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John S. Kennedy, Chamhersburg, Pa. (communication to the Secretary): The washing-plant described by Mr. Johnson is a good illustration of the advantages derived from a well-designed and care-

Jan 1, 1895

By Arthur F. Wendt

The following experiments and researches were originally conducted by Dr. Heinrich Rcessler, chief of the German Gold and Silver Parting Establishment at Frankfort-on-the-Main, for the sole purpose of abating the nuisance created by the discharge into the air of the sulphurous and sulphuric acids generated in the process of parting bullion by sulphuric acid. The results achieved have, however, an important bearing not only on this process, but are of value in the manufacture of sulphuric acid and sulphate of copper from sulphurous gases derived from any source. It has now been in successful operation for a term of years at Dr. Roessler's own works, and has been lately introduced with satisfactory results at the royal mints of Kremnitz and Munich, and the well-known establishment of Johnson Mathey & Co., of London.

Jan 1, 1884

By Ravindra M. Nadkarni, Milton E. Wadsworth

The kinetics of cetnentation of copper with iron were observed to follow first-order kinetics and increase with speed of agitation to a limiting value. Maximum rates agree closely with theoretical values based upon a model of aqueous solution diffusion through a litniting boundary film. Back reaction kinetics are shown both theoretically and experimentally to be independent of ferrous iron concentration in solution. The inlportance of attnospheres of air, oxygen, nitrogen, and hydrogen was studied and the results have been correlated with several impovtant oxidation processes involving metallic iron and copper. The kinetics of the reaction of ferric ion with metallic iron were found to be slow in the absence of metallic copper and essentially proportional to the surface area of metallic copper present in the system. THE precipitation of copper on iron is classic as an example of a relatively ancient art applied successfully for centuries with little fundamental understanding of the important parameters involved. There is some indication that the process has been a commercial means to produce copper since the sixteenth century.' The amount of fundamental work on the cementation of copper with iron is not great. Wartman and Roberson2 carried out a series of detailed copper cementation experiments using natural and synthetic mine water. The following were presented as the three principal reactions: Reaction [I] is the desired cementation reaction and accordingly 0.88 lb of iron would produce 1 lb of copper. In actual practice iron consumption would more normally fall in the range of 1.5 to 2.5 lb per lb of copper. Wartman and Roberson attributed the excess consumption of iron to Reactions [2] and [3]. They found that Reactions [I] and [2] proceeded at approximately the same velocity while Reaction [3] was much slower and would be diminished by controlling the contact time. It was also pointed out that increased agitation is beneficial in removing hydrogen bubbles and barren layers of solution at the iron surface as well as removing contaminants resulting from the hydrolysis of iron. Episkoposyan3 and Episkoposyan and Kakovskii4 studied copper and silver cementation on rotating iron disks in chloride solutions. The kinetics based upon a diffusion model were first order and varied linearly with surface area and with angular velocity raised to the one-half power according to the Levich equation. The experimental activation energy for both copper and silver was approximately 3 kcal per per mole. Excess iron consumption was found to increase with temperature. The rate of cementation first increased with increasing acidity and then diminished at high acid concentrations. sutolov5 has presented an excellent review of the Leach-Precipitation-Flotation (LPF) process including a discussion of copper cementation from an electrochemical point of view although few experimental results were presented. From voltage considerations he predicted that cementation should not be influenced by the concentration of ferrous iron in solution. He considered several secondary reactions including Reactions [2] and [3] and pointed out the importance of oxidation of ferrous iron to ferric with oxygen. In addition it was suggested that Reaction [2] was enhanced by the dissolution of metallic copper by ferric iron which in turn consumed excess iron by the cementation reaction, Eq.[1]. Cementation of copper on metals other than iron has been studied by several investigators but, as in the case of iron, the amount of fundamental work is not extensive. Bashkova and kovalenko6 and Bashkova7 studied the cementation of copper on indium from copper and indium sulfate solutions. The rate was found to be first order and to increase with acidity. This was associated with a decrease in potential (EIn — ECu) and the simultaneous reduction of hydrogen ions at low pH. The rate of cementation also decreased with increasing indium concentrations which was postulated to be due to the decrease in the rate of diffusion of the ions in solution. Below 97°C the experimental activation energy was found to have the unusually low value of 2 kcal per mole and was attributed to diffusional control. Above 97°C the rate increased suddenly and was explained as a change in the rate-controlling step to a chemical reaction. In Part I of this study Nadkarni et a1 .1 have reported on preliminary results obtained in a laboratory study of the kinetics of the cementation process. The rate was found to be first order, proportional to the surface area of the iron, and to increase with speed of stirring until a maximum rate was observed. At low stirring speeds the deposit was spongy and adherent. At medium speeds the copper peeled off in bright strips and at high speeds finely divided copper was produced and continually removed from the surface. The amount of excess iron consumed increased with speed of stirring and with temperature. The average experimental activation energy combining results from several types of iron was 5.8 + 1.6 kcal per mole suggesting diffusional control through a limiting boundary film. Traditionally copper cementation has been carried out over the centuries in gravity-fed launders of various design containing scrap iron. More recently rotating drum precipitators and activated launders8'10 have been used. In the latter, copper-bearing solutions are

