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By T. G. Digges, M. R. Achter

ALTHOUGH zone melting has found favor in recent years because of its convenience and its faster rate of production of single crystals, the older technique of strain annealing still has a number of advantages. It has been reported1 that the lattice of a crystal prepared in this manner has fewer defects than one grown from the melt and, of course, the control of the external geometry is easier. Also, the diameter of the crystal which can be grown by zone melting has a theoretical limit determined by the surface tension, thermal conductivity, and specific gravity of the material, while the size of that which can be grown in the solid state is limited only by practical considerations. In a program for the study of the structure-sensitive properties of niobium and its alloys it was desirable, for ease of handling, to have available single crystals of large diameter. This requirement dictated the choice of the strain-anneal technique. Induction heating was chosen in the present work in preference to other methods because of its deep penetration of large-diameter sections. A five-turn coil, powered by a motor generator operating at 10,000 cps, is contained in a vacuum chamber. The work is lowered through the coil for both the recrystallization and the crystal-growth steps. Starting with electron-beam melted material, the bars are cold-swaged, recrystallized, strained in a tensile machine, and then subjected to the growth step. Single crystals have been grown under the following conditions: Reduction in area during swaging— 79 to 99 pct, recrystallization temperature—1500o to 1667°C at the rate of 1.25 in. per hr, strain—1.0 to 2.5 pct, growth temperature—1600o to 2400°C at rates from 0.15 to 1.25 in. per hr. Starting grain sizes achieved after the recrystallization step varied from 0.6 to 1.55 mm. The starting grain size was found to be critical; if it is too fine and has any residual cold work, as shown by the presence of a fiberlike texture, a single crystal cannot be grown. Using this technique niobium single crystals have been grown from 0.250 in. diameter and 12 in. long to 1.00 in. diameter and 5 in. long as shown in Fig. 1. The 1-in. crystal is the largest to be reported for a refractory metal as compared to 0.500 in. for molybdenum grown by zone melting.2 As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and Smallman,3 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point ahead of the interface between the single and polycrystalline portions. Finally, it is returned to the chamber and growth is continued "around the corner". The amount of bending which can be imparted to the rod is limited by coil geometry which up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. The perfection of these single-crystal specimens as a function of process variables is being measured by X-ray and metallographic techniques and the results will be reported in a forthcoming paper. This work was partially supported by the Advanced Research Projects Agency.

Jan 1, 1964

By Jean Howard

ALTHOUGH zone melting has found favor in recent years because of its convenience and its faster rate of production of single crystals, the older technique of strain annealing still has a number of advantages. It has been reported1 that the lattice of a crystal prepared in this manner has fewer defects than one grown from the melt and, of course, the control of the external geometry is easier. Also, the diameter of the crystal which can be grown by zone melting has a theoretical limit determined by the surface tension, thermal conductivity, and specific gravity of the material, while the size of that which can be grown in the solid state is limited only by practical considerations. In a program for the study of the structure-sensitive properties of niobium and its alloys it was desirable, for ease of handling, to have available single crystals of large diameter. This requirement dictated the choice of the strain-anneal technique. Induction heating was chosen in the present work in preference to other methods because of its deep penetration of large-diameter sections. A five-turn coil, powered by a motor generator operating at 10,000 cps, is contained in a vacuum chamber. The work is lowered through the coil for both the recrystallization and the crystal-growth steps. Starting with electron-beam melted material, the bars are cold-swaged, recrystallized, strained in a tensile machine, and then subjected to the growth step. Single crystals have been grown under the following conditions: Reduction in area during swaging— 79 to 99 pct, recrystallization temperature—1500o to 1667°C at the rate of 1.25 in. per hr, strain—1.0 to 2.5 pct, growth temperature—1600o to 2400°C at rates from 0.15 to 1.25 in. per hr. Starting grain sizes achieved after the recrystallization step varied from 0.6 to 1.55 mm. The starting grain size was found to be critical; if it is too fine and has any residual cold work, as shown by the presence of a fiberlike texture, a single crystal cannot be grown. Using this technique niobium single crystals have been grown from 0.250 in. diameter and 12 in. long to 1.00 in. diameter and 5 in. long as shown in Fig. 1. The 1-in. crystal is the largest to be reported for a refractory metal as compared to 0.500 in. for molybdenum grown by zone melting.2 As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and Smallman,3 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point ahead of the interface between the single and polycrystalline portions. Finally, it is returned to the chamber and growth is continued "around the corner". The amount of bending which can be imparted to the rod is limited by coil geometry which up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. The perfection of these single-crystal specimens as a function of process variables is being measured by X-ray and metallographic techniques and the results will be reported in a forthcoming paper. This work was partially supported by the Advanced Research Projects Agency.

