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By G. F. Bolling

Single crystals of each metal were deformed at 77°K and heated at constant rates, variously in the range 0.125" to 4o°Kper min from 77" to -390oK, while being monitored in an X-ray diffractometer. Changes in diffraction-peak heights and line breadths were used to ascertain the temperature ranges of recrystalliza-tion. The results were subjected to the analysis of nicholas' in order to obtain the rate-controlling activation energies,Q. In this analysis no recourse to a separate and distinct nucleation stage is required and the results of studying recrystallization proved consistent with the hypothesis of a constant number of nuclei or equivalent hypotheses. The values Pb = 5.5 ± 0.5 keal per mole Zn ~ 7.5 Sn - 5 Bi - 9. 5 correspond for lead, zinc, and tin to activation energies obtained elsewhere for grain boundary migration, and for bismuth and lead to previous studies of re-crystallization by Barrett.6 This correlation allows the conclusions that interference from recovery was minimal and that the observed recrystallization rates in these pure metals are effectively governed by grain boundary migration. Good agreement was not found between the results of this kind of study in zone-refined aluminum and previous work; and supplementary isothermral experiments involving hardness tests and metallography did not resolve the discrepancy. Nevertheless, at least a range,Q = 11.5 ± 2 keal per mole, can be assigned to the activation energy for boundary migration in aluminum. An experimental study of one aspect of the recrystallization process is presented here for four metals of different crystal structure. The metals chosen for study were all zone-refined to reduce impurity effects, but the attendant high purity presented a difficulty. For any reasonably high driving force a "re-crystallization temperature", TR, is in the range of 0.25 T,, where T, is the absolute melting point, and study was therefore restricted to lower temperatures. An X-ray technique under constant heating-rate conditions adequate above 90°K was devised for the study; in consequence, a newer type of analysis following Nicholas1 had to be used to obtain quantitative information about activation energies. The standard methods of studying recrystallization have involved the comparable analyses of Johnson and Mehl2 and Avrami3 which are reviewed by Burke and Turnbull.* The general analysis4 which is applied only to isothermal studies using any of various investigative techniques states:

Jan 1, 1968

By T. S. Lundy, R. E. Pawel, F. R. Winslow, C. J. McHargue

The volume-diffusion coefficients of Nb-95 and Ta-182 in niobium have been measured over the temperature range 878° to 2400°C. High-temperature specimens (T 21500°C) were sectioned by conventional lathe and grinding techniques while low-temperature specimens were sectioned by an anodizing and stripping technique previously described. Over a range of more than ten orders of magnitude in diffusivity, the self-diffusion data is well-represented by the equation: D = (1.1+ 0.2) exp [- (96,000 * 900)/RT ] cm2/sec Upward deviations from this line are explained by short-circuit diffusion in combination with the loss of resolution of the sectioning techniques. Oxygen contamination within the range 100 to 450 ppm was found to have little or no effect on the self-diffusivitj 01 niobium. In a limited number of measurements, the diffusivity of Ta-182 in niobium was found to be about half that of Nb-95 in niobium. These data may be described by D = (I.0+0.90.5)exp [- (99,300 * 2400) /RT ] PREVIOUSLY reported studies of self-diffusion in niobium were by Resnick and Castleman1 and Peart, Graham, and Tomlin.2 The data of Resnick and Castleman over a temperature range 1585" to 2120°C show considerable scatter but. can be represented by D = (12.4 *0.8) exp [-(105,000+3OOO)/RT] cm2/sec The limited data of Peart, Graham, and Tomlin follow the equation D = 1.3 exp (-95,00O/RT) cm2/sec In view of recent diffusion data for ß zirconium3 and 0 titanium4 in which Arrhenius-type plots do not yield straight lines and of the potential high- temperature uses of niobium and its alloys, we thought it important to investigate the diffusion behavior of this bcc refractory metal over a large temperature range. This has recently been done for molybdenum,5 chromium,6 vanadium,"" and tantalum.9 Niobium was a particularly suitable material for this study largely because of the development of an anodizing and stripping sectioning technique which enables diffusivities as small as l0-19' sq cm per sec to be determined accurately.10 In addition to self-diffusion data, data were obtained for the diffusion of Ta-182 in niobium and for the effect of varying oxygen content on self-diffusion. I) EXPERIMENTAL PROCEDURE Materials. The niobium was obtained from three sources: 1) melting stock from Shieldalloy Corp., 2) electron-beam melted single crystals, 1/2 in. diameter, from Semi-Elements, Inc., and 3) oxygen-doped, electron-beam melted single crystals from Materials Research Corp. The melting stock was electron-beam melted and specimens 5/8 in. diameter by 1/2 in. long were machined from the center of the bar. The analysis supplied by the vendor and an interstitial analysis of one of the specimens are given in Table I. The single crystals (type 2 above) were cut with a jeweler's saw to specimens about 3/8 in. long. The interstitial analysis of this material is given in Table 11. This material was used

Jan 1, 1965

By W. M. Lehrer

RECENT development of high-temperature brazing alloys has required information regarding the eutec-tic temperature and composition of the Pd-rich section of the Pd-B system.. Literature on this subject was found to be scanty with no complete system yet determined. Buddery and welch1 report an inter-metallic compound occurring in the Pd-B system at 6.33 wt pct B (PdsBz). Another source, Sieverts and Bruning,2 indicates that after annealing at 700°C, a 1.6 and a 2.0 wt pct B alloy were two phase whereas a 0.75 pct B alloy was single phase. Recent work3 using a hot-stage microscope has proposed a eutectic temperature of 743OC. This method utilized the observation of the onset of incipient melting at grain boundaries. The eutectic composition, however, was not determined. METHODS AND PR0CEDURES Five alloys were prepared by triple inert arc-melting high-purity palladium (95.98 pct) with additions of 2 to 6 pct purified amorphous boron. The alloys were crushed within a hardened steel mortar with a steel pestle. The 2 pct alloy, however, was too tough to be crushed in the above manner so was crushed by successive reductions through a rolling mill. Approximately 17 to 18 g of the crushed alloy was used in the thermal analysis. The alloys were melted in pure quartz crucibles. The thermocouple protection tubes were also of quartz and fused along the inside wall of crucibles to prevent floating of the thermocouple. This was an expediency as centering of the thermocouple in the melt would have been preferable. Melting was done in a tube furnace with a slow flow of tank helium maintained as a protective atmosphere. Heating and cooling rates were maintained at 3.5OC per min through the critical temperature ranges by means of a synchronous motor hook-up to a furnace controller. All specimens were heated to 100°C over the indicated liquidus on heating prior to reversing to the cooling cycle. Specimens emerged from the furnace with mirrorlike brightness attesting to the protective quality of the helium atmosphere. Thermal arrests were detected by the differential thermocouple technique using chrome l-alumel couples and nickel as the reference specimen. Arrests were recorded on a Leeds-Northrup automatic X-Y recorder. The specimen temperature and temperature difference were read to + 7.5OC and ± 1.5OC, respectively. These readings were well within the sensitivity of the instrument amplifier. Chromel-alumel couples were used in lieu of Pt-Rh as very few arrests were contemplated in excess of 1200" to 1300°C, the approach of instability. No standardization was performed on these thermocouples subsequent to their use. RESULTS The thermal arrest temperatures obtained are plotted in Fig. 1 as a function of wt pct B. The composition function was obtained by chemical analysis of portions of the specimens after the thermal analysis was completed. The 2 to 6 pct nominal alloys were found to have 1.80, 2.35, 3.65, 4.18 and 5.90