Jan 1, 1968

By Rees D. Rawlings, C. W. A. Newey

The aging characteristics of an Fe-11 at. pct Mo alloy have been studied by means of light metallography together with density, Young&apos;s modulus, and hardness measurements. The results were consistent with the precipitation of a single intermetallic compound during aging; overaging was slow relative to that in other iron-based binary alloys. The solution treatment temperature had a small effect on the rate of hardening whereas deformation prior to aging had a marked effect on both the rate of hardening and the peak hardness. The density data indicate that the compound precipitated is Fe3MO2 and not the Laves phase Fe2Mo. Analysis of the modulus and density results gave values for the time exponent for precipitate growth of approximately 1.0 and 1.5 for the alloy aged with and without prior deformation, respectively. DETAILED studies of precipitation hardening in bcc matrices have been confined largely to the effects of carbides and nitrides. In view of this and the growing technological interest in intermetallic compound strengthening, e.g., in maraging steels, a study of precipitation in iron-based alloys with a low interstitial content has been undertaken. This paper is concerned with the aging behavior of an Fe-11 at. pct Mo alloy; the mechanical behavior of the alloy will be reported later. The early work of sykes on Fe-Mo alloys showed that precipitation of the intermetallic compound was accompanied by an increase in hardness and a decrease in volume of the material. More recent surveys of the strengthening associated with precipitation have been made3-5 and, in particular, Elsen and wassermann4 showed that deformation prior to aging increased the rate of hardening. These latter workers also followed the precipitation process by means of dilatometry, electrical resistivity, and lattice parameter measurements. Their results confirmed that there is a decrease in volume on aging. Except for the work of Hornbogen on an Fe-20 at. pct Mo alloy, neither clustering nor the precipitation of a nonequilibrium phase has been observed in Fe-Mo alloys. Studies of alloys of lower molybdenum content475 indicate that the equilibrium intermetallic compound is precipitated during aging. However, there is some doubt concerning the nature of the equilibrium precipitate phase. According to the phase diagram constructed by Hansen,8 the phase should be precipitated. This phase has a rhombohedra1 crystal structure which is characterized by the formula Fe706,&apos; although the composition of the molybdenum-rich boundary corresponds approximately to Fe3Mo2. The version of the diagram proposed by Sinha, Buckley, and Hume-Rother indicates that the A phase, a Laves phase Fe2Mo, should be precipitated. Their observation of a Laves phase supports the earlier findings of Bechtoldt and Vacher,13 although, in a recent study of the system by means of diffusion couples, Rawlings and Newey did not detect the phase. The work presented here describes the effect of solution-treatment temperature, aging temperature, and prior deformation on the aging characteristics of the alloy as revealed by light metallography together with hardness, density, and Young&apos;s modulus measurements. In addition the density data are used in an attempt to determine the compound precipitated during aging. EXPERIMENTAL PROCEDURE A 29-kg ingot of the alloy was cast at R.A.R.D.E., Fort Halstead, from deoxidized, Japanese electrolytic iron and sintered molybdenum. The ingot was homogenized for 6 hr at 1473°K and then worked, with intermediate anneals, into 6- and 16-mm-diam rods and 6-mm plate. Chemical analysis of the alloy gave, wt pct: Mo, 17.5 (11 at. pct); C, 0.003; Si, 0.002; S, 0.005; P, <0.002; and02, 0.0098. Solution treatments were carried out under a dynamic argon atmosphere in a vertical, "crusilite" element, furnace which had a facility for rapid quenching into iced water. Except for the study of the effect of solution treatment temperature, all specimens were solution-treated at 1573" * 2°K for 1 hr. Salt baths were used for the aging treatments. Specimens for hardness, density, and Young&apos;s modulus measurements were produced, after heat treatment, from the stock rod or bar using a precision silicon carbide slitting wheel. As described later, the quenching treatment produced local plastic strain in the stock material; consequently, care was taken to ensure that the specimens were not prepared from these regions. Those specimens used in the studies of the effects of prior deformation on the aging behavior were strained in compression in a Denison universal testing machine. Specimens for light metallographic observations were mechanically polished on successively finer grades of diamond paste down to and then etched in either alcoholic ferric chloride or in a 2 pct nital solution. Vickers diamond pyramid hardness data were obtained using a 30-kg load. At least five impressions were averaged for each determination. Density measurements were made using a displacement technique in which each specimen was weighed in air and in dibromoethane at 296°K. The specimens were cylindrical and weighed 3 to 4 g; all weighings were made on a balance reading to 1 x 10"5 g. For each specimen the mean value of five weighings was used to calculate the density. The density of the dibromoethane was determined using the displacement procedure and a standard nickel specimen. The error in an absolute density value was estimated to be HI.01 pct. To obtain the density as a function of aging time a single specimen was used and the density meas-