Jan 1, 1964

By James Kemp

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

Jan 7, 1915

V. H. GOTTSCHALK, Rolla, Mo. (written discussion*).-In connection with Mr. Waring's quotation of Urbain's work, attention may be drawn to a remark found in the report of the session of the Société de Chimie Physique,1 held in December, 1909, that, while all blendes contain gallium in larger or smaller quantities, those blendes carrying indium are generally free from germanium, and vice versa. Urbain, furthermore, . expresses his conviction that this behavior, being related to the condi-tions of deposition of the ore, should be an important factor in determining the origin and mode of formation of zinc blende deposits., In. searching the literature for the naturally expected sequel to these remarks, there is found a report on the extraction of germanium from blende, after many months' work, on a commercial scale;2 then a paper3 on some Spanish blendes, all containing cadmium, examined by Urbain's 'method (this paper contains, also, very important work on the com-position and color of blendes, as well as on the occurrence of organic .matter and of inclusions in such blendes), and a second paper on Spanish blendes in general, in which this original point of Urbain's concerning the relative quantities of the three rare elements is taken up.4 Angel del Campo finds that of 68 specimens examined, four only were entirely free of germanium, gallium, and indium;. 38 had small proportions, while 19 were notably, and seven relatively rich in the three rare metals. He found the relative frequency to be: gallium in 60, germanium in, 50, and indium in 38; all three occurred in 29 cases; germanium and gallium together in 18; gallium and indium together in four; germanium and indium together without gallium, in none; four had gallium only, three had germanium only, and one had indium only; in 23 it appeared feasible to extract these elements. Finally, it may be worth mentioning that the discovery of gallium in commercial aluminum5 brought forth two

Jan 1, 1918

By D. F. Atkins, B. A. Rogers

The constitutional diagram presented herein is relatively simple. Complete mutual solid solubility exists for an interval below the solidus line, a continuous curve with a flat minimum near 22 pct Cb and 1740°C. Upon cooling, the solid solution breaks up, except at the columbium-rich side, from two causes: zirconium-rich alloys transform under the influence of the ß-a transformation in zirconium; alloys of intermediate composition decompose into two solid solutions below 1000°C. The combined effect is the formation of a eutectoid at a temperature of 610°C and a composition of 17.5 pct Cb. The eutectoid horizontal extends from 6.5 to 87.0 pct Cb. Some age hardening effects have been observed in the zirconium-rich alloys but the positions of the solvus lines remain uncertain. IN recent years, zirconium has been produced in much larger quantities than were available previously. Correspondingly, the incentive for studying its alloy systems has increased, as the number of recent publications on alloy systems testifies. However, only a partial diagram of the Zr-Cb system has been published and relatively few references have been made to alloys of the two metals. Hodge' investigated the Zr-Cb system up to about 25 pct Cb. His data on melting points were not sufficiently numerous to distinguish with certainty between the alternatives of a narrow eutec-tic horizontal and a wide flat minimum in the solidus curve. Although Hodge considered his results on transformations in the solid state to be only tentative, he suggested that the eutectoid in the zirconium-rich alloys lay at about 625 °C and 10 pct Cb and estimated that the solubility of colum-bium in zirconium at 625 °C was near 6 pct. According to Simcoe and Mudge,2 less than 0.5 pct Cb is soluble in zirconium at 800°C. These authors observed an increased strength in both the 0.5 and I pct Cb alloys made with hafnium-containing zirconium. According to Keeler,3 the strength of zirconium is increased by addition of columbium to a content of at least 3 pct. Keeler' also observed a maximum in hardness at about 10 atomic pct Cb and commented on the brittleness of alloys of this composition. Anderson, Hayes, Rober-son, and Kroll5 investigated the tensile properties of Zr-Cb alloys containing 5.1 and 12.9 pct Cb at room temperature and at 343°C. The 12.9 pct alloy had a high tensile strength at room temperature but also a low percentage of elongation. All alloys had high elongation at 343 °C. Littona measured strength and elongation values of annealed alloys containing up to 27.5 pct Cb and found low elongation values for all of the alloys of high columbium content. Some observations on the resistance of Zr-Cb alloys to corrosion in water at high temperature have been published by Lustman, De Paul, Glatter, and Thomas' who found that additions of columbium up to 1 pct had only a minor effect on the corrosion resistance of zirconium. Preparation of the Alloys Raw Material: Zirconium of a relatively good grade was available for making the alloys. It was obtained as scrap pieces that had been left over from an operation that included production by the iodide process, melting under a protecting atmosphere, and fabrication to plates. The individual pieces had hardness values of 24 to 32 Ra and a typical analysis is shown in Table I. The columbium also was scrap trimmed from sheets. It was furnished by the Fansteel Metallurgical Corp. and had a high ductility but its analysis was known only approximately. The metal probably contained about 0.5 pct Ta, perhaps 0.25 pct C, and a few hundredths percent each of iron, silicon, and titanium. Melting: The alloys were melted in a tungsten-electrode copper-crucible arc furnace similar to units that have been described recently in the metallurgical journals.'.' The crucible of this furnace is provided with a cavity in which a getter charge can be melted before the melting of the alloy charges. Hardness measurements on the ingots indicate that the getter charge takes up a considerable fraction of the oxygen and nitrogen from the helium atmosphere of the furnace. The alloys used in the investigation are given with their intended compositions, hardness, and melting points in Table 11. Fabrication: All alloys of the Zr-Cb system appear to be amenable to fabrication. At least, all of the compositions listed in Table II could be reduced to wires in a rotary swaging machine. The starting material was either slabs cut from ingots and ground by hand to rough cylinders or narrow strips trimmed from sheets made by cold rolling slabs. However, not all of the alloys could be fabricated satisfactorily by the same method. From 0 to 4 pct Cb and from 20 to 30 pct Cb or more, the alloys could be swaged cold from ¼ in. cylinders to 0.80 mm wires with only one intermediate annealing, sometimes with none. From 40 to 90 pct Cb, the alloys were difficult to swage either hot or cold but could

