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By K. A. Jackson, J. D. Hunt

A general theory for the growth of lamellar and rod eutectics is presented. These modes of growth depend on the interplay between the diffusion required for phase separation and the formation of interphase boundaries. The present analysis of these factors provides a justification for earlier approximate theovies. The conditions for stability of rod and Lanlellar structures are consitleved in terms of the mechanisms by which the structure can change. The mechanisms considered include both small adjustments to the lnnzellar spacing due to the motion of lamellar faults, and catastrophic changes due to instabilities. It is concluded that stable growth occurs at or near the minimum interface undevcooling for a gizierz growth rate. The conseqrlences of the existence of a diffusion boundary layer at the interface are discussed. The experimental results for the variation of growth rate, undercooling, and Lanzellar spacing are cornpared with the theory. We believe that the theory presented in this paper provides an adequate basis for understanding the complex phenomena of lanzellar and rod eutectic growth. The growth of lamellar eutectics has been the subject of several theoretical and many experimental studies. The foundations for the theoretical work were laid by zenerl and Brandt2 in their analyses of the growth of pearlite. Zener estimated the effect cf diffusion, and took into account the surface energy of the lamellar structure. He found that the lamellar structure could grow in a range of growth rates at a given undercooling provided the lamellar spacing was appropriate for the growth rate. Since pearlite grows with only one growth rate and one lamellar spacing at a given undercooling, there is clearly an ambiguity in the theory. Zener removed this ambiguity by postulating that the growth rate was the maximum possible at the given undercooling. He predicted then that the product of the growth velocity v and the square of the lamellar spacing A should be constant, i.e., A2v = const. Brandt2 started out by assuming that the interface between the lamellae and austenite was sinusoidal. Because of this, the ambiguity encountered by Zener did not arise. Brandt was able to obtain an approximate solution to the diffusion equation, but, since he did not take into account the surface energy, his considerations are incomplete. Tiller3 applied some of these ideas to the growth of eutectics, and proposed a minimum undercooling condition to replace the maximum velocity condition used by Zener. These conditions are formally identical. Hillert4 extended the work of Zener. He found a solution to the diffusion equation assuming the interface to be plane. Taking surface energy into account, and applying Zener's maximum condition, he was able to calculate an approximate shape of the interface. Jackson et al.5 used an iterative method employing an electric analog to the diffusion problem to refine the calculation of interface shape. It was found that the interface shape calculated from a plane-interface solution to the diffusion equation was negligibly different from the exact solution. The method provided an analog only for eutectics for which the volumes of the two phases are equal, growing from a melt of exactly eu-tectic composition. There has also been considerable experimental work on eutectics, Several experimenters8-10 found that A2v is constant as predicted by Zener.1 Hunt and chilton10 demonstrated that ?T/v1/2 is also a constant for the Pb-Sn system as predicted. Lemkey et al.11have recently found A2v to be constant for a rod eutectic. In the present paper, we present the steady-state solution for the diffusion equation for a lamellar eutectic growing with a plane interface, for the general case, that is, with no restriction on the relative volumes of the two phases, and with the melt on or off eutectic composition. A similar solution is also found for a rod-type eutectic. Expressions are obtained for the average composition at the interface and the average curvature of the interface. These equations for the average composition and curvature are similar in form to those derived by Zener1 and Tiller,3 and provide a justification for some of the approximations made by these authors. The mechanisms by which the spacing in a lamellar structure can change are considered. The important mechanism for small changes in lamellar spacing involves a lamellar fault. Examination of the stability of lamellar faults leads to the conclusion that the growth occurs at or near the extremum.* The insta- bilities which can develop in a rodlike structure are also discussed, resulting in the conclusion that this structure also grows at or near the extremum. Comparison of the conditions for rod and lamellar growth permits a prediction of the surface-energy anisotropy required to produce rods or lamellae for various volume-fraction ratios. The diffusion equation predicts the existence of a diffusion boundary layer at the eutectic interface unless the eutectic has 0.5 volume fraction of each phase and is growing into a liquid of eutectic composition. This boundary layer is such as to make the composition in the liquid at the interface approximately equal to the eutectic composition. This boundary layer permits changes in composition during the zone refining of eutectics. Photographs of the eutectic interface of a growing transparent organic eutectic system have been made. Both the components of this eutectic are transparent organic compounds that freeze as metals do.12 The in-