Jan 1, 1969

By Kiyoshi Azuma, Hiroshi Kametani

The variation of the dissolution behavior of a ferric oxide with calcining temperature has been investigated. Samples were prepared by thermal decomposition of ferric hydroxide, nitrate, oxalate, and sulfate at low temperature, followed by the calcination in the temperature range between 600" and 1200°C. The samples of eight series and a fine crystalline sample of hematite were dissolved in 1 N hydrochloric acid at 55.2°C and the results are represented on double-log graphs for convenience. It is confirmed that all dissolution courses follouj either the accelerated process or the parabolic process except in the special case of the crystalline hematite which dissolced in accordance with the uniform dissolution of a particle. Examinations of the physical properties of the oxide powders revealed that the surface area measured by the permeability method is strikingly relevant to the dissolution behavior of the oxide. In the previous paper,&apos; detailed data were presented on the effect of the kind of acid, the solution temperature, and the concentration of acid on the dissolution of two ferric oxides. It was also shown that these sam ples dissolved in strikingly different ways. The present investigation was carried out on the dissolution of various calcined samples prepared from various ferri salts by various methods to ascertain the course of dissolution. Pryor and Evans2 pointed out a change of the dissolution rate at around 700°C for a series of calcined ferric oxides prepared from the hydroxide. Several papers374 reported also the dissolution of ferric oxide samples. It seems, however, that a systematic account of the relationship between the dissolution behavior and physical properties of the oxide has not yet been given. This paper presents the variation of the dissolution of the oxide in relation to the calcining temperature and the change of physical properties of the calcines. EXPERIMENTAL Raw materials were prepared by precalcination of ferric hydroxide, thermal decomposition of ferric nitrate, oxalate, and sulfate, and aerial oxidation of ferric chloride vapor, at as low a temperature as possible. The products were crushed, ground, if necessary, and sieved with a 100-mesh Tylor screen prior to calcination, after which the specimens were dissolved in acid solution. The following is a detailed description of the preparation of the samples. Sample H. About 500 g of ferric chloride (guaranteed reagent) were dissolved in 5 liters of deionized water and filtered. Ferric hydroxide was precipitated by addition of the minimum amount of ammonium hydroxide solution, and the precipitate was washed continuously till chloride ion was not detected by silver nitrate solution, and then filtered. The filter cake was dried at 120°C for a week and ground, and the -100 mesh portion was used. Sample S. Ferric sulfate (guaranteed reagent) was pyrolytically decomposed in a crucible at 700°C for 24 hr and the product was sieved. In this case the following calcination was carried out at temperatures over 700°C. Sample B. Commercial ferric oxide (guaranteed reagent). About 15 kg of ferric nitrate were decomposed in a furnace maintained at 800°C for 2 hr. The actual temperature of the decomposition was not measured. The product was crushed and sieved, and the -100 mesh portion was used. Sample N. About 50 g of ferric nitrate (guaranteed reagent) were decomposed in a beaker in a sand bath until a red-brown dense solid was produced. This product was crushed and sieved, and subjected to complete decomposition at 500°C. The precalcined product was again sieved and used. Sample N2.5. Since the decomposition temperature was not controlled for sample AT, a different sample was prepared in a temperature-controlled furnace. The subscript represents the decomposition at 250°C. The product was treated in the same manner as sample N. Sample Nc. Under atmospheric pressure it is prac-tically inevitable that ferric nitrate hydrate melts to form a brown liquid at about 50°C before pyrolysis. For this reason, the salt was first slowly heated under reduced pressure (about 10-3 mm Hg measured in a trap refrigerated by dry ice-alcohol) to achieve dehydration without melting. About 5 hr were required for the dehydration and the partial decomposition. Then the temperature was elevated to 500° C in air for complete decomposition. The relatively porous product was sieved and used. Sample Ov. About 200 g of ferric oxalate hydrate (extra pure) were dehydrated under reduced pressure (as described above) followed by thermal decomposition at 500°C for 6 hr in air. The decomposition of this salt was accompanied by liberation of carbon monoxide, by which the ferric salt was initially reduced to a black powder. The powder changed in turn into brown ferric oxide as the gas liberation decreased and reoxidation predominated. The product consisted of sparkling fine particles passing through a 100-mesh screen. However it was ground and sieved as for the other samples. Sample D. Commercial fine powder for magnetic tape purposes. The preparation was as follows.5 Ferric chloride vapor and preheated excess air were mixed and passed into a reaction tube where oxidation took place at 450°C. The fine powder formed was collected in a cottrell chamber. The product was vacuum-degassed at 450°C for 1 hr and sieved.

Jan 1, 1969

By Arnt Solbu, Jomar Thonstad

The reaction between CO, and aluminum in cryolite-alumina melts in contact with aluminum has been studied by passing CO2 over the melt. In unstirred melts a homogeneous reaction between dissolved metal and dissolved CO2 was observed. In stirred melts in which convection was induced by bubbling argon through the melt, the dissolved metal apparently reacted mainly with gaseous CO2. The rate of formation of CO increased slightly with increasing depth of the melt, and it did not depend on whether CO2 was passed over or bubbled through the melt. The rate of formation of CO increased with increasing area of the metal/melt interface and with the application of anodic current to the metal. It is concluded that the dissolution of metal into the melt is the rate-determining reaction. THE current efficiency in aluminum electrolysis is determined by the rate of the recombination reaction between the anode gas and the metal: 2A1 + 3CO2—A12O3 + 3CO [1] as originally stated by Pearson and waddington.1 The occurrence of this reaction in cryolite-alumina melts in contact with aluminum was first verified experimentally by Schadinger.2 Thonstad3 has shown that the reaction may proceed further to give free carbon: 2A1 + 3CO— A12O3 + 3C [2] Normally only a few percent of the CO formed undergoes such reduction. The mechanism of these reactions has not yet been clarified. Aluminum, as well as CO,, is soluble in the melt. The solubility of aluminum in cryolite-alumina melts at around 1000°C corresponds to 75 x 10- 6 mole A1 per cu cm,4 while that of CO2 is only 3 x 10-6 mole CO, per cu cm.5 Taking into account the stoichiometry of Reaction [I], the ratio between dissolved aluminum and dissolved CO2 available for the reaction in a saturated melt is about 40. Therefore, as will be shown in the following, the reaction probably mainly occurs between gaseous COa and dissolved aluminum. The dissolved aluminum presumably consists of subvalent ions of aluminum and sodium.4&apos;6 Since the interpretation of the present results is not dependent upon the nature of this solution, the dissolved metal will be designated solely as Al+ in the following. The reaction can then be divided into four steps: A) dissolution of metal, e.g., 2A1 + Al3 — 3A1+ [3] B) diffusion of dissolved metal through a boundary layer; C) transport of dissolved metal through the bulk of the melt; D) Reaction [1]. If dissolved CO, takes part in the reaction, three additional steps embodying the dissolution and transport of CO2 must be added. schadinger2 observed, when bubbling CO2 through the melt, that the rate of formation of CO (in the following designated rfco) did not depend on the distance from the metal surface. The results also indicate that the rate of bubbling did not affect the rfco. When passing CO, over the melt, Revazyan7 found that the loss of metal did not depend on the depth of the melt above the metal or on the flow rate of CO2, and concluded that Step A is rate-determining. In an unstirred melt, however, Gjerstad and welch8 found that the rfCo decreased with increasing depth of the melt, indicating that step C was rate-determining. It thus appears that the rate control of the process depends on the experimental conditions, particularly on the convection. In the present measurements the reaction has been studied in unstirred as well as in stirred melts. EXPERIMENTAL AND RESULTS The experiments were carried out at 1000°C in a Kanthal furnace with a 10-cm uniform temperature zone (±0.l°C). The melts were made up of "super purity" aluminum (99.998 pct), hand-picked natural cryolite, and reagent-grade alumina. In experiments where alumina crucibles were used, the alumina content in the melt was close to saturation (13.5 wt pct9); otherwise it was 4 wt pct. Pure Co2 (99.85 pct) was passed over the melt, and the exit gas was analyzed for CO2 and CO by the conventional absorption method.3 From the weighed amount of CO (as CO2) the rfco was calculated as the number of moles of CO formed per min per sq cm of the surface area of the melt. The amount of carbon formed by Reaction [2] was not determined. As already indicated the rfco is much higher than the rfC, by Reaction [2]. Since the rfC probably is proportional to the rfco, the measured rfco should then the proportional to, but slightly lower than, the total rate of Reactions [I] and 121. In general the scatter of results obtained in duplicate measurements was ±5 to 10 pct, while within a given run a precision of ±3 to 5 pct was obtained. The various crucible assemblies that were used will be described below. Measurements in Unstirred Melts. When carrying out aluminum electrolysis in small alumina crucibles. Tuset10 observed that after solidification the lower part of the electrolyte was gray and contained free metal, while the upper part near the anode was white and contained no metal. One may test for the presence of free metal by treating with dilute hydrochlorid acid.