Jan 1, 1956

By E. Klar, A. B. Michael

Differences in the electrical conductivities of copper powder sintered under reducing, selectively oxidizing, and neutral atmospheres are related to impurities in solution or as precipitated oxides. The precipitation of impurities as oxides during sintering in nitrogen is proposed for maximizing the conductivity of sintered copper. Conductivity equations for two-phase systems are summarized. Selected equations are applied to porous sintered copper and composite structures. A recent review of the influence of impurities on the electrical conductivity of copper by Gregory et al.1 emphasized that an impurity in solid solution has a much more pronounced effect on reducing the electrical conductivity than when present partly or wholly as a second phase. When impurities in solid solution can be precipitated as oxides, the copper is purified with respect to these elements and the conductivity is increased. Cast and wrought copper, therefore, frequently contain an intentional residual oxygen concentration to oxidize and precipitate impurities less noble than copper. Copper powders generally also contain impurities which can contribute to a reduction in the electrical conductivity of the sintered material. The most deleterious impurities commonly found in commercial copper powders which markedly decrease the electrical conductivity when in solid solution but which can be precipitated as oxides include iron, tin, antimony, arsenic, cobalt, and nickel. In addition to impurities, porosity in sintered copper also contributes to a reduction in the electrical conductivity. The work reported herein discusses the influence of impurities, sintering atmospheres, and porosity on the electrical conductivity of sintered copper. These are important factors for controlling the electrical conductivity of materials such as sintered copper electrical contacts. Several publications on the electrical conductivity of sintered copper and composite materials with random pores or obstacles have incorrectly considered the conductivity to be proportional to the volume fraction of conducting material. However, analyses and equations have been proposed, the earliest of which is perhaps Lord Raleigh's of 1892,' which more accurately describe the conductivity of two-phase systems. These equations which in many cases allow one to closely estimate the electrical conductivity of porous sintered materials and two-phase composites will be reviewed and related to the measured electrical conductivity of sintered copper, copper-graphite. and Ag-W composites. INFLUENCE OF IMPURITIES AND OXIDIZING, REDUCING, AND NEUTRAL ATMOSPHERES Zone-Melted and Leveled Copper. The electrical conductivities of an electrolytic copper and a lower-purity compacting grade of copper powder after consecutive treatments in reducing or selectively oxidizing atmospheres are compared in Fig. 1. The powder and drillings from the electrolytic copper ingot were melted and solidified in a graphite crucible under hydrogen. The vertical zone leveling technique of multiple passes in opposite directions was used to obtain a uniform distribution of impurities. The electrical conductivity was measured on machined specimens 3 by 0.10 in. diam of the zone-leveled material and after the same specimens were consecutively treated as follows: 1) heating in hydrogen at 1600°F for 3 hr; 2) heating in air in a sealed tube so that 0.04 pct 0 was introduced; heating was started at 1000°F for 1 hr and continued at 1800°F for 8 hr; the stepwise diffusion treatment was used to avoid loss of copper due to evaporation of copper oxide at higher temperatures; and 3) final heating in hydrogen at 1600°F for 3 hr. A L&N Kelvin Bridge, type 4306, and a test fixture with knife edges 2 in. apart were used to measure the room-temperature conductivity with an estimated accuracy of ±0.5 pct. In all cases the conductivity of the electrolytic copper was approximately 100 pct of IACS. The conductivity of the impure copper was 80 pct of IACS both in the cast state and after heating in hydrogen. However, after the heating in air, the conductivity of the impure material was 100 pct IACS. After again heating in hydrogen, the electrical conductivity decreased to 60 pct of IACS. This decrease is attributed both to the dissolution of impurities and observed intergranular cracks due to the phenomenon of hydrogen embrittle-ment in copper. These data show that the electrical conductivity of commercial copper as represented by a compacting type powder can be increased significantly by the precipitation of impurities as oxides through heat treatment in an oxidizing atmosphere. Sintered Copper Powder. A commercial compacting type of copper powder pressed to various densities was sintered either in nitrogen, dissociated ammonia, or dissociated ammonia followed by a selectively oxidizing atmosphere of air in sealed Vycor tubes so that 0.06 pct O was added to the material. The electrical conductivity was measured perpendicular to the pressing direction on as-sintered specimens of approximately 3 by 0.25 by 0.15 in. The fully dense material was obtained by zone melting and leveling

