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By C. G., Fink

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution.

Jan 1, 1950

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By R. R. Sayers

VENTILATION may be defined as the process by which vitiated air of an inclosed or partly inclosed space is continuously replaced by fresh air. Fresh air has been defined as invigorating pure air. Pure dry air at sea level contains the following gases:1 Analysis of Air at Sea Level PER CENT. Oxygen 20.94 Nitrogen 78.09 Carbon dioxide 0.03 Argon 0.94 Helium, krypton, neon, xenon, hydrogen, hydrogen peroxid, ammonia, ozone traces CARBON DIOXIDE LIMIT For many years carbon dioxide was used as an index of the purity of the air vitiated by the metabolism of people. It was, however, well known that the untoward effects produced on those exposed to such air was not due to the concentration of the carbon dioxide. It has been found that the untoward effects on the comfort and efficiency of those so exposed are due to the increased temperature and humidity. It has been found that men can breathe air containing many times the amount of carbon dioxide found in our worst ventilated theaters and assembly halls, which, according to Rosenau, do not contain above 0.5 per cent. carbon dioxide.

Jan 7, 1926

By G. W. Brownell, H. T. F. Lundberg, R. W. Pringle, K. I. Roulston

The rapid improvement of the airborne scintillometer and the perfection of its efficiency for counting low energy gamma radiation has made it possible to work out a technique to map in great detail the radiation pattern at the earth's surface. On such maps low radiation over certain areas appears to indicate the existence of oil accumulations, forming a pattern similar to that obtained by the geochemists.

Jan 12, 1953

By W. C. Hagel, H. J. Beattie

Seven austenitic alloys of varions base compositions and minor-alloy additions were solution-treated, aged systematically between 1200oand 1800oF, and examined by X-ray and electron metallography. Intragranular preczpitations of µ, Laves, s, ?', Ni3Ti, and x phases were observed as a function of composition and aging time and temperatwre. Phase solubility limits were detevtnitzed within 100Fo intervals. These inter metallic compounds fall into two distinct general classes, and whichever class predomznates depends on base composition. It has become increasingly evident that multicom-ponent austenitic alloys are well characterized by their precipitation processes. Since certain groups of elements act as one, the relationships among these processes are reasonably simple; complete identification of such processes is usually attainable by a systematic aging study with a combination of techniques centered on microscopy and diffraction. Several nickel- and cobalt-base alloys illustrating cellular precipitation and its interaction with general precipitation were reported previously.1 The group of alloys covered in the present paper demonstrates precipitation-hardening reactions involving two distinct classes of intermetallic compounds where the predominating class appears to depend on base composition. This dependency ties in with a crystal-chemistry regularity first observed some twenty years ago by Laves and Wallbaum but never amplified to our knowledge. Results of electron-microscope and X-ray diffraction studies on systematically aged hot-rolled alloys known commercially as S-816, S-590, Rene-41, Incoloy-901, M-308, and M-647 are reported here. Some of these alloys have previously undergone minor-phase analyses by other investiators. Alloy S-816 was investigated by Rosenbaum, Lane and Grant,3 and Weeton and Signorelli.4 Rosenbaum found only CbC in hot-rolled bars. Lane and Grant found CbC and a small amount of M6C in the cast structure and stated that both carbides form during aging, most of the precipitation being CbC. Weeton and Signorelli found CbC, M23C6 and a weak indication of a phase after a slow step-down cooling cycle from 2250°F. Rosenbaum also investigated hot-rolled samples of S-590 and identified CbC and M6C. Preliminary information on Rene-41, gained partly from the present work, was reported by Morris.5 Long-time precipitation phenomena in Incoloy-901 at 1350°Fwere investigated by Clark and Iwanski.B heir raw data re- semble those of our present heat with 0.1 pct B, while their interpretation of these data resembles our interpretation of data from another heat with only 0.001 pct B; they made no statement as to boron content. No previous minor-phase studies of alloys M-308 or M-647 have been reported. EXPERIMENTAL METHODS Table I gives alloy compositions in both weight and atomic percent. Specimens were solution-treated from 1700º to 2200ºF, aged at logarithmic-time intervals up to 1000 hours between 1200 and 1800 F, and examined in accordance with procedures previously described in detail. ' ' Phase extractions were carried out in electrolytic cells containing 800 ml of either 7 pct HC1 in denatured ethanol or 20 pct H3PO4 in water. After electrolysis for 48 hr at 0.1 to 0.2 amp per sq inch, residues were separated by filtration or centrifuging. X-ray powder patterns of residues were recorded on a diffractometer for accuracy and on film for sensitivity. Lattice parameters were calculated by least-squares analyses of indexed sin 8 values, and relative abundances were estimated from intensities of strongest lines of each phase. These phase abundances denote relative amounts with respect to each other rather than to the alloy. Mechanically polished specimens were etched in a freshly mixed solution of 92 pct HC1, 5 pct H2SO4, and 3 pct HNO3. Parlodion replicas for the electron microscope were chromium-shadowed in high vacuum at a glancing angle of 20deg. All electron micrographs are reproduced here with the shadowing source above. The correspondence betweenelectronmicrostructures and phases identified by X-rays was established by a high redundancy of correlation between relative amounts at different stages of aging and examination above and below critical transformation or solubility temperatures. EXPERIMENTAL RESULTS S-816 and S-590—The phases found in S-816 and S-590 after various aging and solutioning treatments are listed in Table 11. These data and the observed