Jan 1, 1969

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

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

Jan 1, 1969

By J. R. Bell, W. J. Childs, J. H. Bucher, G. A. Wilber

A technique for determining recrystallization times as short as 0.10 sec was developed utilizing the "Gleeble", a commercially available testing system designed for the study of short-time, high-temperaLure themal and mechanical processes. The procedure consisted of heating a small tensile specimen to a given temperature of hot deformation, loading to a given reduction in area, unloading, delaying various intervals at temperature, and then reloading- to failure. The magnitude of the ultimate load obtained upon reloading decreased with delay lime as recrys-lallization proceeded. The technique was applied to austenite recrystallization in AISI 1010 and AISI 1010 uith 0.02 pct Cb steels. For each steel the reduction in area given the specimen on the first pull was mainlairred at 30 ± 5 pct and recrystallization times deterntined at various temperatures. The results indicaled a significantly slower rate of recrystallization for the columbium-modified composition, suggested the presence of- a recovery stage in the softening process , and indicated a greatly increased softening rate at a temperatuve where significant allotropic transformation to a partially ferritic Structure could occur. In recent years increasing attention has been paid to the fact that the process of recrystallization of austenite deformed at elevated temperatures is far from instantaneous at many practical hot-working temperatures.1-3 This realization has given rise to such terms as hot cold-working1 or warm-working,2 These terms generally describe processes where the recrystallization rate at the temperature of deformation is slow enough to have an appreciable effect on mechanical properties despite a relatively high deformation ternperature. The mechanical properties of interest can be either the properties at the deformation temperature as in hot-workability studies4 or the room-temperature properties after cooling as in the many recent studies of various thermomechanical processes172 where heat treatment and deformation are intentionally combined to give a unique set of room-temperature properties. Because of this interest in processes where the austenite recrystallization kinetics can be an important variable, the development of quantitative methods of following the course of short-time, high-temperature recrystallization has received increasing attention.l,3,5 The experimental methods to date have, in general, relied upon rapidly deforming the austenite, holding at temperature for various brief intervals, quenching as G.A.WILBER and W. J. CHILDS, Members AIME,are Research-Fellow and Professor, respectively, Rensselaer Polytechnic Institute, Troy, N. Y. J. R. BELL and J. H. BUCHER, Member AIME, are Research Engineer and Research Supervisor, respectively, Graham Research Laboratory, Jones & Laughlin Steel Co., Pittsburgh, Pa. Manuscript submitted March 13, 1968. IMD. rapidly as possible, and then using room-temperature measurements to follow the recrystallization process. Although such methods can be successfully applied to certain alloy steels, the existence of the allotropic transformation during cooling of plain-carbon or low-alloy steels tends to obscure the results. Thus, such room-temperature measurements as hardness and X-ray line widths do not correlate well with the extent of austenite recrystallization before quenching,5 and results based on room-temperature microstruc-tural observations are dependent upon the success in correlating the observed structure with the prior aus-tenitic grain structure.1,3,5 The purpose of the present work was to develop a quantitative method for the determination of short-time, high-temperature recrystallization rates, based on measurements made at the temperature of deformation. EXPERIMENTAL TECHNIQUE The basic technique consisted of heating a small tensile specimen to a given temperature of hot deformation, loading to a given reduction in area, unloading, delaying various intervals at temperature, and then reloading to failure. The data were obtained in the form of traces of load and elongation as a function of time. Due to the high deformation temperature, the strain hardening introduced during initial loading was progressively annealed out with holding time after unloading and the loads obtained upon reloading decreased as this softening proceeded. Although the value of the second load at any Consistent point On the load-elongation curve could have been used as a measure of the degree of softening, the most convenient to use was the ultimate load. The softening indicated by the decrease in the second ultimate load with time is essentially a process of annealing of cold-worked material at a high deformation temperature. Although some recovery grain growth may contribute to such a softening process, it is generally considered that the major softening which must take place to achieve complete removal of substantial Strain hardening will occur by the formation of new, stress-free grains. As the results of this work indicate that essentially complete removal of strain hardening did in fact occur. the primary softening process will be attributed to recrystallization, and specific reference made where it appears that other mechanisms may be contributing to the total observed softening. It would, of course, be of interest to attempt to correlate the results of this work with the actual austenite fraction recrystallized as determined by other techniques. This was not attempted in the present work because it would have required running a large number of additional specimens and, as discussed previously, there is limited assurance that the results would accurately reflect the prior austenite fraction recrys-