Jan 1, 1969

By W. A. Selvig

BY plotting fixed carbon against British thermal units of coals free from mineral matter, and ranging in rank from anthracite to lignite, it is found that the coals of higher rank, from anthracite to the higher rank of the high-volatile bituminous coals, inclusive, can be separated into groups according to their degree of metamorphism by reference to their fixed carbon. Such charts show also that the coals lower in rank can be best separated into groups with respect to B.t.u., especially when plotted on the moist basis, that is, coal containing its natural bed moisture. A tentative scheme for coal classification was presented at the October, 1932, meeting of the Technical Committee on Scientific Classification, of the American Standards Association Sectional Com-mittee on Coal Classification. This scheme was sponsored by Sub-committee IV on Tentative Classification of Coals, under the chairmanship of W. T. Thom, Jr. It proposed the grouping of coals according to rank by reference to fixed carbon and B.t.u., on the basis of coal containing its natural bed moisture but free from mineral matter. This scheme proposed classifying coals into four broad classes: (1) anthracitic, (2) bituminous, (3) subbituminous, (4) lignitic.. The anthracitic class was divided into three groups designated as meta-anthracite, normal anthracite, and semianthracite. The bituminous class also was divided into three groups, low volatile, medium volatile, and high volatile. The high-volatile group was further subdivided into four subgroups according to moisture content, as follows: (1) less than 5 per cent, (2) 5 to 10 per cent, (3) 10 to 15 per cent, and (4) 15 per cent and more. The subbituminous class was divided into two groups, group, 1 including subbituminous coals having calorific values of 10,500 B.t.u. or more, and group 2 including those with less than 10,500 B.t.u. , The lignitic class of coal was divided into two groups both below 8,000.B.t.u., the one group consisting of consolidated and the other of unconsolidated

Jan 1, 1934

By M. G. Corson

THE theory of hardening by interference with slip which has been so clearly developed by Jeffries and his co-workers requires that an alloy to be amenable to age or heat hardening should contain among its components some that will stay in solid solution at high temperatures and precipitate as a secondary phase on cooling. This secondary phase may be either a more or less pure individual element (chromium in the case of copper, anti-mony in the case of lead), or some intermetallic com-pound. Those cases of hardening which depend on the precipitation of a compound are not only the most frequent, but are also far superior in the efficiency of hardening obtained. However, the slip interference theory as stated in its most general form is not sufficient to foretell new cases of this type of hardening and also will not explain some phenomena of a more intricate nature. It is not sufficient that a secondary phase might be absorbed by the main one at high temperatures and precipitated at the lower ones. The kinetics of this precipitation and the accompanying. physical phenomena of dimensional changes play independent and highly important parts. These kinetics, while not yet sufficiently studied to he formulated in the shape of physicochemical equations, might find their expression-in a qualitative systema-tization of the phenomena of precipitation according to two different viewpoints. To begin with, we encounter the question as to the velocities of the precipitation and of the growth of the phase precipitated. To harden a metal in an efficient manner we must be able to control the precipitation on one hand and also to bring the total of the secondary phase to such a number and size of the particles pre-cipitated as, will produce a desirable hardening effect under commercially feasible conditions of. age or heat hardening. From this viewpoint six different cases may be dis-cerned.