Jan 1, 1962

By M. R. Louthan, C. L. Angerman

In polycrystalline Zircaloy-2 the orientation of zirconium hydride precipitates is influenced by an applied stress during hydride precipitation; hydride platelets are oriented nearly parallel to a compres-sive stress and perpendicular to a tensile tress. 1,2 A similar effect has been observed in the Ti-H system, where precipitation of the low-density hydride platelets occurred on habit planes made energetically favorable by the application of stress. 3 Recently, stress activation of hydride habit planes in zirconium and Zircaloy-4 was also demonstrated. The hydrides precipitated on {101l), {112l} and (2131) planes in both zirconium and Zircaloy-4; however, no platelets were found near the prism-plane positions in the Zircaloy-4 samples. Investigations at the Savannah River Laboratory, using polycrystalline Zirc_aloy-2 samples, have confirmed the (101l) and (1121) habit planes but also showed that the prism planes were active hydride habit planes. Using single-surface stereographic analysis and back-reflection Laue techniques, most of the previously reported habit planes for a zirconium were observed.4"1 and one additional plane, the (1013) plane, was noted, Table I. All the habit planes observed had the form (101l) or { 112l) indicating that these planes are the habit planes for hydride precipitation in poly-crystalline Zircaloy-2. The specimens used in these studies were cut from large-grained weld areas of seam-welded tubing and were hydrided in either a static steam autoclave at 400°C and 1500 psig or in a modified Sieverts apparatus at 400°C.

Jan 1, 1967

THE total crude production from the Dutch East Indies, and the British Protectorates of Sarawak and Brunei for 1932 is given in the following table: BARRELS BARRELS (42 GAL.) (42 GAL.) North Sumatra 4,226,935 Ceram 326,207 South Sumatra 13,956,157 Sarawak 2,739,650 Java 3,845,568 Brunei 1,322,725 Dutch Borneo (main island) . 9,406,733 Dutch Borneo (Island of Tara- kan) 6,579,184 Total 42,403,159 Production, which had shown a rapid increase from 1921 to 1929, has since been reduced. Exploitation drilling in the majority of the larger fields was suspended and existing production kept within predetermined limits by beaning. Most of the smaller fields were shut down entirely. The depth of producing levels varies widely in the different fields. Shallow fields with drilling depths to 500 meters (1650 ft.) are still numer-ous as well as those with depths between 500 and 1000 m. (3300 ft.). A few of the newer fields reach greater drilling depths. up to 1600 m. (5250 ft.). The deepest exploration well drilled to date (Djambi field, South Sumatra) reached a depth of 2332 m. (7650 ft.) before abandon-ment in March, 1930. The specific gravities of the various crude oils produced range between 0.65 (86.2° A.P.I.) and 0.95 (17.5° A.P.I.). The lighter crudes have a high gasoline content and fuel oils are derived from the heavier crudes, which usually are rich in paraffin.