Jan 1, 1969

By C. L. Sollenbeger, R. B. Greenwalt

PERHAPS the most widely used dispersants or gangue depressants in nonmetallic flotation are sodium silicates, which vary in silica-to-soda ratio from 1 to 3.75. Typical manufactured silicates in order of decreasing solubility and increasing amounts of silica are Metso, silica-to-soda ratio of 1.00; D, 2.00; RU, 2.40; K, 2.90; N, 3.22; and S-35, 3.75.* References in flotation literature1,2 to the use of sodium silicates are often weak because they fail to mention the type of silicate used. Metso and silicate N have occasionally been mentioned, but when the type of silicate is not mentioned, it is usually assumed to be N, the cheapest of the soluble silicates and the one recommended by sodium silicate manufacturers as a flotation agent. In the All is-Chalmers Research Laboratories a systematic study was made of the effect of different alkali-silica ratios on the concentration by flotation of two scheelite ores. One of these was a high grade ore from the Sang Dong mine in Korea. The effect of such factors as pH; addition agents; and conditioning time, temperature, and pulp density on the flotation efficiency of this ore have been described previously. The other ore was a low grade ore from Getchell Mines Inc., Nevada. The mineralogy and techniques of concentrating this ore have been described by Kunze. Hereafter these ores will be referred to as the Korean and Nevada ores. Experiments were made with both to determine the effect of three factors—-type of silicate, concentration of silicate, and pH of the pulp—on recovery and grade of tungsten in a rougher concentrate. Average WO, content of the Korean ore was 1.50 pct and of the Nevada ore 0.27 pct. The predominant tungsten mineral in both ores was scheelite, which was accompanied by a small amount of powellite. The powellite and scheelite were finely disseminated through both ores and required a —200 mesh grind for liberation. Major gangue minerals in the Korean ore, in decreasing order of abundance, were amphi-boles, quartz, biotite, garnet, fluorite, and calcite. Bulk sulfides composed about 3 pct of the total weight. Gangue in the Nevada ore, in descending order of abundance, was garnet, alpha quartz, calcite, phlogopite, wollastonite, and amphiboles. Sulfide minerals were 3 to 4 pct of total weight. Batch flotation experiments were made with 500-g samples of ore, each sample wet-ground to 90 pct passing 200 mesh. The finely ground ore was floated in a Fagergren batch cell at 25 pct solids. The natural pH of the Nevada ore was 8.9 and of the Korean ore, 8.5. The D, RU, K, N, and S-35 sodium silicates were obtained in colloidal dispersions with varying amounts of water. The most alkaline, Metso, was in dry powdered form. For convenience in addition, 5 pct solutions by weight were prepared from each of the silicates, on the basis of dry sodium silicate dissolved in the correct amount of distilled water. Chemical analyses of the various silicates are given in Table I, together with the pH of the 5 pct solutions. A preliminary bulk sulfide float was made with secondary butyl xanthate as the collector and pine oil as the frother. The WO] analysis of the sulfide concentrate was nearly 1 pct for the Korean ore and about 0.1 pct for the Nevada ore. The tungsten contained in the sulfide concentrate constituted about 3 pct of the total tungsten in each ore. No effort was made to recover these tungsten values. The scheelite was floated with oleic acid. Adjustments in pH were made with sulfuric acid or sodium carbonate. A 1 pct solution of 85 pct Aerosol OT was sprayed on the froth and sides of the cell during the scheelite float to aid in dispersing the minerals and to decrease the entrapment of gangue particles. Six tests were planned for each of the six types of silicate in which concentrations of 1, 2, and 4 1b of silicate per ton of dry ore were investigated at both 6.5 and 10 pH. All tests were made at room temperature. The performance of each silicate was judged from the grade and recovery of WO, in the scheelite rougher concentrate. Tungsten recovery was calculated on the basis of the scheelite remaining in the ore after the preliminary sulfide float. Testing of each silicate at three levels of concentration and two levels of pH required 36 tests with each scheelite ore. Variance analyses were performed on the concentrate grades and recoveries to determine whether or not the type of sodium silicate, the concentration of sodium silicate, or the pH significantly affected recovery or grade. Results Concentrate Grade: A variance analysis of the concentrate grades for the Korean ore showed that concentration of the silicate and pH of the ore pulp were major factors in producing a high grade concentrate. Also, the silica- to-so da ratio was important as an interaction with pH. The concentrate grade vs silica-to-soda ratio is plotted in Fig. 1. The curves show that the concentrate grade improved with an increase in concentration of sodium silicate and also