Jan 1, 1960

By Jeffrey L. Thompson, Kenneth A. Gutschick, Robert C. Freas, Robert S. Boynton

Lime, the "versatile chemical," is, generally speaking, a calcined or burned form of limestone commonly known as quicklime, calcium oxide or calcia, or, when water is added, calcium hydroxide or slaked lime. Almost 40 different lime products are available, a fact which has contributed to the rather loose use of the term lime as well as to much confusion and misunderstanding. The term is frequently, albeit erroneously, used to denote almost any kind of calcareous material or finely ground form of limestone or dolomite. Lime is usually made from high-calcium or high-magnesium limestone, generally having a minimum of 97% combined carbonate content. Normally, high-calcium limes contain less than 5% MgO. When the lime is produced from a high-magnesium limestone, the product is referred to as dolomitic lime. Calcination, or the production of lime, has its origins in the earliest days of alchemy, with the general reaction class having been identified in an Arabic text printed in 1000 A.D. It was much later, however, in the mid-1700s to the mid-1800s before this basic reaction became understood from a scientific perspective. The production of lime has been so basic and simple that its underlying scientific principles have over the years received only intermittent investigation. Rather, much of the thought and inquiry has been directed toward the development of kilns. Thus, it has only been in the last 15 to 20 years that lime has received any concentrated scientific investigation relative to the thermodynamics and kinetics of the calcination and hydration reactions. Calcination refers to a broad class of reactions, of which the lime/limestone reaction is just one, wherein a substance is heated to less than its melting point, resulting in a weight gain or weight loss. In the calcination of limestone to produce lime, the basic chemical reaction is as follows: [CaCO3 (limestone) + heat (1000° to 1300°C)= 100 CaO (quicklime) + CO2 T 5644 or CaCO3 • MgCO3 (limestone) 10084 + heat (900°C to 1200°C) CaO • MgO (quicklime) + 2CO2 T 56 4088] While there is nearly universal agreement about the equilibrium conditions related to the limestone/lime reaction above, there have been numerous and varied calcination models developed for the reaction. Recent investigations have resulted in the development of the model shown in Fig. 1. From this model it can be seen that calcination is a function of both temperature and CO2 pressure. It does not, however, provide any indication of the rate at which the reaction takes place. Calcination is strongly time variant with different limestones. In a very broad sense this relates to the fact that the calcination reaction starts on the exterior surface of the limestone and then proceeds toward the center. As the calcination reaction takes place, the CO2 released at the reaction interface must make its way through the lime to the exterior surface. Therefore, because calcination is limited by gas diffusion to the surface of the partially calcined limestone, natural impurities in the stone, differences in crystallinity, grain boundary chemistry, density variations, and imperfections in the atomic lattice all play a significant role in

Jan 1, 1983

By Culver, Richard S.

In spite of the widespread interest in rock bolt research, relatively little is known about the critical region surrounding the bolt anchor. In analyzing the stress distribution around an opening resulting from rock bolt support, it is commonly assumed that the bolt is fixed at a point far enough from the surface so that the anchor does not influence the performance of the bolt. Furthermore, a bolt anchor is assumed to per- form satisfactorily if it will hold the design load with a minimum amount of load relaxation, commonly called bleedoff. From the standpoint of the design engineer both of these assumptions are reasonable, but they ignore the fact that the extremely high stresses in the region of the anchor are capable of generating fractures in the rock. Lang estimated the bearing stresses for a slot and wedge anchor on a one-inch-diameter bolt to be as high as 125,000 psi. This paper describes a more thorough analysis of the magnitude of the stresses around the anchor and the nature of the potential fractures that might result.