Jan 1, 1967

By R. J. Brison, O. F. Tangel

The development of a new method of mineral separation was sponsored by the International Salt Company, which requested Battelle Institute to investigate means for improving the quality and appearance of rock salt from the Company's Detroit mine. Although developed specifically for removing impurities from rock salt, the general method may be applicable to other separation problems. The principal impurities in rock salt from the Detroit mine are dolomite and anhydrite which represent 2 to 5 pct of the weight of the mined salt. In the size range from 1/4 to M in. (the range of primary interest in this project) the impurities are only partially liberated from the halite in normal production. Further size reduction to improve the liberation of impurities is not practicable in view of the market requirements for the coarse grades of rock salt. Laboratory separations in heavy liquids showed that, to improve the quality and appearance of the rock salt substantially, it would be necessary to remove not only free gangue particles but also a large proportion of the locked-in particles. Because rock salt is an inexpensive commodity, a low-cost process was required. Gravity methods were, of course, considered. The heavy-liquid separations indicated that a split at an effective specific gravity of 2.2 to 2.3 would be required. (The specific gravity of pure halite is 2.16.) Heavy-media separation was investigated but had the disadvantages that it was necessary both to operate with saturated brine and to dry the cleaned salt, and that the cleaned salt was darkened by the magnetite medium. Air tabling was tried but did not give the desired separation. It soon became apparent that established methods would not provide a satisfactory solution and work was undertaken on the development of a new process to solve the problem. PROCESS DEVELOPMENT Preliminary Experiments: At the start of the investigation, an analysis of the problem indicated that the diathermacy of rock salt—that is, its ability to transmit radiant heat—might form the basis for an efficient separation process. Under this theory, the impurities might be selectively heated by radiant heat. The particles could then be fed over a belt coated with a heat-sensitive substance so that the warm impure particles would adhere preferentially to the coating. After the initial experiments, made by heating the rock salt with an infrared lamp and separating the product on small sheets of resin-coated rubber, proved encouraging, a small continuous separation unit was set up. This comprised 1) a simple heating unit consisting of a vibrating feeder covered with aluminum foil and an infrared lamp mounted above the feeder and 2) a separation belt 6 in. wide and 36 in. long. A sketch of the device is shown in Fig. 1. Results with this apparatus confirmed the fact that a good separation was possible. It was apparent, however, that a considerable amount of experimental work would be needed to develop the scheme to a practical and economical process. The Process: Basically, the process consists of two main steps: 1) selective heating by radiation and 2) separation of the heated particles on a heat-sensitive surface. Because neither of these steps had previously been utilized commercially in mineral processing, it was necessary to do basic research on both aspects. Factors studied in the investigation included type of heat source, design of heating unit, design of separation belt, selection of heat-sensitive coating, removal of heated particles from the belt, contact between particles and coating, and maintenance of the heat-sensitive surface. Part of the experimental work was carried out on a small-scale unit consisting of the 36x6 in. belt and auxiliary apparatus, and part on a larger unit. For simplicity, discussion of work on both of these units is grouped together. SELECTIVE HEATING Radiant-Heat Source: The essential requirements for a radiant-heat source were 1) that the radiant heat be in a wave length range which is effectively absorbed by the impurities but not absorbed appreciably by the rock salt and 2) that it be dependable, practical, and economical. Selection of a heat source of suitable wave length range was one of the first considerations. It is well known that pure halite is highly transparent to radiant energy in wave lengths from 0.3 to 13 microns. However, the available data on infrared transmission by dolomite and anhydrite, particularly in the range below two microns, were not complete enough to serve as a reliable basis for selection of a heat source. Although it may have been possible to obtain sufficient data on infrared transmission and absorption to enable one to select the best heat source, a more direct procedure was used. This consisted simply of exposing the crude rock salt to each of several types of radiant-heat source on the small continuous separation device. The heat sources investigated, approximate source temperature used, and calculated wave length of maximum radiation are tabulated in Table I. Of the two types of tungsten-filament lamps investigated, both the short wave length photoflood lamps and the longer wave length infrared lamps were satisfactory from the standpoint of selectivity