Jan 1, 1959

By H. Biloni, R. Morando

The surface structure and substructure of Al-Cu alloys solidified as conventional ingots and under particular conditions such as those used by Bower and Flemings are studied. The influence of lampblack coating on the mold walls is especially considered and the results compared with those obtained in copper and graphite molds where no coatings exist. When high heat extraction conditions exist the observations show that mechanism of copious nucleation is responsible for most of the chill zone. When the heat extraction through the mold walls is low, a coarse grain structure with dendritic morphology arises, with a size that depends on the degree of convection present, analogous to that analyzed by Bower and Flemings. In both cases the effect of the convection on the macroscopic and microscopic appearance is discussed. The ingot macrostructure consists of one or more of three zones: "chill zone", "columnar zone", and central "equiaxed zone". The mechanism of the columnar-equiaxed transition has been subject of considerable interest and at present at least three theories exist about the formation of the equiaxed region: 1) the constitutional supercooling theory1 maintains that the equiaxed crystals nucleate after the columnar zone has formed, as a result of the constitutional supercooling of the remaining liquid; 2) chalmers2 pointed out, however, that there were several objections to this proposal, and that consideration should be given to the possibility that all the crystals, equiaxed as well as columnar, originated during the initial chilling of the liquid layer in contact with the mold; 3) Jackson et aL3 and O&apos;Hara and ~iller~ suggested that a remelting mechanism of the dendrite arms is responsible for the formation of the equiaxed region. After the work of Cole and Bolling and other authors6 it became evident that convection (natural, reduced, or forced) plays a very important role in the transition from columnar to equiaxed and on the size of the resultant equiaxed structure. Until recently the accepted explanation of the chill zone was that it occurs as a result of copious nucleation in the liquid layer in contact with the mold walls.798 The columnar region is a subsequent result of the growth of favorably oriented grains and, as a result of a selection mechanism studied by Walton and Chalmers,9 elongated grains with marked texture are formed. Recently, however, Bower and Flemings" using an ingenious laboratory experiment introduced the idea that the "copious nucleation" mechanism is not responsible for the formation of the chill zone and that the presence of convection, introducing some form of "crystal multiplication", plays a decisive role in the formation of the chill zone. Unfortunately, it is important to consider that for their conclusions Bower and Flemings extrapolated the results obtained in their special experiments to the case of conventional ingots, and that these authors only analyzed the macrostructures of the specimens. Let us consider the work by Biloni and chalmers" concerning predendritic solidification. These authors were able to show that a study of the segregation substructure of A1-Cu gives information about the nucleation and growth of crystals formed in contact with a cold surface. A spherical predendritic region characterizes the first part of every grain nucleated in contact with the surface as a result of the chill effect. The aim of this paper is to elucidate through the observation of the segregation substructure the conditions under which (in the Bower and Flemings type of experiments and in conventional ingots) either the nucleation or the multiplication mechanism gives rise to the structure in contact with the mold walls. I) EXPERIMENTAL TECHNIQUES The experiments were performed on two alloys: Al-1 wt pct Cu and A1-5 wt pct Cu. The purity of the aluminum was 99.99 pct and the copper 99.999 pct. The results obtained with both alloys were similar. In the Bower and Flemings type of experiments the apparatus employed to obtain rapid solidification against a surface was similar to that used by those authors. The liquid was drawn by partial vacuum into the thin section mold cavity. Plate casts were 5 cm wide and usually 7.5 cm high. The thicknesses of the cast were 0.1 and 0.3 cm. Two different materials were used for the mold, copper and nuclear-grade graphite. The internal mold surfaces were polished and left uncoated for some experiments. In other experiments, the copper or graphite surface was coated with a thin film of lampblack material. In some of these particular experiments one of the mold walls was left with an uncoated region (usually in the form of a cross). The conventional ingots were cast in graphite or copper molds. In different experiments the mold walls were sometimes uncoated or coated with lampblack material. The results obtained in conventional and Bower and Flemings copper molds were compared with those obtained with copper molds coated with a very thin film of graphite; the results obtained were essentially similar. The size of the conventional ingots was 5 cm diam and 7 cm high in all cases. The cast surfaces produced by the Bower and Flemings type of experiments and conventional methods were observed macroscopically and microscopically without any metallographic preparation. As Biloni and Chalmers showed," the observation of the chill surface can give considerable information about the structure and segregation substructure.