Jan 1, 1968

By Michael A. Gustafson, Fernando B. Sotelino

INTRODUCTION The degree of success of any new project will ultimately depend on two factors: (i) the underlying economic strength of the project; and (ii) how successfully the parties involved can coordinate their interests to establish a financing structure which indeed capitalizes on the project's inherent economic attractiveness. A project's underlying economic attractiveness is determined by its inherent comparative advantage in accessing the factors of production, combining these factors of production to create a product and marketing this product. Initially, the decision regarding whether to go ahead with the project - the go/no go decision - has to be based on its total ability to generate cash flow returns to project participants to compensate them for resources committed and risks undertaken. The extent to which project sponsors will actually benefit from the project's inherent economic attractiveness is fundamentally dependent on their ability to establish the long-term financing arrangement which best meets the objectives and constraints of each project participant and sources the most advantageous funding. The decision regarding the financing of the project, the "how-to-go" decision, is then an attempt to find the capital structure, consistent with market terms and conditions and sound financial management policies which will best: (i) match planned outflows with cash inflows; and (ii) maximize the return for project sponsors. This article makes use of a case study to illustrate the analytical process involved in dealing with the go/no go and the how-to-go decisions on a project. Though most commonly applied to project finance situations, the guideline described herein is equally applicable to other financing situations, such as leveraged buyouts and debt restructurings, where timely repayment of debt depends largely on the future cash flows to be generated by the entity being financed. Our case study is of a hypothetical expansion of an existing copper mining operation in Latin America. The company, Latin American Copper (LAC) currently has 147 million metric tons of proven sulphide ore reserves. The existing mine complex consists of an open pit mining operation and a conventional flotation plant with a processing capacity of 20,000 metric tons of ore per day. LAC sells copper concentrates primarily to Japanese custom smelters. The mine has been in operation for 5 years, fine copper production last year was 108,240 metric tons, and LAC currently has assets of $175 million and net worth of $135 million. Due to a recent increase in proven reserves, LAC is considering doubling the treatment capacity of its flotation plant to 40,000 tons per day, and expanding its mining capacity to meet the additional concentrator capacity (the "Project"). Project capital expenditures and incremental working capital have been estimated at approximately $210 million. The construction period is expected to cover one year, including a three-month start-up phase. The Project is to be funded by a combination of equity, senior debt, including both supplier credits and/or commercial bank term loans, and subordinated debt. LAC's shareholders are willing to commit a maximum of $50 million to the Project. A government development agency, which is also a minority shareholder, might be willing to lend approximately $40 million to LAC in the form of subordinated notes, depending on the ability of the Project to generate foreign exchange reserves. Commercial banks cannot be expected to offer loans with maturities longer than ten years. The Project is expected to increase the value of the firm because: (i) It will solidify the Company's position as a low-cost copper producer by taking advantage of economies of scale. As a result of the expansion, cash production costs are expected to decrease 7.0[c]/lb. and all-in costs 11.0[c]/lb; (ii) The potential earnings stream from the sulphide ore reserves will be realized

Jan 1, 1985

By Clarence W. Dunham

BECAUSE of the earthquakes that occur at Chuquicamata, the design of the smelter stacks constituted the most difficult structural problem of the entire sulphide ore project. Slight tremors occur almost daily and shocks of moderate magnitude are not uncommon. Naturally, the operation of the smelter depends upon the safety of these stacks, and their resistance to earthquakes was the critical feature of their design. Adequate data of the magnitudes of past shocks at Chuquicamata were not available. However, considering the information that was obtained from experiences in other parts of Chile, a period of one to two seconds was adopted as a basis for the design. To complicate the problem further, the stacks had to provide for operations under a wide variety of conditions ranging from the possibility of running one reverberatory furnace and two converters initially to perhaps five or six furnaces and eight or ten converters simultaneously in the completed plant. No one could tell for certain just what the ultimate capacity might have to be because the plans permitted a large extension beyond the first installation if this became necessary. Studies of the stacks were made for many conditions. At first it was thought that one stack 600 or 650 ft high should be used initially for both the furnaces and converters, with a second similar stack to be built for the future extension. This height would provide adequate draft in the rarified atmosphere at the plant's elevation of 10,000 ft. It would also disperse the gases high in the air. Preliminary studies of this large stack showed that such a structure was possible if made of steel but it would be exceedingly costly. Furthermore, the effects of the tendency for the top to whip under the action of earthquakes might be serious, and the design had to be based upon assumptions which might not be trustworthy. Such a tall stack was finally abandoned in favor of a larger number of smaller ones. Initially, one stack will service the first three or four furnaces. Another will handle the gases from four or five converters. The smelter has been located in such a position that the prevailing winds carry the fumes away from the remainder of the plant. A height of 300 ft for the stacks was finally selected. The top diameter is approximately 24 ft 9 in. clear inside of the lining. The converter stack is located upon a hill alongside the smelter. This provides an effective increase in height because its base is approximately 66 ft above the yard level. The base of the reverberatory stack is at the latter elevation. Stacks made of reinforced concrete or of steel were investigated, and so were many shapes for them. As these studies progressed, the lightness of a steel structure, and the ductility of the metal itself, led to the decision to use steel for the main part of the stacks. The fact that serious damage to one of the stacks would cause the plant to shut down, caused special studies to be made of the stress conditions that might exist around the breeching which had to be nearly 15 ft wide and 40 ft or more high where it joined the stack. This height was necessary in order to provide adequate transition from the horizontal flow of the gases to the vertical direction without undue eddies. This opening constituted a serious source of weakness in the structure. If made with sufficiently strong reinforcement around its edges, there would be a hard spot in the structure that might cause trouble because of shaft vibrations.

Jan 1, 1952

By J. O. Betterton, D. S. Easton

A detailed investigation was made of the phase diagram of silver-zirconium, particularly in the region 0 to 36 at. pct Ag. The system was found to be characterized by two intermediate phases Zr2Ag and ZrAg and a eutectoid reaction in which the -zirconium solid solution decomposes into a-zirconium and Zr2Ag. It was found that impurities in the range 0.05 pct from the iodide-type zirconium were sufficient to introduce deviations from binary behavior, and that with partial removal of these impurities an increase in the a-phase solid solubility limit from 0.1 to 1.1 at. pct Ag was observed. The phase diagram of the silver-zirconium system is of interest as an example of alloying a transition metal from the left side of the Periodic Table with a Group IB element. Silver would normally act as a univalent metal, its filled 4d-shell remaining undisturbed during the alloying. However, there is a possibility that some of the 4d electrons might transfer to the zirconium. An insight into such a question can occasionally be obtained by comparison of phase diagrams. The silver-zirconium system forms part of a more complete review of various solutes in zirconium in which these valency effects were studied.' Earlier work on the silver-zirconium system was done by Raub and Enge1,2 who investigated the silver-rich alloys. After the start of the present experhents, work on this system was reported by Kemper3 and by Karlsson4 which for the most part agrees with the phase diagram presented here. EXPERIMENTAL PROCEDURE The alloys were prepared by arc casting on a water-cooled, copper hearth with a tungsten electrode and in a pure argon atmosphere. Uniform solute composition was attained by multiple melting on alternate sides of the same ingot. Progressive improvements in the vacuum conditions inside the apparatus during the course of the experiments reduced the Vickers hardness increase of the pure zirconium control ingot from 10 to 20 points, observed initially, to negligible amounts at the end of the experiments. Such hardness changes in zirconium are a well known indication of purity. For example, -01 wt pct additions of oxygen, nitrogen, and carbon increase hardness by 6, 10, and 3 VPN respectively. '9' Further verification that the final casting technique did not add a significant quantity of impurities was obtained when pure zirconium was arc cast and then isothermally annealed in the vicinity of the allotropic transition. The transition was always observed to take place over the same temperature range as in the original crystal bar. The alloy ingots were annealed in sealed silica capsules for times and temperatures which varied between 1 day at 1300°C and 60 days at 700°C. The best method found to prevent the reaction of the zirconium with the silica was foil wrapping of molybdenum or tantalum. With this method, samples of pure zirconium were found to be unchanged in hardness after annealing for 3 days at 1200°C. In most of the experiments the protection of these foils was supplemented by an additional layer of zirconium foil inside the molybdenum or tantalum foil. The alloys, foil, and the capsule were outgassed at pressures in the range 10 to l0-7mm Hg in the temperature range 800" to 1100°C before each anneal in order to remove hydrogen and other impurities, and to provide a suitable container for the high purity, inert atmosphere, which is essential in the annealing of zirconium. The temperature measurements were made with Pt/Pt + 10 pct Rh thermocouples calibrated frequently during the experiments against the melting points of zinc, aluminum, silver, gold, and palladium. For the longer anneals the sum of various temperature errors was generally well within ± 2°C. For short-time anneals and during thermal analysis the overall temperature error is considered to be within ± 0.5°C. The compositions of the alloys from the quenching experiments were determined by chemical analysis at Johnson Matthey and Company, Ltd., under the direction of Mr. F. M. Lever. The actual metallo-graphic samples were individually analyzed in every case, and prior to the analyses two or more sides of each specimen were examined to insure that the specimen was not segregated. The sum of the solute and solvent analyses was in each case within the range 99.9 to 100.1 pct. In the course of the experiments, minor impurities in the range 0 to 500 ppm were found to have significant effects on the zirconium-rich portion of the phase diagram. Similar effects had been encountered previously in other zirconium phase-