Jan 1, 1961

By G. Derge, Ling Yang, G. M. Pound

The specific conductance and its temperature dependence were measured over the entire composition range of the molten Cu2S-CuCI system. At a typical temperature of 1200°C, 10 rnol pet of the ionically conducting CuCl reduced the specific conductance from about 77 ohm-lcm-l for pure Cu2S to about 32 ohm -1cm -1, and 50 mol pet CuCl reduced the conductance to that for pure CuCI—about 5 ohm 1cm1. The nature of electrical conduction in molten Cu2S, FeS, CuCI, and mixtures was studied by measuring the current efficiency of electrolysis at about 1100°C. The Cu2S, FeS, and mattes were found to conduct exclusively by electrons, but addition of 1 5 wt pet CUS to Cu2S produces a small amount of electrolysis. Addition of CuCl to Cu2S suppresses electronic conduction, and ionic conduction reaches almost 100 pet at a CuCl concentration of about 50 mol pet. These facts are interpreted in terms of electron energy level diagrams by analogy to the situation in solids. RESULTS of electrical conductivity studies on molten Cu-FeS mattes as a function of composition and temperature have been reported.' The specific conductances ranged from about 100 ohm-' cm-' for pure Cu2S to 1500 ohm-' cm-1 for pure FeS. This is in sharp contrast with the low specific conductance of molten ionic salts for which the transfer of electricity is by migration of ions in the field. In general, these ionically conducting molten salts, such as NaC1, KC1, CuC1, etc., have a specific conductance of the order of magnitude of 5 ohm-' cm-'. It was concluded on the basis of this evidence that molten FeS and Cu,S exhibit electronic conduction. Pure molten FeS has a small negative temperature coefficient of specific conductance, resembling metallic conduction, while pure molten Cu2S has a small positive temperature coefficient, resembling semi-conduction. The molten Cu2S-FeS mattes follow a roughly additive rule of mixtures, both with respect to specific conductance and temperature coefficient. Savelsberg2 has studied the electrolysis of molten Cu2S and Cu2S + FeS. He concluded that while molten Cu2S is an electronic conductor, there is some ionic conduction in molten Cu2S + FeS3 owing to the formation of the molecular compound 2Cu2S.FeS and its dissociation into Cu1 and FeS2-1 ions. The present work does not verify his results. Chipman, Inouye, and Tomlinson" have studied the specific conductance of molten FeO and report a high specific conductance, about 200 ohm-1 cm-1 of the same order of magnitude as that found for molten mattes, and a positive temperature coefficient. They interpret these results in terms of p-type semiconduction in the ionic liquid by analogy to the situation in solid FeO.1 imnad and Derne' detected appreciable ionization in molten FeO by means of electrolytic cell efficiency measurements. In order to verify the conclusion that electrical conduction in molten Cu2S and mattes is electronic, and to gain further insight into the structure of molten sulfides, the following investigations were carried out in the present work: 1) The specific conductance, s of the molten system Cu2S-CuC1 was measured as a function of temperature over the entire composition range. As discussed later, molten CuCl is an ionic substance. It was thought that if molten Cu2S were simply ionic in nature, addition of small amounts of CuCl might not have a catastrophic effect in lowering the high conductance of the Cu2S. On the other hand, if much electronic conduction occurs, addition of the ionic CuCl should have a large effect in destroying the electronic conduction. 2) The electrolytic cell efficiency of the following molten systems was measured at about 1100°C in specially designed cells: Cu3; Cu2S + FeS, 50:50 by wt; FeS; Cu2S + CuS, 15 wt pet; Cu2S + CuC1, 5.9 to 46.4 mol pet; and CuC1. This gives a direct measure of the fraction of current carried by ions in these melts. Further, the cell efficiency, extrapolated to zero ionic current, is given by cell efficiency = (s leasile + s elexstronic). [1] s lucile for molten CulS would be expected to be no greater than that for molten CuC1, whose s lonle is about 5 ohm-' cm-1, as will be seen in the following. u,.,,.,.,.......for molten Cu,S is of the order of 100 ohm-' cm-'.' Thus, a large increase in cell efficiency from 0 to values of 10 to 100 pet upon addition of CuCl to Cu2S would indicate destruction of the electronic conductance. Conductance Measurements Experimental Procedure—The apparatus and experimental method were the same as those described in detail in connection with the study of electrical conduction in molten Cu,S-FeS mattes.' A four terminal conductivity cell and an ac poten-

Jan 1, 1957

By A. W. Schlechten, Ernest J. Breton Jr.