Jan 7, 1928

By John Henderson

Densities of melts 0f the lime-iron oxide-silica system in contact with solid iron have been measured by the maximum bubble pressure method in the temperature range 1250° to 1440°C and the composition range 0 to 40 mol pct lime, 15 to 100 mol pct iron oxide, and 0 to 55 mol pct silica. Densities range from 4.65 g cm 3 for wustite at 1440°C to 2.75 g cm-&apos; at 1350°C for a melt containing 30 mol pct lime, 20 mol pct iron oxide, and 50 mol pct silica. The results are interpreted in terms of a postulate that the melts can be regarded as a random array of oxygen ions in which regions of local order exist to satisfy the coordination requirements 0.f the cations. An understanding of the nature of metallurgical slags is basic to the development of a sound theoretical description of heavy metallurgical extractive and refining processes. Because these liquids are complex, direct measurements of their properties has not thrown much light on their structure. This has led to the approach of measuring the properties of simpler liquids, and building up their complexity until slag compositions are reached. In this way the density of liquid iron silicates was measured in a previous study1 and the present work represents a further stage in this synthesis. EXPERIMENTAL The technique used in the measurement of density was the maximum bubble pressure method. Details of the apparatus and procedure were similar to those previously reported,&apos; with the exception that a constant voltage transformer was used to supply the power input to the furnace and six silicon carbide resistance elements were used in place of the molybdenum winding. With these modifications melt temperature could be maintained within 1 centigrade degree during the course of a run. The silica used to prepare the melts was washed natural quartz ignited at 1000°C; wustite was prepared by air-melting A.R. grade ferric oxide in an iron crucible and lime was prepared by air ignition, at 1000°C, of weighed quantities of A.R. grade calcium carbonate, previously air-dried at 110°C. The finely ground constituents were intimately mixed in a glass ball mill prior to melting. Temperatures quoted are accurate to * 5°C and the standard deviation of the density values, calculated by the method of least squares, ranged from 0.5 to 1.8 pet. However, replicate determinations of density on different melts of the same nominal composition at the same nominal temperature did not vary by more than 1 pct, Table I, and this figure has been taken as an estimate of the accuracy of the density results. The density of carbon tetra-chloride was also measured as a check on the absolute performance of the experimental method. At 20°C a value of 1.593 * 0.002 g cm"3 was obtained; this compares with the literature value2 of 1.595 g cm"3. Results of experiments designed to measure the dependence of the density of lime-iron oxide-silica melts, in contact with solid iron, on composition and temperature are shown in Table I. Because iron sometimes precipitated in the sample during quenching, the Fe203 chemical analyses were only poorly reproducible and should be taken as a guide rather than as absolute values. Fig. 1 shows the data from various sources for the density of liquid iron silicates and Fig. 2 shows isodensity contours at 1410°C for lime-iron oxide-silica melts, calculated by graphical interpolation of smoothed curves drawn through the experimental results, together with the 1400°C results of Adachi and ogino3 and Pope1 and Esin.4 Fig. 3 shows the isothermal variation with composition of the volume of melt per gram ion of oxygen at 1410°C and Fig. 4 shows regions in which the temperature coefficient of this volume is negative, positive, or negligible (<0.005 cm3 deg-I). DISCUSSION a) Disparity Between Reported Density Results. Consider the system iron oxide-silica, the results for which are summarized in Fig. 1. Although there is some difference in the temperatures at which the various densities apply, this difference is not sufficiently large to account for the observed discrepancies. The reliability of the present results for the low-silica region has been confirmed by measurement of the density of liquid wustite by three different techniques. At 1410°C the density measured by a balanced-column method was 4.55 g cm"3, by a combination balanced-column and gas-densitometer method 4.59 g emd3, and by a pycnometer method 4.53 g cm"3. Schenck, Frohberg, and Hoffermann&apos; have also reported a value of 4.55 g cm"3 for the density of liquid wustite at 1400°C. It must be concluded, therefore, that neither Pope1