Jan 1, 1959

By E. Buehler, H. J. Levinstein

The temperature ranges in which the three inter-metallic phases in the Nb-Sn system form have been determined and the composition and structure of two of the three phases has been established. The kinetics of the formation of Nb3Sn in cored wire samples has been studied in the temperature range of 800° to 1050°C. From 800°to 950°C the rate of formation increases by four orders of magnitude. The rate-controlling step for the formation process in this temperature range appears to be the diffilsion of tin through NbSn. At higher temperatu~es a change occurs in the mechanism of the formation process such that up to a temperature of 1050°C the rate of formation of Nb3Sn does not increase above the rate observed at 950°C. For temperatures helow 950°C the current-carrying capacity of the wire increases with increased percent reaction reaching a maximum value when the formation process is 90 to 95 pct complete. The maximum current-carrying capacity obtainable in this temperature range is independent of the temperature. Above 950°C tlze current-carrying capacity obtainable in the wire decreases with increasing temperature of formation. A model is proposed which accounts for the ohserved behavior. RECENTLY, Buehler et a1.l reported the results of an investigation of the process variables which influence the superconducting properties of Nb3Sn-cored wire. These results indicated that at least four variables affect the properties of the manufactured wire. These include composition, particle size of the starting powder mix, temperature of heat treatment, and time of heat treatment. In order to understand completely the role of these variables, it is necessary to have an accurate knowledge of the phase equilibria in the Nb-Sn system. At the present time, phase-equilibrium diagrams for the Nb-Sn system have been published by a number of investigators.2-5 The diagrams differ as to the number of phases present, the composition of the phases, and the temperature range of stability of the phases. The present investigation was undertaken in order to resolve these differences. Since the investigation of Buehler et al. demon- strated that the length of time at the temperature of heat treatment affected the superconducting properties of Nb3Sn, it is apparent that it is necessary to understand the kinetics of the formation process as well as the equilibrium conditions before a complete understanding of the system is possible. As a result, the kinetics of formation of the various phases in the system were also studied in this investigation. EXPEFUMENTAL PROCEDURE Diffusion couples and sintered powdered compacts were employed in the phase-diagram investigation. The diffusion couples were made by filling 1/8-in.-ID monel-sheathed niobium tubes with tin. The monel sheath was employed to facilitate drawing.' The tubes were then drawn to a tin-core diameter of 32 mils. Samples approximately 3 in. long were then cut from the drawn composite. The tin was drilled out of the ends to a depth of 1/4 in. and niobium-wire plugs were inserted into the ends and peened over. The monel was removed by etching in concentrated nitric acid, after which the samples were sealed in evacuated quartz bulbs and heat-treated in a resistance-wound tube furnace. The samples were quenched into ice water upon removal from the furnace. The diffusion couple samples were examined metallographically employing a chemical etching solution consisting of 10 ml of saturated chromic acid per g of NaF. In addition, two anodizing solutions were used for phase-identification purposes. The first was the picklesimer7 solution; the second consisted of equal parts by volume of 30 pct H2O2 and concentrated NH4OH to which 1 g of NaF was added per 25 ml of solution. The anodizing conditions for the second solution were 2 v and 100 ma with a tin cathode. The powdered compacts were made by pressing previously mixed powders of 99.9 pct pure Sn and 99.6 pct pure Nb supplied by the United Mineral Co. into cylinders 3/8 in. in diameter by 1/2 in. long. The cylinders were then sealed in quartz tubes and heat-treated in the same manner as the diffusion couples. The samples were examined metallographically and by X-ray diffraction techniques. Since it was desirable to be able to correlate the kinetic data with current-carrying capacity, the type of specimen chosen for this part of the investigation had to be a compromise between the optimum system for studying kinetics and one which was suitable for making current-carrying capacity