Experiments on the separation of copper and zinc ions by selective action of ion exchange resins showed the carboxylic type to be more effective than the sulphonic resins. The latter demonstrated a greater capacity over a wider pH range. Data show the effectiveness of resins as a means of concentration. IN recent years the restrictions of stream pollution laws and the high price of metals have created an interest in ion exchange as a means for metal recovery. Some applications have proved successful. In Germany during World War 11, 17 tons of copper per day were recovered from rayon mill wastes by means of ion exchange resins;' and for some time in this country a large ion exchange unit has been in operation for the recovery of copper from rayon waste water. The possibilities of applying ion exchange to the recovery of metals occurring in plating rinse water is particularly promising. In most of these applications only the metal being recovered occurs in the waste. The ion exchange resins act merely as a means of concentrating the metals to a point where they can be recirculated. It would be highly desirable to use ion exchange as a means of not only concentrating but also of separating metals. With the exception of the impressive separations accomplished in connection with the atomic energy program, very little has been done on metal separations.' Therefore, an investigation was undertaken at the Missouri School of Mines and Metallurgy to determine if either of the two main types of ion exchange resins could be used to separate metal ions in solution. The selective removal of copper ions from a mixture of copper and zinc on carboxylic and sulphonic-type resins was investigated as a function of flow rate, pH, copper-zinc ratio, and concentration. It was shown that zinc can be separated from copper and that very large ratios of concentration can be obtained using ion exchange resins. Since ion exchange is relatively new to the field of metallurgy, a brief review of the subject will be included. Theory of Ion Exchange A comprehensive theory for ion exchange has not been developed as yet, but the mechanisms are analogous to metathetical reactions: R Na + Cu++ *=? K(SO3)2 Cu + 2Na+ R is the designation for the ion exchange resin. If a copper solution is passed over a resin bed in the sodium form, two ions of sodium will be released for every ion of copper removed. For the most part this reaction follows the laws of mass action and of electrical neutrality. Consequently, if an excess of sodium ions is passed over a bed containing copper, the reactions will be reversed, and the resin will be regenerated to its original form. A few empirical rules governing the exchange reaction have been set forth: 1—In general ions with a high valence will replace ions with a lower valence. 2—Ions having higher activity coefficients have a higher replacement potential. 3—In a series of mono-valent ions, those with the smallest radii of hydra-tion will tend to replace those having larger radii of hydration. 4—Where ions are similar in most respects, those with the higher atomic weight sometimes will take precedence. This last rule is not as definite as some of the others. These rules apply to rather dilute solutions at moderate temperatures and assume all ions to be present in about equal concentrations. Higher concentrations and temperatures may in some cases reverse the normal exchange reactions. Ion exchange materials are unique in that their efficiency increases as the concentration of the solution decreases. For many exchangers, most efficient operation is obtained at concentrations in the order of one thousandths of a percent. Most applications, though, are made in solutions containing considerably higher concentrations than this. Coste9 as shown that ion exchange resins will remove aluminum and iron effectively' from solutions of up to 10 pct chromic acid. Ion Exchange Resins Ion exchange resins are insoluble, porous, resinous structures to which active groups have been attached. Active groups such as (—SO,,)- and (COO)- pick up cations; hence structures saturated with groups such as these are called cation exchangers. Structures saturated with groups such as (—NH,)' which pick up anions, are referred to as anion exchangers. The resinous structure of necessity is resistant to strong acids, bases, oxidizing, and reducing agents, and most of the common organic solvents. An idea of the stability can be gaged from the fact that resins last for many years under constant use without detectable chemical or physical breakdown. The ion exchange reaction is not confined to the surface of these synthetic resins. Its porous structure permits active groups in the center of a particle as well as those on the surface to remove ions. A high capacity resin such as Amberlite IR-120 will remove up to 3.3 lb Cu per cu ft of resin. In this investigation several approaches to the problem of separating copper from zinc by ion exchange were considered. First, if a reagent could be found which would complex one of these metals and not the other, then by passing this reagent through a bed of exchanger containing copper and zinc, the