Jan 1, 1933

By A. V. Bradshaw, R. I. L. Guthrie

The behavior of large bubbles in the size range 4 to 25 cm3, rising through molten silver, has been studied. It was found that rising velocities were equivalent to those in aqueous systems of low viscosity. Mass transfer coefficients for oxygen bubbles dissolving in silver were found to be 0.036 ± 0.007 cm sec-1, being close to those predicted for transfer through the front surface of the spherical cap bubble only. It is suggested that the surface active nature of oxygen in silver could account for the relatively low coefficients obtained. MANY metallurgical processes involve interactions between gas bubbles and liquids. Examples include the removal of carbon monoxide in Open Hearth Steelmak-ing, the removal of sulfur by blowing air through copper matte during converting, and the removal of hydrogen from steel during vacuum degassing or inert gas flushing. The steps involved in such refining processes include; transport of the dissolved species to the bubble interface, adsorption and chemical reaction of the species at the interface, desorption of product molecules from the interface, and transport of product gas into the bulk gas phase of the bubble. It has been concluded1 that all the interfacial steps involved proceed so rapidly at steelmaking temperatures that transport of the solutes, present in the metal, become the important rate controlling factors provided nucleation phenomena are not restrictive. The O-Ag system was chosen for the investigation into gas bubble-molten metal interactions due to the relatively high solubility of oxygen that enables rates of oxygen transfer to be measured from changes in bubble volume. Other advantages of this system include the absence of a stable oxide phase at an oxygen pressure of 1 atm and the relatively low melting point of the metal which permits the use of a metallic container, providing that it is resistant to oxidation. In those metallurgical processes where bubbles have an important influence, bubble volumes are usually greater than 5 cm3. For this reason the present study relates specifically to single large bubbles of oxygen rising in silver. These bubbles adopt the characteristic spherical cap shape similar to that shown in Fig. 1 for a 30 cc bubble rising in water. After an initial investigation to determine the velocities of inert (nitrogen) bubbles rising in molten silver, experiments were carried out with oxygen and the rates of mass transfer between the oxygen bubbles and the silver were measured. EXPERIMENTAL Apparatus. The apparatus, Fig. 2, for containing molten silver, was constructed from "Nimonic 75" Alloy (75 pet Ni, 20 pet Cr, 5 pet Fe, Mn) and provided for the release of single bubbles from an hemispherical cup, situated at the bottom of the column. The cup was turned by translating the rotation of the drive shaft through 90 deg. This was accomplished by the use of a bevelled gear system, and a smooth drive was provided by the lubricating action of the silver on the gears. Since reliable high temperature seals at 1000°C were found to be impracticable, the filling and drive shaft tubes were extended outside the 3.5 kw resistance wire tube furnace, where connections were made using easily accessible O-ring seals. The apparatus remained gas tight to the atmosphere at pressure differentials far in excess of those used. The filling tube was connected via a small bore tube to the differential pressure transducer. Gas could be bubbled into the inverted cup from two i-in. tubes which passed down the inside of the column to preheat the gas. The temperature of the silver was maintained at 1020°C during all experiments. Measurement of Bubble Volume. In order to calculate mass transfer rates, it was necessary to obtain a continuous record of the bubble's volume during its passage through the column of molten silver. The method adopted for measuring the bubble volume involved closing off the top gas space to the atmosphere prior to each experiment, and recording the variation in gage pressure of this space during the formation and rise of the bubble. Since any change in bubble volume results in an equal change in top space volume, Boyles Gas Law may be applied (for isothermal con-