Jan 1, 1964

By T. Toda, R. Maddin

A study has been made of the microstructure and mechanical properties of splat-cooled aluminum-base gold alloys with gold concentration from 0.25 to 5.0 wt pct. These alloys have been quenched from the liquid state by a torsion-catapult technique, which has made it possible to pepare specimens suitable for mechanical property measwements. From the electron micrographs it has been shown that the solid solubility of gold in aluminum can be extended to 2.5 wt pct (0.35 at. pct) by splat-cooling, while the maximum equilibrium solubility is known to be less than 0.3 wt pct (0.04 at. pct). The very fine grain size (several tenths of a micron), the extended solid solubility, and the fine dispersion of a second phase (AuAl2) contribute concurrently to a substantial strengthening effect. In Al-5 wt pct Au splat-cooled specimens of less than 50 thickness, the yield strength is 17 kg per sq mm or 6 times as large as the strength of bulk specimens. For the Al-1.0 to 2.5 wt pct Au solid solution obtained by splat-cooling, the yield strength reaches 7.5 kg per sq mm after an aging treatment (for 10 hr at 200°C), while it is 3.7 kg per sq mm for the corresponding bulk specimens. A great deal of research has been done in recent years on the structure and the properties of metals and alloys rapidly quenched from the liquid state.' The term "splat-cool" has been used with the meaning of a rapid quenching from the liquid state., The splat-cooling techniques have produced large numbers of new structures, which are expressed in terms of metastable phases,3 concentrated solid solutions,4 amorphous phases,5'6 new phases,7 and so forth. Nearly all previous studies have concentrated on the physical properties; i.e., crystallography, structure, electrical resistivity, magnetism, and so forth, of the splat-cooled metals and alloys. The mechanical strength of splat-cooled metals and alloys has hardly been investigated except for some recent work by MOSS' on A1-V alloys. The principle common to all experimental techniques developed to obtain very rapid quenching rates is based on the heat transfer by conduction. Liquid must be in good thermal contact with a substrate of high heat conductivity. Both of the published devices known as the "gun" and the "piston and anvil" techniques suffer from certain shortcomings. For example, the specimen obtained by the gun technique is very small and flaky, and hence inadequate for mechanical properties measurements. On the other hand if the material is forced to yield a continuous speci- men by the piston and anvil technique, it is probable that some plastic deformation occurs during the quench. A novel method for rapid quenching of a liquid metal or alloy, the "torsion-catapult", has been devised by Roberge and Herman9 at the University of Pennsylvania. In the apparatus the melt is thrown out of a curved furnace by a catapult and impinges on a copper substrate. The apparatus has the advantage of producing a continuous foil which is relatively large in size and of a quality suitable for the measurements of mechanical properties. The quenching rate is estimated to be of the order of l05 to l06 ºC per sec, (comparable to rates achieved by the piston and anvil technique). In selecting an alloy to be studied we were made aware of the fact that gold was believed to be "insoluble" in in and consequently age hardening in the A1-Au system appeared to be interesting. Quite recently Heirnendahl13-15 revealed that the solid solubility, as determined by transmission electron microscopy, was 0.3 wt pct Au at 640°C and 0.25 wt pct Au at 600°C, decreasing with decreasing temperature. In an A1-0.2 pct Au alloy after quenching from a solution treating temperature of 600°C the yield stress was 2 kg per sq mm, and it increased up to 6 kg per sq mm after aging for 1 to 10 hr at 200°C. The precipitation occurred in the form of platelike particles mainly on (100) matrix planes. The intermediate phase n', the equilibrium phase n (AuAl2), and lattice relationships between both precipitates and the matrix were also investigated by electron microscopy. One of the purposes of the present research is to determine whether or not the solid solubility in this system, in which gold has a very small solubility in

Jan 1, 1970

By William H. Shockley

[SECRETARY'S ]NOTE.-The following notes, arranged and edited in this office, but not yet revised by the author, were placed at my disposal with much modest hesitation (due to their incomplete and fragmentary character), upon my earnest request, and my argument that such recent and trustworthy data concerning a new and important mining industry ought not to be withheld from our Transactions, simply because they are not sufficient to constitute a, complete academic treatise on the subject. This argument is recommended to the attention of many other members, who are waiting for the opportunity to contribute something "monumental" to our Transactions. In a number of instances, death has nulli¬fied this ambition, and the intended "monumental" contribution has turned out to be an obituary notice by the Secretary, instead of a valuable record of the professional experience thus hopelessly lost to the world.-R. W. R.] The official publications of the the Russian Government give fairly complete statistics of the dredges operated in the Empire; and in a recent English bluebook, Mr. Cook's report on Siberian Trade presents a brief account of dredging in Siberia. The data in Table I. (not given by Mr. Cook) have been taken from the Gold Mining Messenger (Russian) for July, 1905. These interesting statistics, though incomplete, show that the Yenisei dredges are working on poor ground and yield small returns. According to report, but few yield a profit exceeding 10 per cent. per annum on the capital invested. In the summers of 1904 and 1905, I traveled in the Urals as far north as lat. 61° N., long. 61° E., on the the Lozva river, a part of the vast system of the 01) river. This clear-water stream starts from the summits of the Urals at an altitude of 4,000 ft., and flows through a flat country, densely wooded with larch, spruce, pine, fir, birch and poplar. The river is full of fish, and is navigable for good-sized steamers as far as Ivdell. Winter lasts from early November to late April, the temperature rang¬ing from -60° F. to a summer maximum of 90° F. The rain¬fall is 20 in.. The climate is healthy, although mosquitoes,