Jan 1, 1964

By D. L. Harris, A. M. Gaudin

Observations were made of the distribution of mercaptan containing S35 between aqueous solution and mineral and between aqueous solution and the gaseous phase. Although equilibrium may not have been attained, adsorption of the reagent was shown to occur reasily from air or aqueous solution on sphalerite, zincite, and willem-ite and to correspond to flotation. Adsorption on quartz did not similarly occur. THE following results, presented here in condensed form,&apos; were obtained in a preliminary study of the adsorption of n-hexane thiol, hexyl mercaptan, on sphalerite, zincite, willemite, and quartz, from aqueous solution and from a gas. Interest in this subject was aroused by a Belgian report&apos; of effective use of hexyl mercaptan for flotation collection of oxidized zinc minerals. The relatively low boiling point, 149°C, of the mercaptan3 suggested the desirability of extending the usual measurements of partition of collector between aqueous solution and gas and between gas and mineral. It is believed that this paper presents the first measurements of this type on a flotation system. Attempts were made to carry out the measurements at equilibrium, but as the work progressed it became increasingly doubtful that this desirable condition had been achieved. To control composition and extent of the gas phase, the apparatus was a wholly-enclosed thermally-controlled glass system. Because of these constraints and the desirability of dealing with pure minerals, a scale of operations was chosen in which a few grams of deslimed mineral were used in each test. It was also necessary to choose a particularly sensitive method for mercaptan analysis, and in fact a method that would permit the experimenters to follow the approach to equilibrium. For these reasons mercaptan marked by radiosulphur 35 was used. An analysis was made for the radiosulphur by a modification of the method of Gaudin and Carr. Coarsely-crystallized sphalerite was handpicked, stage-crushed in the dry state, wet-screened on a 200-mesh sieve, and deslimed in water at about 5 microns. Further treatment consisted of a wash in dilute aqueous hydrogen peroxide, drying, removal of the dark-colored fraction in a Frantz magnetic separator, washing in very dilute hydrochloric acid, repeated washing in distilled and conductivity water, and drying. The last washings showed a conductivity equivalent to a few ppm NaC1, that is, much more than would be provided, theoretically, by a saturated ZnS solution. The material was stored dry in sealed bottles. Analyses were as follows: Zn, 62.3 pct; Fe, 0.43 pct; Cd, 0.44 pct; S, 31.2 pct; Mn, 0.001 pct. The specific surface (BET method) was 2000 cm2/g. Zincite from Franklin furnace of the New Jersey Zinc Co. was hand-picked, dry-crushed, wet-screened at 100 mesh, and deslimed at about 10 microns. After drying, the associated zinc, manganese, calcium, and silicate minerals were removed in a Frantz magnetic separator. The purified zincite was washed in distilled water and conductivity water to a conductance of less than 2 ppm equivalent NaC1, dried, and stored. Analyses were as follows: Zn, 75.1 pct; Fe, 0.9 pct; Mn, 2.78 pct. The specific surface (BET method) was 1740 cm 2/g. Willemite, also from Franklin furnace, was purified similarly. Analyses were as follows: Zn, 52.5 pct; Fe, 0.12 pct; SiO², 27.3 pct; loss on ignition, 0.13 pct. The specific surface was 1760 cm 2/g. Conductivity water (double-distilled) and demin-eralized-distilled water were used in most of the tests. The specific resistance was not less than 600, 000 ohms, and usually above 1,000,000. Radiosulphur-marked hexyl mercaptan (1-hexane thiol) was synthesized by Tracerlab, Inc., Boston. Two lots were secured several months apart. The last lot, consisting of about 0.5 g of the mercaptan, had a total activity of about 10 millicuries. Tracerlab Co. guaranteed only the activity; hence a quasi -vapor pressure determination (based upon an S analysis) of the mercaptan was made. The calculated value, 4.2 mm of mercury at 25.5&apos; C, has been compared with that of a sample of Highest Purity 1-hexane thiol from Fisher Scientific Co. The latter had a vapor pressure of 4.5 mm of mercury at 2.5 C. Analytical Procedures The sample containing radiosulphur-marked mercaptan was oxidized to convert the mercaptan sulphur to sulphate, carrier barium sulphate being added to provide a suitable quantity of total barium sulphate in a filter cake. The precipitate was filtered and dried, and counting was carried out either in a streaming-gas (Q-gas) counter for high sensitivity or with an end-window G-M counter for convenience. The oxidized and precipitated mercaptan gave a radioactive count of 65 counts per minute per microgram in the end-window Geiger-Mueller counter and 1100 counts per minute per microgram in a Q-gas counter. For standardization of the mercaptan solution, 15 replicate analyses were made. The average deviation per measurement was about 1600 cpm in 65,000 cpm, the probable error in the mean being 275 cpm. It

Jan 1, 1955

By J. D. Doherty

A. R. POWELL*—Mr. Doherty has outlined in a most thorough manner valid arguments for the development of an industry in this country making syn. thetic liquid fuels from coal. No thoughtful person will dispute the statement that it is essential to carry on fundamental and applied research and acquire engineering "know-how" by the erection and operation of two or three large plants in the near future. Considerations of national security indicate that this should be done, irrespective of any temporary present surplus of natural petroleum. It is the belief of the discusser and of many others interested in coal technology that our energy picture of the future will include an increasing utilization of coal directly, without any conversion to liquid fuel, as a source of energy. A fact that is sometimes forgotten is that petroleum fuels have often been cheaper than coal in many locations and over long periods of time, and this price factor has been of great importance in expanding the use of petroleum fuels at the expense of coal. Synthetic liquid fuel made from coal must necessarily be several times as costly as the coal from which it is made, and this fact alone will have a profound effect on the future energy pattern of our country. This complete change in the economic relationship between solid and liquid fuels will lead to the substitution of coal itself for many uses now supplied by the relatively cheap petroleum fuels. From the standpoint of conservation of our natural resources, the substitution of coal itself for liquid fuels wherever possible when the age of synthetic liquid fuel arrives is also logical. At least 50 pct of the energy of coal is lost during conversion to liquid fuel. Nor is this com-pensated for by a higher utilization effi-ciency of the liquid fuel in most cases. For example, modern steam-boiler plants can operate at equal fuel efficiencies with either coal or fuel oil.