Jan 1, 1970

By Frank S. McKenna, Myron A. Pugacz, Clarence E. Jackson

THE notched-bar impact test has proved worth while in certain applications as a test for control of the quality or the heat- . treatment of steel. In view of the serious thought that even so simple a test as the tensile test, has evoked during the past years, it is not surprising that the notched- bar impact test should have inspired much experimental work. The correlation of the great number of data has not been successful, although steady progress has been made toward a better understanding of this test. Progress has been made, especially, in the isolation of the effects of the many variables that control the results. The stress system imposed on a specimen with a notch is so complicated and un- predictable that no simple evaluation of the test has been possible. Because of this uncertainty, many engineers hesitate to use the notched-bar impact test, and this attitude may well continue until a better understanding of the effects of the variables in the test are available. Without doubt, any additional data that may be presented should be accompanied by as complete a description of the details of test as possible, so that it may be added to the general fund of information that is to serve as the basis for the theory of the notched-bar impact test. The many factors that may control the test results have been pointed out repeatedly. The importance of the effect of the type and dimensions of the specimen has been recognized. Most of the work reported by American investigators has been limited to small- size (Charpy) specimens tested as a simple beam; two types of notches (Fig. I) have been commonly used. Considerable data have also been presented by many investigators using a small specimen tested as a cantilever beam; this commonly being called the Izod test. Here, however, a shear component of stress makes the stress system even mare complex than that present in the simple beam type of test, hence a critical analysis is difficult. Much work has also been reported by investigators using the tension type of specimen. A second variable that must be con- trolled is the testing temperature. An indication that the tests were performed at room temperature is not sufficient, since in many steels a variation of a few degrees in the actual testing temperature may be sufficient to give an entirely different range of results. Other factors. such as the com- position and condition of the material being tested and the speed of test, should also be considered. Many investigators have contributed data and theoretical discussions on the problems encountered in notched-bar test-

Jan 1, 1944

By H. I. Aaronson, H. A. Domian, G. M. Pound

Zener's two-parameter theory of the y a reaction in Fe-X alloys is extended to encornpass austenite-stabilizing as well as fewite-stabilizing elements, and is then cottzbitzed with statistical thermodynamic theories of Fe-C alloys to permit development of a ther-modynamic description of the proeutectoid fewite reaction in Fe-C-X alloys. Equilibrium tielines are calculated for tile a + y rep'on from experimental data and frort extrapolations of the y/y +a equilibrium surface. Sectzovs of the y/y + 0 surface are calculaled for the tzetastable sstuation LYL u-kich alloyrtg eleitzents do not partition betzseen azrstenite andfer-rite. The finding that the metastable y/a + y curves Lie close to their equilibriuwz counterparts when X = Si, .Vo, Co, Al, and Cu but well below them when X = A/ln or Ari pr-elides a thermodunamic explanation for the expcri1?7e?ztally obserted absence of partition during the proeutec toid ferrite reartlon in the fortner alloys and for the occurrence of partition at hzgher ternperatures in the latter alloys. Cotarison ofno- patitzoa free-energy changes and y/y i a curr,es in Fe-C-X alloys with the equilibrium 11al1es of these quantities in Fe-C alloys furnishes additional qualitative insight into the irqluence of allojling elements upon the kinetics of the proeutectoicl ferrite reaction. THE introduction of a substitutional alloying element, X, appreciably complicates calculation of the thermodynamics of the formation of proeutectoid ferrite from austenite. As noted in the preceding paper,' the positional entropy of the interstitial species is the principal component of the free energy of an interstitial solid solution with which theory has so far been able to deal. One would expect, however, that other components of the free energy of this type of solid solution may be significantly altered by the addition of a substitutional alloying element. Even if the assumptions are made, by analogy to the case of Fe-C alloys,' that changes in the positional entropy of carbon represent a significant part of the thermodynamic effects of an alloying element, and that the remaining effects can be taken into account by fitting the equations developed on this basis to experimental data on Fe-C-X phase diagrams or on the activities of carbon in alloyed austenite and ferrite, the experimental information available on either of these quantities is not yet sufficiently accurate or extensive, respectively, to make such an approach useful. An attempt made by Zener on the former basis to explain the effects of alloying elements on the thermodynamics of Fe-C alloys in terms of a temperature-independent "free-energy change" (actually enthalpy hane') required to transfer 1 mole of an alloying element from austenite to ferrite, in which the "free-energy change" was determined by fitting the theoretical relationships developed to Fe-C-X phase diagrams, thus proved inadequate in part because of deficiencies in the available ternary-phase-diagram data.= Other difficulties of a more fundamental nature, however, also indicated the desirability of a different approach to the problem.3y4y6 zener6 subsequently proposed that the free-energy change associated with y — a transformation in pure iron can be decomposed into magnetic and nonmagnetic components. Alloying elements were assumed to affect those components separately. One parameter was used to describe the quantitative effect exerted on each component. These parameters were evaluated from Ms (martensite-start) temperature data and from other experimental information usually either readily available or measurable with acceptable accuracy. Zener applied this treatment only to the calculation of Fe-X phase diagrams in which X is a ferrite-stabilizing element. In the present study, this treatment is extended to include austenite-stabilizing elements, and then combined with treatments previously considered for Fe-C alloys1 to permit calculation of the thermodynamic quantities of interest in the austenite - proeutectoid ferrite transformation in Fe-C-X alloys, where a number of representative, and commonly used alloying elements are chosen for X, including Si, Mn, Co, Mo, Al, Cr, and Cu. The results are used to explain important features of the partition of alloying elements between austenite and proeutectoid ferrite, as reported in a companion paper7 on the basis of electron-probe analysis, and to provide some additional understanding of the influence of alloying elements upon the kinetics of nucleation and growth of proeutectoid ferrite. Portions of this treatment6 have been clarified in the course of a review by Kaufman and Cohen.3 The consolidated summary of these developments with which this section is begun provides a basis for further clarification of the treatment, from which extension to include austenite- as well as ferrite-stabilizing elements is a natural consequence. The division of the free-energy change associated with the 7 - a transformation in pure iron, into two independent components is formally stated as:

Jan 1, 1967

By R. M. Waterstrat

The phase VPt has been reported to have a crystal structure of the B19 (AuCd) type at low temperatures.''' A recent investigation3 has indicated that this phase forms by an ordering reaction from the disordered fcc Pt(V) solid solution which is stable at high temperatures. olander4 has shown that there exists a close structural relationship between the orthorhombic B19 structure and a fcc structure possessing the L1 , (CuAu) type of atomic ordering. One may derive the B19 structure by a shear-like displacement of the atoms in the (002) plane of the ordered fcc lattice along the (010) direction through a distance equal to one eighth of the unit cell dimension, see Fig. 1, followed by an orthorhombic distor; tion of the cube axes such that a = 2.693A. h = 4.413A. and c =4.767A (estimated uncertainty 0.005A). Filings of this phase were produced by grinding a VPt alloy having the B19 structure with a diamond dental grinding disc. When these filings were subjected to X-ray diffraction examination, a pattern of a severely cold-worked fcc structure was obtained. higher solution temperature used (1200 C) or to a much lower oxygen pressure than he reported, due to transfer through many bends and tubes in his complicated apparatus. An interesting observation was made when an oxygen addition was attempted in a cylindrical sample of columbium in the cold worked condition rather than in the annealed condition. The interior of the sample re-crystallized during the oxygen addition at 900°C. The periphery, however. (1 mm) did not recrystallize. A similar sample without oxygen recrystallized throughout the entire cross section. It appears that the re-crystallization is hindered by interstitial oxygen. Presumably, the interior recrystallized before appreciable oxygen could diffuse into the core. This work was supported by the United States Atomic Energy Commission. When the filings were annealed in a high vacuum furnace for 15 min at 110O0C, however. they returned to the B19 structure perhaps as a result of reordering. Subsequent less-severe cold-working of these filings by grinding in a hardened steel mortar and pestle at room temperature produced a transformation into a cold-worked L1, structure which was slightly tetragonal. Thus it appears that the degree of deformation may influence the final structure. Considerable line-broadening was observed in X-ray diffraction patterns obtained from the cold-worked filings and therefore no attempt was made to obtain accurate lattice parameters. Vacuum annealing treatments at 1100'C intended