Jan 1, 1952

By H. W. Reinhardt, J. W. Dally

A dynamic photoelastic analysis of stress waves interacting with a free surface is described. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb N,). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. The mechanics of rock breakage by means of explosives has received considerable treatment by many investigators including Duvall, Obert, Broberg, Rinehart, and Langefors1-11 over the past two decades. Indeed in more recent years several texts12-15 have been written on the topic, treating a wide variety of subjects which are logically related to the modern technique of rock blasting. In rock blasting the chemical energy of a concentrated explosive contained in a relatively small diameter borehole is utilized to fragment the rock. The explosive is transformed into a gas with enormous pressures which exceed 10-5 bars18 This high pressure shatters the rock in the area adjacent to the borehole and produces dilatational and distortional stress waves which propagate radially away from the borehole. The state of stress associated with these outgoing waves produces a system of cracks which extend for a few feet from the borehole. The breakage produced in this manner is limited as the dynamic stress in the pulse attenuates markedly with distance. In the absence of a free surface, the stress wave propagates away from the source without further fracture. With a free face of rock near the drill hole, another mode of breakage occurs which is due to scabbing failure of the layer of rock adjacent to the free face. These scabbing failures are produced by the reflection of the incident waves and the conversion of compressive stresses into tensile stresses sufficiently large to fracture the rock. The detailed nature of the interaction of the stress waves with the free surface is complex and difficult to treat analytically. However, dynamic photoelasticity offers an experimental approach which gives a fullfield visual display of propagating stress waves and the reflection process. Applications of static photoelasticity to solution of problems related to mining technology have become relatively common (see, for instance, Refs. 17 and 18) with a plastic model loaded to produce a state of stress representative of that occurring in the workings of a mine. The application of dynamic photoelasticity is ex tremely limited. Tandanand and Hartman19 have used a multiple spark camera to study fracture in glass and plastic plates impacted by a chisel-shaped tool. This paper describes a dynamic photoelastic analysis of stress waves interacting with a free surface. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb-N6). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. Experimental Procedure The model illustrated in [Fig. 1] was fabricated from a sheet of Columbia Resin CR-39 to represent a bench with a fixed bottom. Properties of the CR-39 pertaining to these dynamic experiments are listed in [Table 1]. Scribe lines on 1-in. centers are used to identify locations along the bench face. The bench height was 8 in., the burden was 3 in., and the overall dimensions of the sheet, 16 and 18 in., were large enough to eliminate reflections from nonessential boundaries during the period of observation of the dynamic event. To simulate a charge in a borehole, a groove 0.062 in. wide and 0.080 in. deep groove was cut into the sheet from one side. The lower end of the groove was 1 in. or 1/3 the burden distance below the bottom of the bench. The upper end of the groove was 3 in. or one times the burden distance below the upper level of the bench. The groove was packed with 60 mg of Pb No per in. of length, and ignited with a bridge wire detonator. Four different ignition procedures were used to examine the effects of detonation direction on the stress wave interaction with the free face of the bench. In Test 1 the line charge was ignited at the top and the line charge detonated downward. In Test 2 the line charge was ignited at the bottom and the charge burned upward. In Test 3 the charge was ignited in the center with the top half burning upward and the bottom half burning downward. Finally in Test 4 the line charge was ignited at both ends simultaneously. Sixteen high-speed photographs of the photoelastic fringe patterns representing the stress wave propagation were recorded for each of the tests. A Cranz-Schardin multiple spark gap camera 20,21 was operated at framing rates which were systematically varied from 110,000 to 250,000 frames per sec during each test.