Jul 1, 1906

By L. C. Chang, T. A. Read

Diffusionless transformation in Au-Cd single crystals containing about 50 atomic pet Cd was investigated by means of X-ray analysis of the orientation relationships, electrical resistivity measurements, and motion picture studies of the movement of boundaries between the new and old phases during transformation. The nucleation of diffusionless transformation by imperfections and the generation of imperfections by diffusionless transformation were discussed. THAT connections exist between plastic deformation and diffusionless phase changes has long been recognized. Thus it is often possible to produce a diffusionless phase change in a temperature range, above that in which the change occurs spontaneously, by cold-working the initial phase. Certain aspects of the dislocation theory of the plastic deformation of crystalline solids also provide for a rather direct connection between the processes involved in plastic deformation and in diffusionless phase changes. Heidenreich and Shockleyl have pointed out that simple edge dislocations in f.c.c. metals are probably unstable, and that the more probable lattice imperfections, called extended edge dislocations, consist of two half dislocations separated by a distance of the order of magnitude of 100A. The region about two atomic planes thick between the half dislocations because of this stacking fault may be described as having the hexagonal close-packed structure. Presumably the stacking faults observed by Barrett" fter cold-working f.c.c. Cu-Si alloys resulted from the passage of such half dislocations through the lattice of the initial phase. It is now becoming clear that the development of a detailed theory of the atomic movements involved in diffusionless phase changes will require a consideration of the role played by lattice imperfections, just as such considerations are necessary to the understanding of plastic deformation mechanisms. This point of view has been recently set forth, for example, by Cohen, Machlin, and Paranjpe3 who pointed out the role which might be played by screw dislocations in nucleating diffusionless phase changes. The present paper reports on some aspects of the diffusionless phase change in single crystals of the beta phase alloy Au-Cd which serve to emphasize further the importance of lattice imperfections in diffusionless phase changes. The diffusionless phase change of Au-Cd possesses several remarkable features. One of these is that the interface between the high-temperature beta phase and the low-temperature orthorhombic phase typically moves with a low velocity, in contrast to the behavior observed in the transformation of austenite to martensite. Motion pictures of this slow interface motion have been prepared in the course of the work reported here. Another important feature of the Au-Cd transformation is the small amount of undercooling observed. The reverse transformation occurs on reheating to a temperature only 20" higher than the transformation temperature observed on cooling, and under some circumstances the hysteresis observed is substantially less than this. This narrow temperature range between transformation on heating and cooling is presumably in part a consequence of the fact that the transformation requires a lattice shear of only about 3". Finally, the orthorhombic product phase possesses unusual mechanical properties, as was first pointed out by olander' and Benedicks." After completion of the transformation on cooling the specimen can be severely deformed, yet on the release of load it springs back to its original shape in a rubber-like manner. Explanation of this phenomenon will require an understanding of the lattice imperfections in the orthorhombic structure and, correspondingly, of those in the initial body-centered cubic structure. Single crystals of Au-Cd alloy containing 47.5 and 49.0 atomic pct Cd were prepared from fine gold (99.95 pct purity) and chemically pure cadmium (99.99 pct purity) by melting the alloy in an evacuated and sealed fused quartz tubing and growing into single-crystal form by the Bridgman method. The Au-Cd alloy containing 47.5 atomic pct Cd undergoes a diffusionless transformation from an ordered body-centered cubic structure to an orthorhombic structure when it is cooled to about 60°C, while the reverse transformation takes place when the alloy is heated to about 80°C, according to electrical resistivity studies. The structures of these two phases have been studied by Blander,4 reinvestigated by Bystrom and Almin.e he lines of Debye photo-gram of powdered samples of Au-Cd alloy containing 47.5 atomic pct Cd prepared in this laboratory were identified and agreed fairly well with those of

Jan 1, 1952

By H. I. NORTON, H. O. Hofman

ZINC smelters in the central western. States have established a very high standard of purity for blende-concentrates, viz., zinc 60, iron less than 3, and lead less than 1 per cent. The very low percentage of iron is made possible by the blende containing less than 0.5 percent of isomorphous iron sulphide and by the sparing occurrence of pyritic material in the large blende-deposits of southwestern Missouri and southeastern Kansas. The blende in these districts occurs in sub-Carboniferous limestone, and is associated with chert, residual clay, calcite, pyrite or rnarcasite and bitumen. The different minerals are coarse and therefore readily separated by mechanical washing from the blende, with the exception of pyrite and marcasite, as blende has a specific gravity of from 3.9 to 4.1, marcasite, from 4.85 to 4.90, and pyrite, from 4.95 to 5.10. The common procedure of dressing the ores is to crush in a breaker, size in a trommel with 0.5-in. holes, pass the over-size through roughing-rolls and then jig the ore, now reduced to 0.5 in. maximum size, in roughing multiple-sieve jigs. The products of these are waste-tailings, sine-discharge coarse concentrates, side-discharge coarse middlings and bottom-discharge fine middlings. The coarse concentrates are sent to the market. The coarse middlings are crushed in middlings-rolls and brought back into the system by feeding into the main trommel. The fine middlings are cleaned upon finishing-jigs. Any pyrite or marcasite present follows the blende and increases the percent-

Mar 1, 1905

By M. J. Marcinkowski, E. N. Hopkins

An investigation has been made of the ß(fcc) — a(hexagonal) transformation which occurs in lanthanum using both electrical resistivity and transmission electron microscopy techniques. It has been shown that the ß phase can be retained below the transformation temperature by rapid quenching but that the sample immediately begins to transform to the a phase. The transformation is observed to nucleate in the vicinity of inclusions. Based on the above observations, a detailed model of the transformation has been advanced which involves the nucleation of an extrinsic stacking fault bounded by a pair of Shockley partial dislocations in the vicinity of some heterogeneity, i.e., an inclusion. The stress field of the resultant dislocation pair acts to nucleate extrinsic faults in adjacent planes and leads quite naturally to the B-a conversion with a minimum of strain energy induced in the crystal. LANTHANUM possesses an fcc structure ß) (8) upon cooling transforms to a hexagonal modification (a) in much the same way as cobalt. The one exception, however, is that the stacking sequence of the closest packed planes in a La is ABAC ABAC, and so forth,1 whereas in cobalt it is ABAB, and so forth, i.e., hep. Mainly on the basis of transmission electron microscopy techniques, there seems to be little doubt that the 0 — a transformation in cobalt involves a dislocation mechanism2 although its exact nature still remains obscure. Although the ß - a transformation in lanthanum is somewhat more complex than that occurring in cobalt, it was thought that its very uniqueness would be helpful in understanding fcc — hexagonal transformations in general. Such a general understanding of these transformations is important since they represent what are perhaps the simplest of the martensitic class of transformations. The experimental techniques used were those of electrical resistivity and transmission electron microscopy. EXPERIMENTAL PROCEDURE The lanthanum used in this investigation was prepared by the calcium reduction of lanthanum fluoride in a tantalum crucible under an argon atmosphere as described by Spedding et al. The residual calcium was removed by vacuum remelting in a tantalum container. Portions of the metal were then analyzed by emission spectroscopy as well as vacuum fusion. The amounts of the various impurities that were found are listed in Table I. A portion of the lanthanum ingot was swaged at room temperature into 0.030-in.-diam rod for the resistivity samples while the remainder was rolled into 0.010-in.-thick sheet for the transmission electron microscopy phase of this investigation. In order to eliminate the plastic deformation induced in the samples during fabrication, they were sealed in evacuated tantalum lined quartz capsules and annealed for 1 hr at 700° C. Specimen resistances were measured using the conventional "four-wire" technique described by MacDonald, 4 employing a type K-3 Universal Potentiometer and a standard 0.001-ohm resistor, both manufactured by Leeds and Northrup Co. By taking into account all of the possible errors in the apparatus, it was felt that the absolute resistivities of the approximately 0.87-in.-long specimens measured are reliable to 3 pct. Resistances from room temperature to 700°C were measured using a vacuum furnace. In order to avoid sample contamination by the thermocouple, chromel-alumel leads were spot-welded into a tantalum shield which in turn was welded to the lanthanum specimen. Resistances below room temperature were obtained by transferring the sample to a helium gas-filled quench tube and slowly dripping liquid nitrogen into a surrounding dewar flask. A steady reduction of temperature to about —190°C was completed in about 23 hr, and the resistances were measured at various temperature intervals. As will be shown shortly, rapid quenching from above about 350°C was sufficient to suppress the B -a transformation initially but subsequent annealing at lower temperatures leads to a partial ß --a conversion. To investigate this aspect of the transformation, the samples were suspended in the hot zone of a helium-filled furnace from which they could be rapidly dropped into the quench tube mentioned previously which was now