Jan 1, 1970

By K. A. Natarajan, I. Iwasaki

The effect of poisoning on the behavior of platinum electrodes in redox potential measurements in metallurgical systems was studied in the presence of such inorganic surfactants as cyanide and sulfide and such organic surfactants as dodecylammonium acetate, trimethyldodecylammonium chloride, potassium ethyl xanthate, and potassium diethyl dithiophosphate (Aerofloat®). These chemical species represent, more or less, typical constituents encountered in leaching, flotation, and sewage treatment systems. Triangular wave voltammetry was used as the experimental technique to study the nature of poisoned surfaces. Among the species studied hydrogen sulfide and dodecylamine were found to form a resistant surface film affecting charge transfer. Platinum electrodes appeared to have a weaker tendency to adsorb sulfide species in alkaline pH ranges, while cyanide, xanthate, and dithiophosphate affected the normal electrode behavior differently. Possible methods of reactivation of a poisoned electrode by mechanical cleaning are suggested.

Jan 1, 1974

By Robert Glass Cleland

[DATA OF THE YEAR 1950 COMPARED TO 1909 (FIRST CONSOLIDATED REPORT) CONSOLIDATED NET INCOME Without deduction for depletion of mines $ 42,395,465 $7,337,252 After deduction for depletion of mines $ 4,112,604 $7,337,252]

Jan 1, 1952

Jan 1, 1932

By Klaus Schwerdtfeger, Leo Zwell

The equilibrium between Ir-Fe or Rh-Fe alloys, iron oxide (wüstite or magnetite), and CO2-CO atmospheres has been determined at 1200°C. The data are used to derive the activities in these binary solid solutions. Both systems show negative deviations from Raoult's law. The lattice parameters are given for the investigated Ir-Fe and Rh-Fe alloys. IRIDIUM and iron form a continuous series of fcc solid solutions at elevated temperatures.' Rhodium-rich Rh- Fe alloys have fcc structure.' In the medium concentration range an ordered bcc phase is stable at temperatures up to about 1300°C. Phase relations in iron-rich alloys are not well-known. No thermody-namic data are available for these alloys. EXPERIMENTAL METHOD The experimental method used was to measure the equilibria between a gas phase of known CO2/C0 ratio, the alloy, and iron oxide (wüstite or magnetite). In one series of experiments the alloys of known composition were heated in CO 2-CO gas mixtures. After treatment (usually 1 day) the sample was quenched to room temperature and its surface examined visually to determine whether an oxide tarnish had formed. The procedure was repeated at slightly higher CO 2/CO ratios until the CO 2/CO ratio of incipient oxidation was found. Subsequently, the CO 2/C0 ratio was lowered again in small increments until the tarnish was reduced. In other experiments mixtures of alloy and iron oxide powders were pressed into pellets and equilibrated with the CO2-CO gas phase. In order to ensure that equilibrium was attained, two specimens with different starting iron content were heated side by side; in most cases, equilibrium was approached in one pellet by reduction of iron oxide and in the other pellet by oxidation of metallic iron. The sample was quenched to room temperature, and the composition of the equilibrated alloy was determined by X-ray measurements of lattice parameters and comparison of these values with calibration curves obtained from alloys of known composition. The oxides present in the specimens were identified by comparison of their diffraction patterns with those in the ASTM Card File. It may be expected from the noble character of iridium and rhodium that no appreciable amount of iridium or rhodium is dissolved in wiistite and magnetite under the present experimental conditions. The activity of iron in the alloy is then equal to that established in the iron oxide by the COrCO atmosphere. The activities of iron in wüstite and magnetite, as a function of oxygen pressure, were taken from the work of Darken and Gurry,