Jan 1, 1950

By John B. Cook

Most of today&apos;s open pits take the form of conical-shaped excavations in the relatively flat or undulating terrain surrounding them. Ore is usually hauled uphill from the pit bottom by truck, rail, or skip to crushing, beneficiation, railroad loading, and stockpiling facilities near the edge of the pit. There are, however, a few orebodies whose locations in mountainous terrain causes special problems that generate different technical solutions. LAMCO&apos;s 10.5 million metric tons per year high-grade iron mine in the Nimba Range in tropical Liberia is probably one of the most extreme of these exceptions (Fig. 1). At Nimba there is a 2,000-ft difference in elevation between the upper- most levels of the orebodies and the start of the railroad below at the foot of the mountain. Haulage to the crusher is usually downhill at grades of up to 12% dictated by the topography of the rugged terrain. Ore is transported from the crusher down the mountainside by a conveyor sys- tem 10,096 ft long, whose average grade is 18%. The belt is braked by asynchronous generators, feeding power into the local network. The original crusher must be relocated at a lower elevation outside the final pit limit to allow that part of the mountain on which it now stands to be excavated. HISTORY The LAMCO Joint Venture is owned 75% by the Liberian-American- Swedish Minerals Co. (LAMCO) and 25% by Bethlehem Steel Corp. LAMCO is comprised of a 50% interest by the Liberian Government and 50% interest by Liberian Iron Ore Ltd (Fig. 2). This joint venture was launched to develop the high-grade iron ore deposits of the Nimba Range.

Jan 1, 1969

By Bruce R. Lipin

Chromite, the only ore of chromium, occurs almost exclusively in mafic-ultramafic rocks and their weathering products. However, not all kinds of mafic-ultramafic rocks are favorable hosts for possible low-grade chromite deposits. For instance, chromium-bearing basalts are not favorable because they commonly contain <0.3% Cr203, and chromite is almost always less than 50 mp in diameter, if it is present at all. Chromite-bearing ultramafic rocks in stratiform and alpine complexes tend to be either ore grade (>25% chromite) or very low grade (<2% chromite); intermediate rocks are scarce. In most complexes, large tonnages exist only in the <2% chromite rocks and the composition of the chromite in those rocks may be unsuitable for metallurgical use. Some nickel laterite districts contain more than lo8 tons of material with 2.0 to 5.5% Cr203, and hence, chromium could be a byproduct of nickel in some laterite districts. In addition, some chromiferous sand placers may contain tens to hundreds of millions of tons of material between 2 and 5% Cr203

Jan 1, 1983

By B. S. Butler

Apropos of metals low in the series illustrated by Dr. Butler&apos;s Table 11, it is interesting to note that Cress and Feldman29 reported traces of platinum metals in several samples of alunite. They found, chemically and spectrographically, several traces of platinum, palladium, and rhodium in alunite from Sugar Loaf Peak, near Quartzite, Ariz.; silver, platinum, and rhodium in alunite from Rio Grande County, Colorado; and traces of rubidium and gallium in various samples of alunite. These authors stated that the platinum metals appear to be present as Oxides and suggested deposition by hydrothermal solutions under near-surface conditions. AS described by Heineman,30 the wall rock of the Sugar Loaf alunite veins shows considerable alunitic alteration. Pyrite and hematite are relatively abundant in the wall rock but decrease progressively near the veins. Assays of samples of the Sugar Loaf alunite, run by J. B. Cunningham of the University of Arizona College of Mines, showed traces of silver and 0.002 to 0.004 oz of gold per ton, but the chemical form of the gold and silver in this occurrence remains undetermined.

Jan 1, 1957

By O. Z. Klopsch, G. L. Craig

The fabrication characteristics and properties of phosphorized arsenical Lake copper have been compared with phosphorized prime Lake and phosphorized electrolytic seamless copper tubing, in a series of mill-scale tests employing commercial drawing schedules. Phosphorized arsenical coppers containing as much as 0.20 per cent arsenic were drawn with various reductions into 7/8and 3/8in. seamless tubing along with billets of the two types of arsenic-free copper. The effect of arsenic was determined by the average power required to draw given compositions and by the final properties of the respective materials in the annealed condition and after various degrees of cold reduction. Power consumption data show that no more power is required to draw arsenical coppers of this type than the arsenic-free copper. The result? of tensile tests indicate that arsenic increases the strength of cold-drawn tubing somewhat, but has no measurable effect on the properties of annealed tubing; the ductility of the tubing as evidenced by the elongation and other prescribed tests is unaffectetl by 0.20 per cent arsenic.

Jan 1, 1933

Discussion of the paper of Leonard Waldo, presented at the New York meeting, February, 1911, and printed in Bulletin No. 76, April, 1913, pp. 555 to 559. HERBERT HAAS, San Francisco, Cal. (communication to the Secretary*):-Referring to Leonard Waldo&apos;s paper on Temperature Conversion Tables, I believe the following formulas can be easily remembered, and by reference to the thermomter scales of Fahrenheit (F.), Celsius (C.), and Réaumur (R.), their derivation and relation are at once understood n° F. = 4/9 (n°-32) R. = (n°-32) C. n° C.=(9/5 n° + 32) F. = 4/5 n° R. n° R.=(9/4 n° + 32) F. = 5/4 n° C. As the freezing point of water is at 32° F., corresponding to 0° C. and 0° R., 32 must be deducted from the Fahrenheit degrees when these are converted into C. or R. degrees. Likewise, to C. or R. degrees converted into F. degrees 32 must be added. The fractions 4/9 and 5/9 and their reciprocals are obtained thus:

Jan 5, 1913

By F. F. Schmidt, H. R. Ogden, E. S. Bartlett

ThE solubility of carbon in tantalum has been reported to be very low at temperatures below 1500 C,1&apos;2 increasing to at least 0.02 wt pctl at the eutectic temperature of 2800°C. The solubility limits at low temperatures were based on metallo-

Jan 1, 1963

By K. Osseo-Asare

The thermodynamics of solid-aqueous solution equilibria up to 200°C In the systems Me-NH3 H2 0 (Me=Cu, Ni, Co) are summarized with predominance area diagrams generated with the DIAGRAM computer program. The implications of the diagrams to ammonia hydrometallurgy are discussed.