Jan 1, 1969

By N. J. Grant, B. C. Giessen, Paul Predecki

ALLOYS of gold, silver, and aluminum with elements of the groups BII, BIII, BIV, and BV were prepared by a rapid quenching technique (splat) and were examined by X-ray diffraction. Five new intermediate phases were found and will be described briefly herein. For the gold and silver systems, the concentration ranges having an electron/atom ratio e/a of 1.4 to 1.5 ("3/2 Hume-Rothery phases") were studied primarily. Master alloys were prepared from high-purity metals (99.9+ pct or better) by melting either in evacuated fused silica capsules or by nonconsum-able-electrode arc melting in an argon atmosphere. Small pieces, 20 to 50 mg, of each alloy were blast-atomized to form a splat, by a technique similar to that described by Duwez and Willens.1 The technique used for this study is described in detail in Ref. 2; it utilizes a resistance-heated graphite crucible with a small hole at the bottom, directed toward a metal substrate or quenching plate. The prepared alloy rests over the fine hole, through which it is expelled by an explosion shock wave in the form of fine droplets (1 to 50 µ) of molten metal onto a copper or silver substrate, which is maintained at about -190°C. The resulting very high cooling rates (see Ref. 2 for quantitative measurements) can prevent the process of nuclea-tion and growth in many instances, resulting in the formation of metastable phases. The splat particles were transferred to a GE-XRD5 diffractometer and maintained at -190°C, where they were examined with CuKa radiation. The samples were then allowed to warm to room temperature or were heated to higher temperatures until the equilibrium structures formed. Of fifteen alloy systems considered, nonequi-librium structures were encountered in six; these are described below and summarized in Table I. In the system Au-Sb a metastable £ phase (A3 type, hcp, a = 2.898 + 0.002A; c = 4.731 * 0.004A; c/a = 1.633) was found in the concentration range Au + 13 to 15 at. pct Sb. This phase is isomorphous with the stable phases in the systems Au-Cd, Au-In, and Au-Sn, all at an average e/a ratio of 1.4 to 1.5. The concentration range of one-phase metastable was deduced from the small amounts of supersaturated gold solid-solution phase present in the splat product. It was found that ? could also be retained by splatting onto a substrate held at room temperature: however, decomposed into the equilibrium phases Au + AuSb2 after heating to 200°C for 1/2 hr, or on holding the powdered splatted alloy at 20°C for several months. Calorimetric measurements will be made in an attempt to decide the question whether ? is metastable at all temperatures or whether it is a stable phase at low temperatures. There is evidence that another phase, possibly also close-packed but with a different stacking sequence, can be obtained by rapid quenching of alloys with a different antimony content. Klement, Willens, and Duwez3 reported the existence of an amorphous phase on quenching Au-Si alloys (25 at. pct Si) to - 196°C. They found that on heating to room temperature another phase of unknown crystal structure was formed. This was confirmed (see Table I); however, the new crystalline phase, designated as ?, could also be formed simply by rapid quenching to room temperature, and even was found to exist already in the as-cast Au + 20 at. pct Si alloy. It was found that ? decomposed into Au + Si on the specimen surface at room temperature. This behavior, and the question whether or not there is an equilibrium-temperature region for ?, have not yet been resolved. It is probable that ? (Au + 20 to 21 at. pct Si) is cubic of the -brass type (D81-3) with a = 9.60, + 0.01A and N = 52 atoms per cell [compare 6 (CU-Sn)4]. Except for two very weak lines, the powder pattern of about thirty lines could be indexed on this basis; however, a determination of the atom positions has not yet been attempted. For Au-Ge the C phase was observed at about 21 at. pct Ge as reported by Luo et at.5 Lattice parameters a = 2.876A, c = 4.73,A, c/a = 1.64 were found. In the Au-Pb system, formation of a ? phase was not observed, but in the lead-rich region at 75 at. pct Pb, broad peaks belonging to an amorphous phase were found. The maximum diffracted intensity occurred at 28 = 32.4 deg which is about 1 deg larger than the position of the (111) line of lead (Cuka). For Ag-Pb, an amorphous phase analogous to the one found in the Au-Pb system was observed; this metastable phase exists probably at about 75 at. pct Pb. Since no lead-rich alloys were tested, all alloys consisted of silver + amorphous phase at -190°C. In A1-Ge alloys, line-rich and complex powder patterns were obtained at about 30 at. pct Ge; they bear similarities to those of aluminum and germanium, but are of lower symmetry; the existence of more than one intermediate phase is possible. The authors are grateful to the Kennecott Copper Corp. for Fellowship support, and ARPA (Contract

Jan 1, 1965

By John L. Schroder

The demands for increased productivity on the 1967 coal industry have generated new operating trends and fresh approaches to old methods, which have enabled the industry to keep pace with the expanding economy. Changes, while not radical in concept or design, have been plentiful and are marked by the refinement of the already tried, tested and proven. Perhaps not since World War II have there been demands on equipment manufacturers to design and deliver such diversified types of machines as those required by the industry in the past year. Equipment developments-following a plan which calls for higher productivity, lower maintenance costs and greater machine availability- have tended more toward increased horsepower and heavier, more rugged equipment. Electrical and mechanical components, designed in many instances with maximum reliability rather than initial costs as the main criterion, have contributed to the improvements in over-all performance. High-strength, specialty steels are finding use in a wide range of equipment applications. The horsepower capacity of electric motors being installed is more frequently being rated on a continuous basis rather than the former one hr or less and, as a result, fewer failures now occur because of overloading. These developments reflect the pyramiding cost of equipment down-time and represent definitive progress in reducing the magnitude of the problem.

Jan 2, 1968

By T. A. Rickard

Do not write until you have something to say. Think first; then write. In order to be understood, you must know what you wish to say. Clear writing is the consequence of clear thinking. Therefore consider your subject well before you begin to write; ruminate on it; marshal the salient facts in your mind; saturate yourself with the ideas you wish to express and with cognate ideas; then express yourself deliberately. If you are bubbling over with your subject the words will come, but you might as well expect to sail without a breeze as hope to give life to words without the living thought. Here I may advert to the fact that among the uneducated it is a common expectation to acquire the knack of writing without taking the trouble to study the art of literature. I overheard a woman in a suburban train remark to her neighbor: "I&apos;d like to be able to write well without stopping to think about it". She was one of many that would like to do a thing well without the trouble of thinking; but it cannot be done in respect of anything to which thought is essential. The possession of a good voice does not justify a person in expecting to sing successfully to a large audience; before singing in public one has to master the technique of singing; one has to learn first how to breathe properly, how to enunciate, and many other things. The successful singer is an artist, not a megaphone. Most of us would regard a man or a woman without any training in the art of singing as a fool or an impostor if he or she were to give a public concert, yet we do not recognize the equal foolishness and imposture of persons that write books before they have studied the technique of writing. That is why so many books are unreadable, and why many books by clever men are difficult to read. They start to write books before

Jan 1, 1931

By O. E., Kiessling

THE better control of production was made the topic for a special program of the annual meeting of the Institute last February. In the discussion at that meeting it was brought out that in many branches of the mineral industry (as in other industries), there was faulty industrial coordination. Those who were best informed by reason of their intimate connection with coal, copper, oil, iron, lead and zinc, and almost all other of the essential minerals pointed to a condition of chronic over-capacity, to the dissipating use of irreplaceable minerals, to an unstabilized price structure, and to over-stimulatecl production and the destruction of some mineral resources over and above what is thought to be the needs of prudent cur- rent consumption. The discussion went far enough to point out the existence of various problems, and the question then raised was "what can be done by way of self-coordination of industry?" by "production control from within?" or in other words, "how can the mineral industry protect its resources against waste and at the same time protect both the producer and consumer against loss from prices that are too low or too high?"

