors.13 The system is of the eutectic type with a eutectic temperature of 1083.C The composition of the eutectic liquid corresponds to Xcu0 = °.44, and the oxygen pressure of the coexisting gas phase is Po2 = 0.55 atm.13 Equilibrium oxygen pressures for coexistence of solid CuO and solid Cu2O have been determined by Schmahl and Muller,l4 by Gadalla, Ford, and white,l5 by Bidwell,16 and recently by the present authors.13 There is reasonably good agreement among the various sets of data. Free energies of formation of Cu2O(s) from the elements have been derived by Tretyakov,17 by Bidwell,16 by Kiukkola and wagner,18 by Pal&apos;guev and Neuimin," and by Steele and Alcock,20 There is particularly good agreement among the latter three1&apos;-20 sets of data. THEORETICAL BASIS Consider a subsolidus isothermal section of the system Cu-Pt-0, as shown in Fig. 1. Two phase as-

Jan 1, 1970

By Manuel Gomez

This report presents prediction equations for 12 variables that are indicative of metallurgical coal quality. The variables include six for coke strength and six for carbonization product yields. All variables were predicted for coking coals having volatile matter contents from 16.3 to 42.1 percent, dry basis. The prediction equations, developed by mathematical-statistical techniques, were based on information from the proximate and ultimate analyses, the size consist, and the petrographic composition of bituminous coals carbonized in BM-AGA retorts at 800°, 900°, and 1,000° C. The equations were evaluated for validity with independent data derived from the 900° C carbonization of 33 binary blends of various coals and 22 binary blends of Pocahontas No. 3 low-volatile bituminous coal with 11 high-volatile bituminous coals. Results show that metallurgical coal quality can be predicted ahead of mining because data used to derive the prediction equations can be obtained at the time of exploration. Capability to forecast coal quality is useful in mine planning and should provide basic information for optimization of blending and crushing techniques and thus lead to the production of uniform coke.

Jan 1, 1970

By B. C. Allen

Surface free energy and surface self-diffusion of solid molybdenum were studied in the temperature range 1600" to 2400°C using pressure-sintered bi-crystals. Comparison of groove angles formed in various surfaces perpendicular to the grain boundary indicate a maximum of 1 pct variation in surface free energy with crystallographic mientation. This anisotropy tends to decrease with increasing temperature. The surface diffusion of the bicrystals is equivalent to that of sheet with a mild (100) Preferred orientation. Anomalously low values found for bi-crystals with surface orientations of (OOl), (012), and (011) are rationalized in terms of anisotropy in surface free energy. THE effect of crystallographic orientation on surface free energy1,&apos; and surface self-diffusion3,4 has been primarily studied in fcc metals. The object of this work was to study the effect of orientation on surface diffusion and surface free energy of bcc molybdenum using pressure-sintered bicrystals. EXPERIMENTAL WORK Materials and Crystal Preparation. Arc-melted molybdenum rod was obtained commercially and electron beam zone refined at 50 cm per hr at 10- 5 torr to form single crystals about 8 cm long and 0.65 cm diam. Three crystals were prepared with axial orientations about 1 deg from [001.], [011], and. [111]. To reduce the carbon content, the crystals were annealed 2 hr in 1.4 atm flowing wet hydrogen at 2050°C. Then the oxygen content was reduced by annealing for 2 hr in -30°C dewpoint hydrogen at 2020°C. The resulting impurity analysis is given in Table I. Bicrystal Preparation. The single crystal rods were cut into transverse slices with a thin silicon carbide abrasive wheel to produce specimens about 0.6 cm long. They were mounted in epoxy and surrounded by stainless steel washers. Cutting in half was done longitudinally at various angles to known crystallographic planes containing the cylinder axis according to Fig. 1. To reduce surface deformation resulting from the cutoff wheel and thus reduce parasitic grain boundary formation on subsequent annealing, about 0.003 cm was manually ground off each cut surface with 600 grit paper. Care was taken to keep the surface flat. After removal from the mounts, one half was generally ro-tated 180 deg with respect to the other to give a po- tential symmetrical tilt grain boundary between the two halves. In the other cases when low misorienta-tion angles were desired, the crystals were not rotated. On the basis of symmetry, sufficient bicrystals were prepared to cover the entire range of misorientations for symmetrical tilt boundaries. The misorientations, +, ranged from 0 to 45, 0 to 90, and 0 to 60 deg for [001], [011], and [111] bicrystals, respectively. One [Ill] twist bicrystal was prepared from 2 single crystal discs rotated 17 deg relative to each other. Each specimen consisted of two pieces which were placed in a cylindrical tantalum can. Sharp edges were rounded and the fit was made as snug as possible to reduce subsequent deformation during bonding. The assembly and crystals generally were vicuum outgassed at 900" or 1700°C and then electron beam welded in the can at l x 10-4 torr. After being leak checked, the samples were placed in an autoclave and hydrostatically gas-pressure bonded5 in four batches under helium at 10,000 to 18,000 psi at 1650°C for 3 hr. Satisfactory bonds were obtained in many cases, and most of the crystals bonded after two exposures. The results did not appear to be affected by the various pressures used, preannealing conditions, crystal orientation, or time-pressure-temperature route taken to the final bonding condition. After bonding, the tantalum cans were selectively removed in cold concentrated HF. Measurements indicated overall deformation was under 1 pct. The bicrystals were metallographically ground and polished flat and perpendicular to the axis. Examination showed the boundaries were straight and almost free of parasitic grains caused by extraneous local deformation. Annealing. In preparation for thermal grooving, the bicrystals were cleaned and annealed by outgassing at 10-5 torr at 1900°C and heating at 2300°C under 1 atm 99.996 Ar for 0.5 hr. The crystals were held in a closed 4-deck box made of molybdenum sheet, and were heated in a Ta-1OW resistance furnace. The ar-