Jan 1, 1972

By R. L. Moment

The anisotropic elastic behavior of rolled beryllium sheet has been measured, using a pulse echo technique, and compared with X-ray diffraction data. Calculated elastic stiffness constants compared favorably with published values for beryllium single crystals which were attributed to the strong (0002) rolling plane texture. Variations of Young's modulus in the yolling plane could be associated with the velative distribution of (0002) planes out of their ideal position in the rollitzg pkule. WHEN a metal is subjected to cold working such as drawing, forming, or rolling, a crystallographic texture develops which can significantly alter its physical properties. One method for detecting this texture is X-ray diffraction, but Alers and Liu' have recently pointed out how the prediction of anisotropic physical properties from pole figures alone is not always accurate due to differences in interpretation. Variations in Young's modulus with orientation or, more completely, the values of the effective elastic constants of the worked metal, also serve to indicate the presence of a texture. In fact, as Alers and Liu' pointed out, calculated variations in Young's modulus for assumed orientations, when compared with experimental data, can be used to eliminate some of the uncertainty in interpretation of X-ray pole figures. Thus, elasticity measurements can serve not only to clarify any unusual elastic behavior of worked metal, but also to detect and in part determine the nature of its texture. X-ray determination of the texture of rolled beryllium has been reported by Smigelskas and Barrett,2 who found a strong texture of (0002) in the rolling plane with (1070) planes normal to the rolling direction. In the case of metal rolled at room temperature, they reported that [1010] directions also appeared at positions 60 and 120 deg from the rolling direction in the rolling plane, while in more recent work Keeler3 found these directions were also tilted towards the rolling plane. The texture for beryllium rolled at 80O0C, however, only showed (1010) planes normal to the rolling direction and the spread of (0002) planes out of the rolling plane was less. In looking for elastic anisotropy one might consider unidirectional rolling of a metal as introducing an or-thorhombic symmetry through reorientation of the grains, since the three deformations, compression, extension in the rolling direction, and extension in the cross direction, are orthogonal to each other and unequal in magnitude. Thus the rolled sheet could be treated like an orthorhombic single crystal and the nine stiffness constants of the elasticity tensor used to calculate the anisotropy of Young's modulus, the shear modulus and Poisson's ratio. In this case we could write: which is symmetric about its diagonal. Borik and Alers4 have recently used this approach on rolled die steel with very good results. They found, however, that instead of displaying orthorhombic elastic symmetry their specimens could be considered tetragonal in which case Cr1 = c22, c13 = Ca, and c44 =cjj. This conclusion was made solely on the basis of the measured tensor elements, and serves to point out the advantage of this method for studying the anisotropy of rolled metals. Their calculated values for Young's modulus as a function of angle in the rolling plane also checked very well with direct measurements made on different specimens using the resonance technique. In the present study, cross-rolled beryllium was used which had been unidirectionally rolled about 11 pct for the final reduction. This imparted a slight anisotropy in the rolling plane which was detected both by X-ray techniques and elasticity measurements. For purposes of discussion in this paper, the rolling direction is that direction in which the most reduction passes were made and cross direction is the normal to the rolling direction in the rolling plane. It was also decided to consider the rolled sheet as displaying orthorhombic symmetry for the purpose of obtaining elasticity samples with the direction defined as in Table I. Any change in the final symmetry attributed to the sheet would then be made on the basis of the measured elastic stiffnesses. The final data would then be compared with that expected from the X-ray study and that reported for beryllium single crystals. EXPERIMENTAL PROCEDURE Rolling Schedule. The samples used in this study were taken from a large sheet which, because of its size, had to be unidirectionally rolled for the final reduction. The resulting texture was that of cross-rolled metal with a slight unidirectional texture superimposed. A cast beryllium ingot, 9.500 in. sq by 3.325 in. thick, was cross-rolled to 81 pct reduction followed by unidirectional rolling for an additional 11 pct to give a total reduction of 92 pct. The thickness of the final sheet ranged from 0.265 to 0.280 in. Reduction up to 67 pct was done at 980°C and the final 25 pct at 870°C. Analysis for metallic impurities showed aluminum 0.06 pct, iron 0.19 pct, and silicon 0.11 pct, giving a beryllium purity of 99.64 pct.