Jan 1, 1969

By O. Vartianen, R. T. Hukki

A preliminary investigation of the collecting effects of various fatty acids in tall oil has led to a conclusion that the collecting power of fatty acids used in flotation increases with increasing un- saturation of the hydrocarbon chain. Linoleic acid was found to be an excellent collector for oxide minerals. TALL oil is a mixture of fatty and resin acids extracted as byproducts in the sulphate pulp industry. In the field of flotation a well-known example of this type of product is Reagent No. 708 of the American Cyanamid Co. Its successful use as a flotation collector with many nonsulphide minerals has been described by Falconer and Crawford.' The composition of crude tall oil varies within wide limits.' " By a number of methods the crude oil may be refined to produce a variety of refined products. This investigation presents a preliminary comparative study of collecting properties of the fatty acids in tall oil. In Finnish tall oils these constituents are primarily palmitic, oleic, linoleic, and linolenic acids.:' The first is a saturated fatty acid having 15 carbon atoms in its hydrocarbon chain, plus one in the carboxyl group. The others have 17-carbon-atom chains and are unsaturated. It is of particular interest to note that palmitic, oleic, lino-leic, and linolenic acids represent increasing degrees of unsaturation with 0, 1, 2, and 3 double bonds, respectively. To test the collecting properties of the four fatty acids separately, the vacuum flotation technique described by Schuhmann and Prakash4 was used. By this method the boundary between flotation and non-flotation conditions was approximately delineated, with the use of ilmenite and several other minerals. Collector concentration and pH were the principal variables. On the basis of information obtained, actual flotation tests were run on an ilmenite-bear-ing ore in a laboratory flotation cell. Through the courtesy of P. Kajanne from the Department of Chemistry, Finland Institute of Technology, the following reagents were obtained for this investigation: 1—Palmitic acid, of Judex, had a purity of 95 pct as determined by parallel iodo-metric and spectrophotometric measurements. 2— Oleic acid, product of May and Baker Ltd., indicated purity of 98 pct. By iodometric and spectrophoto-metric determinations the oleic acid content was found to be 83.8 pct. In addition, it contained 6 pct linoleic, 1 pct linolenic, and 9.2 pct saturated fatty acids.' 3—Linoleic acid was prepared from soybean oil by low-temperature crystallization. Its linoleic acid content was 95 pct by the methods indicated above. 4—Linolenic acid was prepared from linseed oil by low temperature crystalIization. Its linolenic

Jan 1, 1954

By E. H. Denny

IN the past few years many men, including technically trained engineers, have been asphyxiated in metal mines, coal mines, tunnels and surface wells where a few relatively simple precautions with regard to ventilation and air testing would have saved them. Death from mine gases is analogous in some respects to death from poison and from drowning. The respiratory passages of a victim who has breathed oxides of nitrogen from burning explosives are badly irritated and a few hours or even a day after exposure he may develop a quick and fatal pneumonia; if, however, he enters without respiratory protective apparatus an atmosphere deficient in oxygen (a condition that may occur in unventilated or poorly ventilated parts of all underground mines) he collapses and if not rescued dies more quickly and surely than a lone nonswimmer who falls suddenly into deep water. An example of an atmosphere virtually without oxygen was demonstrated by an air sample taken by a Bureau of Mines engineer wearing oxygen breathing apparatus in a Cripple Creek shaft some years ago, during the recovery of the bodies of two victims of asphyxiation; analysis of the sample by the Pittsburgh laboratory of the Bureau showed the presence of 18.40 per cent of carbon dioxide, 0.27 per cent of oxygen, and 81.33 per cent of nitrogen, although the atmosphere apparently was clear and normal. In a mine one can pass from good, breathable air to an atmosphere that will kill as quickly as one can dive from a board to deep water below. SOME INSTANCES OF ASHYXIATION BY GASES IN METAL MINES The following typical examples of comparatively recent instances of asphyxiation in metal mines were taken chiefly from reports of various kinds of the U. S. Bureau of Mines.

Jan 1, 1938

By J. W. Spretnak, R. Speiser, A. M. Adair

THERE are sufficient arguments and evidence to indicate that boron should be adsorbed to existing austenite grain boundaries during the austen-itizing treatment. Accordingly, it is possible that boron contributes to the hardenability of heat-treatable steels by the reduction of the interf acial energy of austenite grain boundaries, at which sites are nucleated heterogeneously the decomposition products of austenite. Such a reduction in interfacial energy would reduce the total energy that can be borrowed in these heterogeneous nudeation processes and thus retard the initiation of transformation. This investigation was undertaken in an attempt to determine the effect of boron on this interfacial