Jan 1, 1969

By J. E. Schiller, S. E. Khalafalla

To improve technology for treating process water, US Bureau of Mines research has shown that magnesium oxide (MgO) has many advantages over lime or caustic soda for precipitating heavy metals. Sludge produced by MgO occupies only 0.2-0.3 times as much volume as the precipitate made wing a soluble base. While a settled, lime-formed precipitate is easily resuspended, the MgO-metal hydroxide sludge becomes cemented together on standing. Settling of the metal hydroxides from a dilute suspension is more complete than precipitates formed with other bases. Virtually any metal that can be precipitated by raising the pH can be treated using MgO. A three fold to fourfold stoichiometric excess of solid reagent is added. The mixture is reacted for five to 10 minutes. Polymer is added, and settling or filtration completes the process. Because of the greater cost of MgO compared with lime, large-scale practice of this technology will probably be limited to water containing 50 mg/L (3 gr per gal) or less of dissolved metals. For such dilute solutions, chemicals are not a large fraction of total treatment costs, so more desirable sludge properties might justify higher chemical expenses. While the MgO process is technically suitable for widespread application, the extent to which it is adopted will probably be determined by a trade-off between the greater cost of MgO compared with lime and the superior properties of the precipitates and their corresponding ultimate disposal costs.

Jan 1, 1985

By A. D. Rich

The term "bleaching clay" or "bleaching earth," as used in the oil industries, refers to clays that in their natural state, or after chemical or physical activation, have the capacity for adsorbing coloring matter from oil. There are three common types of bleaching clays: fuller's earth, activated clays, and activated bauxite. Fuller's earth, or naturally active clay, is prepared from bentonites (see Chap. 5) that possess natural activity. It is not activated commercially; in fact, earths of this type ordinarily do not respond satisfactorily to acid activation. Fuller's earth is prepared in pulverized as well as granular form for use in the contacting and percolation processes, respectively. Acid-activated clays also are of bentonitic origin. The basic raw clay, however, is of a type that has a very low natural activity but is highly activable by treatment with mineral acid. Commercial acid-activated clays generally possess several times the decolorizing power (bleaching efficiency) of the best quality of fuller's earth. The former are prepared commercially only in the pulverized grade because of the difficulties in obtaining a satisfactory granular product, and hence are used only in the contact process. Activated bauxite is made by heat-treating bauxite ore, which in its natural state has very little natural activity. The commercial product is prepared in granular form for use in the percolation process on petroleum oils. For the most part, bleaching clay is used commercially in the decolorization of animal, vegetable and petroleum oils, fats and waxes. It is applied in two ways: (1) by the percolation method and (2) by the contacting method. Percolation refers to the passage of oil through a bed of granular clay whereas contacting refers to direct agitation of oil and pulverized clay followed by removal of the clay from the oil by filtration. In either case, the decolorizing effect is obtained by intimate contact between the liquid oil and the solid adsorbent. Petroleum oils are treated commercially by either the percolation or the contact process. Animal and vegetable oils are treated by the contact process only. Composition The raw clays from which both fuller's earth and acid-activated clays are prepared are composed of hydrous aluminum silicates containing varying quantities of magnesium, iron, calcium and other elements. These raw materials are usually nonswelling bentonites derived from volcanic ash or lava by weathering and hydrothermal chemical reactions. The bentonites have as their chief mineral constituent montmorillonite, which has the formula [(OH)4Si6A14O20•nH2O], according to Grim. (See Chap. 5, ref. 6, p. 91.) The underlying reasons are not fully known for the natural activity of the fuller's earth type of clay and its usual failure to further activate with mineral acid in contrast to the natural inactivity of the activatable type of clay. However, it may be said that the bentonites that are responsive to the acid-activation treatment generally have not undergone any drastic metamorphism. The chemical composition is not a reliable means of discrimination between a nonactive, a naturally active, and a nonactive but activable clay, therefore it is not possible to forecast the ultimate quality of a clay on the basis of the raw-clay analysis alone. Table 1 gives typical analyses of representative clays of the foregoing classifications.

Jan 1, 1960

By John Chipman

DESPITE the rapidity of chemical reactions at steelmaking temperatures, deoxidation reactions cannot be expected to reach equilibrium immediately after addition of a deoxidizing agent. A considerable period of time may be required merely to obtain complete mixing of the deoxidizing element throughout the volume of steel to which it is added. Evidence in the literature indicates that in some cases the time is long compared with that allowed for completion of the experiment or for teeming of the heat. The great turbulence observed during the filling of the ladle is no guarantee of complete dispersion on a fine scale throughout the heat. During the process there are initially certain volume elements which are high in deoxidizer and others which retain substantially their original oxygen content. Mixing consists of the subdivision and ultimate destruction of these liquid segregates through the process of shear and elimination of concentration gradients by diffusion. The shear process does not continue indefinitely and a quiescent state may be reached in the ladle before all volume elements of divergent deoxidizer and oxygen content are completely eliminated. In furnace deoxidation the time required for complete mixing may be very long unless continuous stirring is employed.' In Fig. 1, let the circle represent one small volume element of aluminum-rich metal surrounded by oxygen-rich steel in which no stirring movement remains. Further mixing requires inward diffusion of oxygen and outward diffusion of aluminum, resulting in precipitation of A12O3 in the diffusion zone. It is important to note that such a precipitate may itself interfere with the diffusion process. Moreover, if the precipitate forms as a film with even minimal mechanical strength, it may interfere not only with diffusion but with shear as well, thus stabilizing compositional differences in volume elements of greater than microscopic size. A film surrounding such a volume element would have little or no ability to rise or to sink unless it enclosed a liquid whose density differed from that of the ambient. Consider now the effect on the overall composition of the melt. Fig. 2 represents the A1-O equilibrium at the temperature of the bath. High-aluminum elements of composition X may exist alongside high-oxygen elements of composition Y in such proportions that the average composition 2 has a much higher A1-O product than that corresponding to equilibrium. The A1-O product supposedly corresponding to equilibrium at 1600 °C was found by Wentrup and Hieber2 to be 10-10, by Hilty and crafts3 to be 2 X 10-9 and by Gokcen and chipman4 to be 2 x 10-14. Only the last named investigators approached equilibrium by means