Jan 1, 1968

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

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

Jan 1, 1956

By T. S. Lovering

GEOCHEMICAL prospecting extends the age-old method of searching out lodes with a gold pan and rationalizes the prospector's hunch that certain plants are associated with ore. It uses sensitive but cheap and rapid analytical methods to find the diagnostic chemical variations related to hidden mineral deposits. Exploration geologists can gain tremendous assistance from this new tool, although its optimum use is not simple. To bring out the geochemical pattern that reveals the presence of a hidden ore deposit with a minimum number of samples requires a combination of shrewdness, chemical knowledge, and exploration geology. The use of sensitive analytical methods for prospecting had its start in the 1930's in northern Europe, where Scandinavian and Russian geologists had some success in these early efforts. Very little geochemical prospecting was carried on in the United States at this time, and no sustained interest was manifest until the close of World War 11, when geochemical investigations were started by the Mineral Deposits Branch of the U. S. Geological Survey. The purpose of these investigations was to apply geochemical principles and techniques to surface exploration for mineral deposits. Both the research on analytical methods and the routine trace analyses for field investigations were at first conducted by a single group, but it later became apparent that the trace analyses could be done by men of less experience than that required for successful research on methods. For the past several years there have been two groups of chemists, and although their functions overlap, three of the chemists are chiefly concerned with research, while four to six other men make the trace analyses for field projects. The chemical investigations, as well as the field projects of the Geochemical Exploration Section, concern only those phases of the subject that are appropriate to a government organization; every effort is made to help private industry, but not to compete with it, in finding orebodies. The chief aim of the Section, therefore, is to develop new analytical techniques and publish the results promptly, to carry out field investigations of the fundamental principles of geochemical dispersion, and to field test promising- techniques under controlled conditions. Some routine geochemical exploration work is carried on in connection with DMEA loans, and in district studies where the project chief wishes geochemical information on certain areas for his report. It should be emphasized, however, that geologists of the Geochemical Exploration Section are primarily concerned with fundamental principles underlying the distribution, migration, and concentration of elements in the earth's crust. To facilitate the use of geochemical methods the USGS has published much information on its methods of analysis and has provided opportunities from time to time for qualified professional personnel to study these methods, to work in the USGS laboratory, or to attend demonstrations of the analytical techniques at the Denver Federal Center. Typical of the research carried on are the problems now being investigated: 1) Development of rapid and sensitive analytical methods suitable to the determination of traces of metals and other minor elements in various materials, such as rock, soils, plants, and water. At the present time attention is being concentrated on U, Bi, Cr, and Hg, and satisfactory rapid trace analytical methods are virtually perfected for U and Bi. Good methods are also available for: Cu, Zn, Pb, Ni, Co, As, Sb, W, Mo, Ag, Nb, Ge, V, Ti, Fe, Mn, S, and P. 2) The relation of geochemical anomalies in plant materials to the geochemical distribution of elements in soils surrounding the plant. 3) A study of the dispersion halos in transported sedimentary cover such as glacial drift and alluvium over known orebodies. 4) A study of the behavior of ore metals in the weathering cycle. 5) A study of the behavior of the ore metals during magmatic differentiation. This requires a study of the distribution of minor metals in fresh igneous rocks and their component minerals in a well established differentiation series and in adjacent country rock. 6) A study of the dispersion of metals in primary halos in the wall rock surrounding orebodies. 7) Regional and local studies of the metal content of surface and groundwater in mineralized and barren areas. Many field projects of the Mineral Deposits Branch also require the services of USGS chemists during their investigation of the geochemical environment of ore deposits. From the work that has been done certain general principles have emerged. Concentrations of an element that are above the general or background value of barren material are called positive geochemical anomalies or simply an anomaly, whereas values less than background are called negative anomalies. The anomalies most commonly investigated in geochemical prospecting are those formed at the earth's surface by agents of weathering, erosion, or surficial transportation, but more and more attention is being given to primary anomalies found