Jan 1, 1928

By J. A. Retty

HOLLINGER CONSOLIDATED GOLD MINES LTD., through two subsidiary companies, has the exclusive right to prospect in two contiguous areas in central Labrador. This paper presents the results of the mineral exploration that has been conducted in these areas to date. One of the subsidiaries of Hollinger. the Labrador Mining and Exploration Co. Ltd., under an agreement with the Newfoundland Commission of Government, holds an area of approximately 20,000 sq.mi., which comprises the western portion of Newfoundland-Labrador and includes the upper basins of the Hamilton and Naskaupi Rivers. (The main area of the deposits so far discovered may be located on a map at about 67° west longitude and 55° north latitude.) The other subsidiary of Hollinger, Hollinger North Shore Exploration Co. Ltd., has licensed from the Province of Quebec an area of approximately 3900 sq.mi. lying directly north of the Newfoundland-controlled area at the headwaters of the George, Whale, and Swampy Bay Rivers. The M. A. Hanna Co., large iron-ore operators of the Lake Superior region, are participating in the project. With the exception of the years 1940 and 1941, field work has been conducted in the Newfoundland area since 1936, and in the Quebec area since 1939. Hollinger assumed the management in 1942. The field base is at Hollinger Lake, some 300 miles north of the tidewater base at Seven Islands, Quebec, which, in turn, is just west of the mouth of the Moisie River, on the Gulf of St. Lawrence. Air transportation is used exclusively to service the operation.

Jan 1, 1945

By J. A. Hutcheson

NO one questions that it is technically possible to achieve the controlled release of atomic energy in a form that can be converted into heat or electricity. However, before this is actually an accomplished fact a great amount of work must .be done. This work falls into two general classifications: research and engineering development. At present a research program is under way in this country, co-ordinated and directed by the Atomic Energy Commission, which, as time goes on, will uncover fundamental knowledge of this new science that is essential before industrial applications of atomic energy are practical. Undoubtedly therefore, as the store of available knowledge increases, a time will come when answers to the many questions relating to practicality of atomic energy in industry can be determined with reasonable certainty. That the application of atomic energy in industry will eventually be proved practical is assumed. What then are the engineering problems that must be solved before the first practical electric power generating station can be built?

Jan 1, 1948

By TRUMAN S. FULLER

THE GREAT INTEREST in decomposition and trans- formation, so evident in the study of alloys during the last two years, was reflected in the many papers on this subject, presented at the first session of the Institute of Metals, Tuesday morning. Dr. F. A. Thomson, of Montana State School of Mines, presented the first paper by C. Wilson, H. F. Silliman, and E. C. Little, "Rate of Precipitation of Nickel Silicide and Cobalt Silicide in the Hardenable Copper-nickel-silicon and Copper- cobalt-silicon Alloys." Dr. R. F. Mehl, in discussing this paper, stated that the title was somewhat deceptive, as it indicated that the rate of precipitation is determined; the method used is a measurement of electrical conductivity and hardness, neither of which is suitable for a quantitative measurement of rates of reaction or precipitation in the solid state. Hardness is also uncertain because it depends so much upon particle size. Of the various methods proposed for the study of rate of reaction and precipitation the evaluation of volume of reaction produced from the area of photomicrograph is the best.

Jan 1, 1933

By AIME AIME

NEW YORKERS look forward to the third week of February as the time of the year when they can count on seeing their friends-from far and near gathered in the city for the four-day annual session of the Institute.., Indeed, the metropolitan district is so large that in engineer who lives in New, Jersey and has his office on the lower end of Manhattan island may easily pass a whole year without seeing an acquaintance who lives in Westchester and has an office near Forty-second Street. If the Institute served no other function than to provide a place where friendship may be renewed, ideas exchanged, and new acquaintances made it would still be worth while. But when about 30 technical sessions at which about 160 papers are read and discussed are compressed into four days the annual meeting is also entitled to high rank as an intensive course of post-graduate instruction in the newest development in mining and metallurgical technology. Last, but not least, it is the occasion of a good time for one and all, even if they do get more than a little behind on sleep before the end of the fourth day. Nine o&apos;clock is the time set on Monday morning for the beginning of registration, but a half-hour before that a number have always &apos;put in an appearance, and this is fortunate, because by 10 o&apos;clock four sessions had begun, those on mining methods, geophysics, a round table on the valuation of coal, and the session of the Local Section delegates. Three committees of the A. S. T. M. were also in simultaneous session, so the meeting may be fairly said to have started "in high."

Jan 1, 1931

By W. B. Heroy

ONLY through the mineral fuels can large amounts of energy be transported to great dlstances and stored for long periods for future use. Coal has the advantages over oil of greater safety of handling and smaller losses in storage. But oil is, in the present stage of technical advancement, the more economical source of liquid fuel for internal-combustion motors. No method for direct use of coal in such motors has been developed that can compete with petroleum products. The automoblle engine and the airplane motor are designed to make the most effective use of gasoline.

Jan 1, 1944

By ROBERT B. COONS

SELECTIVE SERVICE must meet three important demands for man power: (1) Activities concerned with production of war goods. (2) The armed forces. (3) Civilian activities and institutions the continuance of which are essential to maintaining the structure of our American democracy. In the above enumeration of demands I have placed everything, including most of our most prized possessions and activities, after the demand for men for war production and the armed forces. To establish an order between the latter two is difficult. For the time being, at least, the Selective Service policy is to make sure that we avoid the risk of "too little and too late." No soldier, sailor, or marine should be sent from these shores to risk his life without the assurance of having a gun, clothes, food, and medical supplies. Therefore, the premium is now being placed on man power for war production and in our process of selection no stone is left unturned to see that our agencies are fully informed of the needs of war production. Our procedures set up recourses for employers of war-production man power so that their activities need not be disrupted, at least not until they have had time to train replacements.

Jan 1, 1942