Jan 1, 1970

By B. C. Allen

Grain boundary grooving has been studied in chromium, molybdenum, and tungsten under a variety of conditions using high vacuum techniques and tantalum -gettered argon. The average surface free energy of solid chromium, and the chromium-liquid silver interface free energy were respectively found to be 2200 ± 250 and 500 i 130 ergs per sq cm from groove formation kinetics and estimates of pertinent volume difffusion coefficients. The results for chromium were unffected by variations in interstitial content ranging from 0.003 to 0.09 pct C, or 0.003 to 0.03 pct O. Surface diffusion is the primary mechanism of groove formation in chromium under 1 atm argon at 1200" to 140O°C, and is essentially unaffected by 0.003 to 0.09 pct C, 0.003 to 0.03 pct O , metastable nitrogen contents up to -0.01 pct, and up to 2 torr Ag vapor. At higher temperatures, the major mechanism is volume diffusion in argon or evaporation-condensation in stutic vacuum. Surface diffusion occurs in molybdenum at 0.5 to 0.96 and in tungsten at 0.5 to 0.9 of the absolute melting tempera -ture by a single mechanism, possibly by the migration of single adatoms or vacancies. Results were slightly affected by up to 23 tory Sn vapor, and in molybdenum were essentially unaffected by 0.5 Ti or carbon in the range 0.002 to 0.02 pct. Volume difffusion through the liquid is the mechanism of groove formation in chromium-liquid silver at 1200" to 1400°C and in molybdenum-, Mo-0.5Ti-, and tungsten-liquid tin at 1200" to 2000°C. The solid-liquid interface free energies involved were estimated from grooving kanetics. WHEN a grain boundary intersects a solid surface, a groove tends to form along the line of intersection at temperatures above about half the absolute melting point (0.5 TM). The groove progressively grows by preferential atomic migration either by diffusion or evaporation. Establishment of a groove angle occurs in accordance with the grain boundary and surface free energies involved. The motivation for groove formation is a reduction in the total surface free energy of the system. This study is a continuation of previous work on thermal grooving of chromium, molybdenum, and tungsten.&apos; The temperature ranges were extended, and the effect of metallic and interstitial impurities was evaluated. The results were such that certain interface free energies and surface self-diffusion coefficients were deduced from the grooving kinetics. EXPERIMENTAL WORK Materials and Preparation. As indicated in Table I, the 0.05-0.08-cm-thick chromium, molybdenum, and tungsten sheet used was nominally 99.99 pct after recrystallization. Two lots of molybdenum with about the same analysis, Mo-0.5Ti,* and tungsten were ob- *Alloy compsitions are expressed in weight percent . tained commercially. Extruded chromium rod,&apos; prepared from iodide process crystals, was warm rolled to sheet at 700°C. Sheet of three Cr-0 impurity alloys containing up to 0.03 pct 0 was prepared by warm rolling arc melted, extruded, and swaged rod. Two Cr-C impurity alloys containing up to 0.09 pct C were made by equilibrating unalloyed chromium with a known amount of CH4 for 24 hr at 1150°C in previously evacuated quartz capsules. Chromium containing nominally 0.015 and 0.06 pct N was similarly prepared by equilibration with NH3. The sheet was recrystallized to give a stable grain size about equal to the sheet thickness. Molybdenum and Mo-O.5Ti were recrystallized in a tantalum resistance furnace 1 hr at 1 x lo-5 torr at 2300" and 220O°C, respectively. Tungsten was similarly annealed for 1 hr at 2500°C. Chromium and its impurity alloys were outgassed at 1100°C and recrystallized 1 hr at 1700°C under 1 atm Ar. Except for nitrogen, the impurity content stayed roughly constant. Nitrogen in both alloys was reduced to <0.001 pct. In fact, over 80 pct of the added nitrogen was lost after outgassing at llOO°C and annealing sheet 1 hr at 1300°C in argon in the presence of tantalum. Such a rapid loss can be rationalized since -2 torr N are required for equilibrium with 0.04 pct N in solution,3 while the equilibrium pressure is ~10-5 torr over tantalum at 1300°C.4 The recrystallized sheet was cut into small coupons which were metallographically ground and polished on one side with a minimum of grain boundary relief. The surface roughness was on the order of 0.01 µ. The tin and silver used were nominally 99.999 spec-trographically pure. After being outgassed at 1100°C and equilibrated in a molybdenum crucible for 0.5 hr at 1800°C in argon, the tin contained 3 ppm 0, <0.3 ppm N, and 0.1 ppm H. Following outgassing at 900°C and equilibration in a chromium crucible 1 hr at 1400°C in argon, the gas content of the silver was 1 ppm O, <0.5 ppm N, and 0.3 ppm H. Grooving Under Argon or Vacuum. All specimens were placed in unsealed containers made from rod or sheet of the same alloy, thereby enabling the polished surface to achieve gas-solid equilibrium. The annealing fixtures are shown in Fig. 1. The specimen was placed in a resistance furnace with a tantalum or Ta-10W heating element plus tantalum fixtures or radiation shields. Chromium was outgassed at 1100°C, and molybdenum and tungsten were outgassed at 1900°C to 1 x l0-5 torr or at the grooving temperature, whichever was lower. In vacuum anneals, the specimen was then heated directly to the intended grooving temperature. In argon anneals, 99.996 Ar was admitted