Jan 1, 1956

By E. P. Klier, Jane Jellison

The course of the transformations on cooling in a series of Cu-A1 alloys has been followed by means of thermal analysis, X-ray diffraction, and optical metallogrAphy. Specimen size was found to have a pronounced effect on the time of completion of the pearlite transformation due to modification in the unmber of nuclei. The ordeving transformation zvas observed for all cooling rates for all alloys studied, and is considered insuppvessible. At intermediate cooling' rates, a transitional struchire for 011 alloy compositions and based ox the bainite reaction was observed. The alloys of aluminum and copper possess a eu-tectoidal region at from about 9.4 to 16 pct Al. Above the critical temperature, the disordered bcc phase, 0, is stable. At subcritical temperatures, the 0 phase decomposes under equilibrium conditions into the stable phases, a and y,. At the eutectoid composition, these phases develop a lamellar pearlite structure, in appearance much like that found in steels. During rapid quenching from supercritical temperatures, the diffusion processes required for the formation of the equilibrium phases are suppressed, and the 0 transforms to an acicular martensitic phase, designated B or y' depending on the aluminum content, or to a mixture of the two. Early investigators of this system concentrated on determining the equilibrium phase diagram, ''' the structure of the equilibrium phases,3 and later the isothermal decomposition of the 0 phase at subcritical temperatures, or the decomposition of the martensite on tempering. Other work which treated the nonequilibrium transformations concentrated largely on the martensite transformations and the structure of the b and y' phases.15"17 Since the pearlite and martensite transformations in this system resemble those in steels, the one being formed by nucleation and growth of adjacent lamellae of the equilibrium phases, and the other by a diffusionless, shear-type transformation, the present study has been undertaken to investigate the structures formed on continuous cooling, with the objective of constructing cooling transformation diagrams analogous to those derived for alloy steel systems. In particular it was desired to determine whether parallels between the A1-Cu and iron-iron carbide systems on continuous cooling extended to encompass the intermediate phase, namely the bainite structures, which form by a combined martensitic-diffusion mechanism,'' but which are supersaturated with respect to the equilibrium phase upon which their crystal structure is based. To this end the transformations in representative alloys of the Cu-A1 B eutectoid system have been followed, using the methods of thermal analysis, X-ray diffraction, and optical microscopy. EXPERIMENTAL PROCEDURE Materials. The materials tested were those used by Klier and Grmko 5 in their study of the isothermal decomposition of these alloys. The alloys were melted in graphite crucibles and chill-cast into 5 by 2 by 1/4 in. ingots. The ingots were then hot-rolled to sheets 1/8, 1/16, and 1/32 in. thick. The compositions are given in Table I. Specimen Preparation. Specimens for thermal analysis were in the form of small squares approximately 1/4 in. on a side. For the 11.9 and 13.5 Al-Cu alloys, the sheet thickness was 1/16 in. and for the 10.5 A1-Cu alloy the 1/32-in. sheet was used. One lead of a chromel-alumel thermocouple was spot-welded to either face of the square with the specimen itself thus forming the hot junction of the thermocouple. Specimens for X-ray analysis were prepared as filings from martensitic sheet stock and were sealed in glass ampoules under 1/2 atm of argon. Metallographic examination of the powder specimens was carried out on a portion of the heat-treated filings mounted in lucite. All specimens were examined metallographic ally after etching

Jan 1, 1965

By C. M. Loeb, A. M. Gaudin, J. H. Brown

R. E. Carter (General Research Laboratory, Schenec-tady, N. Y.)—Brown, Gaudin, and Loeb in their study of intergranular comminution by heating attempt to find one explanation for all types of rock in terms of the properties of the phases present. The only necessary condition for intergranular cracking by heating is the setting up of high stresses at the grain boundaries. Such stresses may be set up in multiphase isotropic mixtures if the thermal expansions of the phases are different, in non-cubic single phases because of the anisotropy of thermal expansion in the various crys-tallographic directions, and in materials containing quartz because of the a-p' transformation at 575°C. In addition, for intergranular comminution by heating, the cooling and not the heating is most important.

Jan 1, 1960