Jan 1, 1962

By A. A. Burr, D. Caplan

IN carrying out experiments in metal-gas systems, it is often difficult to estimate how long a reaction period must be allowed for equilibration. This is especially true in systems for which the diffusion coefficient is not known. In an investigation of the Cr-O system, the necessary information was obtained in the way described subsequently. Two pieces of chromium sheet of different thicknesses were packed in mixed powders of chromium and Cr2O3 and sealed into an evacuated metal capsule by welding. Austenitic stainless steel proved suitable as a capsule material up to 1350°C and molybdenum at higher temperatures. The capsule then was heated at a specific temperature for a time sufficient to saturate with oxygen the thinner but not the thicker specimen. The time is readily estimated from a preliminary experiment if a sufficient thickness differential is chosen. Under these experimental conditions, the metal sheet is exposed to a partial pressure of oxygen equal to that of the dissociation pressure of the oxide and hence can become saturated with oxygen without developing any second phase. After cooling, both samples were analyzed for oxygen by the vacuum fusion technique. Assuming that the surface of the specimens is kept saturated with oxygen throughout the experiment, the diffusivity can be calculated by application of the appropriate solution to Fick's second law. This is most conveniently accomplished by use of a plot of mean fractional saturation (Cm-Co) / (Cs-Co) vs (Dt) ½/L as given by Darken,' where t is time, L the half-thickness of the sheet, and D the diffusion coefficient. Cm, the mean concentration at time t, is given by the oxygen percentage in the thicker specimen; Cs, the constant surface concentration, is the oxygen percentage in the thinner specimen; Co is the oxygen content of the original chromium sheet. (Cm-Co) / (Cs-Co) is calculated and the corresponding (Dt) ½/L is read from the graph and D thereby calculated. By performing the experiment at two temperatures and plotting log D vs 1/T, the D for any temperature is established. (The activation energy for diffusion may be obtained from the slope of the line.) Once D is known as a function of temperature, it is a simple matter to estimate the correct reaction time for experiments with single specimens at other temperatures by equating (Dt) ½/L to its value for effective saturation. Darken' points out that this is approximately unity. The solubility of oxygen in chromium, as determined from the thin samples at each temperature, proved to be approximately 0.03 pct at 1350°C and less at lower temperatures. Due to low solubility and to the known difficulties of the vacuum fusion method in this low range, the values obtained for D (5x10-0 sq cm per sec at 1350°C) are estimated to be correct only within an order of magnitude. Nevertheless, the method has proved useful in estimating reaction times. Its usefulness will be greater in metal-gas systems where the solubility is appreciable. A second function of the method is to permit the determination of diffusion coefficients in systems for which the conventional techniques are experimentally difficult or impossible.

Jan 1, 1956

By T. S. Fuller

MUCH study has been given by engineers in general, and investigators in particular, to the concentration of stress which occurs under load in structural members having irregularities in section such as notches, shoulders, key ways, tool marks, etc. The result of the effect of both fresh and salt water corrosion upon the endurance properties of various metals and alloys has been ably determined and the general laws underlying these phenomena carefully pointed out by McAdam. From a practical standpoint, 'however, it is after all the endurance value of corroded, non-symmetrical sections which is most pertinent. In the experiments about to be described rotating cantilever specimens of nickel steel of the 3.5 per cent nickel ' 0.35 per cent carbon type have been used. These were machined from bars l 1/8. in. dia. and 9% in. long and were heat-treated by quenching in oil from 825 deg. C. followed by reheating to 650' C. and oil quenching. The tensile and impact properties of this material so heat- treated follow:

Jan 1, 1931

By David Reger

LITTLE new oil was found in West Virginia, during 1923, but there were important discoveries of gas. Most of the large oil producers have contented themselves with pumping old wells or in drilling only enough new wells in defined territory to maintain a fairly constant production, the attitude being that no, profit is made in producing high-grade oil at a low price and that an eventual loss is sustained by draining the reserves of a limited commodity that, at some more favorable time, will be of much value. The representative of one large company said: "We have done nothing but pump old wells during 1923 and we have made no plans for 1924." Careful attention to producing wells has been the rule, there having been few abandonments; the belief is prevalent that small wells will eventually become profitable under more favorable marketing conditions. In natural gas, the opposite point of view prevails. Because of the vast capabilities of the state for producing gas, its output being ahead of all others, great systems of transportation and distribution into the markets of four adjoining states have been built and a demand has been created that no present, or apparently potential, production can satisfy. This demand has become so great that large distributing companies not only discourage new applications for service but advise old customers to install coal furnaces for auxiliary fuel; some have requested public-service commissions to grant higher 'rates against large industrial consumers than those allowed for domestic heating. The response to this known market has been a rapid increase in price, both at the well mouth and at the door of the ultimate consumer, and the industry has become so stable that the only uncertainty, or hazard, appears to be the question of the presence of gas in fair quantity in a given territory under consideration. Several oil companies have now forsaken their policy of selling gas, wells outright when drilled and ;have organized gas departments to drill for gas and to dispose of the daily output by meter to distributing corporations. With such companies and with other producers whose interest is chiefly gas, the year has been busy and profitable. Some new territory of apparently large value has been proved and deeper producing sands in old fields have been tapped.

Jan 3, 1924