Jan 1, 1970

Analyses of scheelite from all the known scheelite fields in the South Island of New Zealand have shown that the scheelites are essentially molybdenum-free. The scheelites are almost stoichiometric CaWO4, except for some strontium replacing the calcium, with a maximum of 0&#183;92 per cent SrO. Variation in strontium content appears to be&apos; related to the metamorphic grade of the enclosing rocks.

Jan 1, 1970

By Morris A. Dodd

The nodulizing process described converts finely divided zinc calcine into a dense purified nodule. These zinc nodules are suitable for direct use in zinc reduction furnaces, especially the horizontal retort type, for the production of metal or American process zinc oxide furnaces for producing lead free zinc oxide. The basic reactions are carried out in a rotary kiln fired with fuel oil or natural gas. The combustion gases travel countercurrent to the flow of the zinc bearing material. Volatile impurities are carried out of the kiln with the combustion gases and a small portion of the finely divided feed material. The gases are cooled and the larger solid particles are separated from the stream before the resultant fume is collected in a conventional cloth filter baghouse. The fume collected can be further processed by conventional wet processes for the recovery of metallic values such as lead and cadmium. In order to nodulize the calcine properly it is elevated to a point of incipient fusion. The agglomerated material falling from the kiln is cooled and then sized by passing through a screening and crushing system consisting of a jaw crusher and a roll crusher in closed circuit with a vibrating screen.

Jan 1, 1970

By S. F. Radtke

The properties and characteristics of lead and zinc have made these metals useful to man in many ways since the days of antiquity. Despite their long history of use, however, these metals have proved to be extremely resilient and responsive to modern needs. New alloys and compounds continue to be developed, adding to the growth of these metals. Consumption data is given for 1969 and compared with one and two decades ago. Trends in major markets also are cited and explained. Uses for lead and zinc which have come into prominence within the past few years are described and explained, with emphasis on the role played by the industry&apos;s cooperative research program. Current efforts in the research phase are discussed, with details given on major efforts for both metals, including new alloys, process developments, applications research, finishes, coating, paints and pigments, batteries and fundamental research. A forecast is given of promising new areas and a projection made on a longer term of new applications that may emerge from current research.

Jan 1, 1970

By V. L. Brant

The estimated total energy demand for the U. S. is 60 quadrillion BTU for 1970 and is expected to more than double by the year 2000. Today the energy crunch is here. It is evidenced by brownouts to conserve electrical energy, and the shortage of gas and oil. Many such headlines, including suggestions for energy rationing, are in the news today. Paradoxically we have an abun¬dant source of energy in the form of coal. Energy consumers, however, are geared to use fuel in other forms. It is the intent of this presentation to discuss processes under development for conversion of the energy contained in these vast coal reserves to more usable forms. Coal conversion to synthetic fuels should be of particular interest to those engaged in mining. Coal consumption in a single conversion plant is expected to range from 10,000 to 40,000 tons per day. Plants will be located at the mine mouth and will operate continuously 24 hours per day, seven days per week. Further, many such plants will be needed., For example, looking at natural gas only, the supply/demand gap is estimated to reach 13 trillion cubic feet per year by 1985. Assuming that gas from coal conversion were to fill only 101, of this gap, 15 plants producing 250 MMSCFD would be required. These plants would consume about 90 million T/Y of coal or 135 million T/Y of lignite. It will indeed be a challenge to mine, suitably prepare, and transport coal at these projected volumes without interruption. Many ideas have been conceived for better utilization of coal and these are in various stages of development. Those supported by public money are covered by the Annual Report of the Office of Coal Research (OCR), Department of Interior. The two processes to be discussed, the Consolidation Coal Company&apos;s (Consol) C02 Acceptor Process (1)(2)(3) and The Pittsburg and Midway Coal Mining Company&apos;s (PAMCO) Solvent Refined Coal Process (4)(5) are both sponsored by OCR.

Jan 1, 1970