Jan 1, 1981

By William E. Ford, Edward Salisbury Dana

WheweUite. Calcium oxalste CaCz04.Hz0. In small colorless monoclinic crystals. Optically +. j3 = 1.555. From haxony, with coal; also from Bohemia, and Akace. Oxammite. Ammonium oxelate, (N&)rC20r.2HzO. From the guano of the Gudape Isbnds, Peru.

Jan 1, 1922

By A. E. Wraith, N. J. Petch, J. D. Embury, E. S. Wright

The two most important parameters controlling the fracture behavior of a solid are its intrinsic properties, e.g.,grain size, and the operative stress system. The latter may be modified in laminates by the presence of weak interfaces. This is studied in notch-impact tests on a mode1 system of mild steel laminates containing a variety of interfaces. The effect of these is evaluated in terms of the ductile/cleavage transition. Two laminate geometries are distinguished, here called "crack-arrester " and "crack-divider". In both, cleavage is inhibited. This arises because of relaxation of a state of triaxial tension. In the crack-avrester laminates, cleavage initiated at a notch is confined to the layer containing the notch. In crack-cliuider laminates, a thick specimen behaves as the Sum of a number of thinner ones. Additional benefit may derive from improved intritnsic propevties of- the lanlinate layers arising from greater deformation in their manufacture. It has long been recognized that the two most important parameters controlling the fracture behavior of solids are their intrinsic properties (e.g., grain size friction stress,3 distribution of second phase particles4) and the operative stress system under which fracture occurs. In solids that show a ductile/cleavage transition, cleavage is favored by the presence of a notch. This is because triaxial tensions, generated by the localized plastic constraint at the notch, are operative when fracture occurs.= Anything that suppresses these triaxial tensions will be unfavorable to cleavage. Such suppression may possibly occur in laminates containing weak interfaces and the purpose of the present paper is to explore this possibility. Two basic laminate geometries, here termed "crack-avrester" and "cvack-divider", are examined. They are illustrated in Fig. 1. With the crack-arrester laminates, there is the possibility that, when the fracture crack approaches the interface, this, if weak, may delaminate due to the tensile stress acting parallel to the plane of the crack.= If this happens, energy will be used in delamination, the crack will be completely blunted, and the triaxial tension associated with the crack will be relaxed. To fracture the second portion of the laminate, crack reinitiation will be necessary and, because of the relaxation of the triaxial tension, this reinitiation will occur under conditions of nearly uniaxial tension, which are unfavorable to cleavage. Thus there is the possibility of cleavage suppression in the second and subsequent subunits of a crack-arrester laminate. With the crack-divider geometry, there is again the possibility of delamination at the interfaces. This will divide the crack into a series of cracks propagating through the individual laminate subunits. If these are sufficiently thin, the triaxial tension will be relaxed towards a state of biaxial tension in each of them. Thus, with the crack-divider laminates, there is again the possibility of cleavage inhibition. In the present work, these possibilities are explored using a notched impact test on mild steel laminates bonded with soft solder, silver solder or copper. Even if delamination does not occur, it is still possible that cleavage may be inhibited in laminates. With the crack-arrester geometry, the cleavage crack in the first layer may be blunted and arrested by plastic deformation in the laminate bond, if this is ductile. Partial relaxation of the stress transmitted ahead of the crack into the second layer will then result and this will reduce the significance of this stress in the fracture of the second layer. With the crack-divider geometry, there cannot be much effect in the absence of delamination unless a large amount of energy is absorbed in rupturing the ductile material. EXPERIMENTAL DETAILS The composition of the mild steel (wt pet) was: 0.04 C, 0.29 Mn, 0.01 Si, 0.006 P, 0.008 S. "As-received" plate was annealed for 2 hr at 900°C and slowly cooled to give a grain size of 0.04 mm. The laminates were made by brazing or soldering together mild steel plates 8 by 3 in. by various thicknesses. These were obtained from the annealed plate by machining, so that the intrinsic material properties were .kept constant. Laminates containing two to six steel layers were studied using standard Charpy V-notch specimens cut from the bonded plates. Standard homogeneous specimens from the annealed plate and subsize ones from the laminate components

Jan 1, 1968