Jan 1, 1956

By P. Duwez, C. B. Jordan

The phenomenon of the change of volume of pressed powder compacts upon sintering is well known in the field of powder metallurgy. Depending upon the metal or metals involved and the pressure used in forming, a compact may, in the course of time of sintering at a given temperature, expand mono-tonically, contract monotonically, or first show a volume change of one sign followed by a change of the opposite sign. It is clearly desirable to have accurate knowledge of the magnitude and sign of the change in dimensions to be expected in any given case, both from the point of view of direct usefulness in the fabrication of parts by powder metallurgy, and from the longer range viewpoint of elucidating the fundamental mechanism of metallic sintering. The present study was therefore undertaken as a first step in acquiring systematic and reasonably quantitative knowledge of the change in density of metal powder compacts during sintering. For practical reasons, copper was selected as the material to be studied first, and its densification followed as a function of temperature and time of sintering in hydrogen and in vacuum. Experimental Procedure The copper powder used was that designated by the manufacturer (Metals Disintegrating Co., Elizabeth, N. J.) as MD-151. This powder was sifted through Tyler standard screens to separate the fraction having particle size range between 200 mesh and 325 mesh, and this fraction was used in all the subsequent work. Compacts weighing about 10 g were then pressed in a 1 in. diam round die, using a pressure of 20,000 psi throughout. Sintering was carried out in commercially built electric furnaces in which the resistance windings are so disposed as to produce a nearly uniform temperature along the axis of the furnace for a length of about 18 in. centrally located. In order to be able to sinter in a controlled atmosphere, a 2 in. stainless steel tubing was inserted in the furnace. Each end of the tube was cooled by a water jacket about 7 in. long, and closed with a rubber stopper. The hydrogen used for one series of specimens was purified as described in Ref. 1. For the other set, a pressure of about 0.5 mm Hg was maintained during sintering by a Welch Duo-Seal Pump. The specimens were heated on square trays made of stainless steel. In placing specimens in the trays, a thin even layer of powdered aluminum oxide was first sprinkled on the bottom of the tray. A copper guard disk about half the thickness of the specimen was then placed in the tray and covered with a second layer of alumina. The actual specimen was then set on the guard disk, and a final coat of alumina sprinkled over the specimen. This technique was evolved for sintering the specimens in such a way as to reduce the influence of unknown extraneous factors to a minimum. If the specimen is placed directly on the tray and sintered, it is found that the resulting shape is that of a frustum of a cone, rather than a section of a right circular cylinder, since friction with the tray prevents the bottom of the specimen from contracting at the same rate as the top. In the arrangement used in these experiments, the guard disk provided a support which shrank at the same rate as the specimen, and the alumina powder reduced to a minimum friction between guard disk and tray, and between specimen and guard disk. The procedure followed in sintering consisted of bringing the furnace to the required temperature, and then inserting the specimen into the central heated portion of the furnace tube in one of the two atmospheres used. At the end of the heating period, the specimen was cooled by bringing it into a portion of the furnace surrounded by a water jacket. These manipulations were carried out without opening the furnace, by means of rods which were attached to the trays and operated through a sliding seal in the rubber stopper. The progress of densification of the copper compacts was studied at 1300, 1400, 1500, 1600, 1700, and 1800°F. At each of these temperatures, a specimen was allowed to sinter for each of the following time intervals: M, 1, 2, 4, 8, 16, 32, and 64 hr. The thickness and diameter of each specimen were measured with micrometers before and after sintering, and each was weighed on an analytical balance after sintering. Results The techniques described in the preceding section were found to give satisfactory results. The specimens were not detectibly warped after sintering, and were usually of uniform diameter (that is, truly round) to within 0.001 in., a very few showing a variation in diameter of ±0.002 in. All specimens were found to have the same diameter

Jan 1, 1950

By T. M. Allen, W. H. White

THE Greenwood-Grand Forks area of southern central British Columbia, known as the Boundary District, has a long history of mining exploration and production. At the turn of the century this was the premier copper mining camp in the British Empire, its total production amounting to some 20 million tons. Most of this ore came from the great Granby mines at Phoenix, but the Motherlode mine at Deadwood camp, 6 miles to the west, and several mines in Summit camp, 5 miles north of Phoenix, made important contributions. The large deposits were exhausted in 1918 and the district since has seen only desultory exploration and salvage operations. The orebodies are mineralized skarn zones in limestone members of a thick series of Upper Paleozoic sedimentary and volcanic strata. Chalcopyrite is the primary ore-mineral. Copper carbonates and silicates occur sparingly in outcrops, but the oxidized zone generally is very shallow. Much of the surface is mantled by glacial drift which in most places ranges in thickness from 2 to 15 ft. In some of the hanging valleys, however, the glacial drift may be as much as 100 ft thick and may assume drumlin-like forms. In 1951 an ambitious program aimed at the discovery of new orebodies and important extensions of abandoned deposits was launched by Attwood Copper Mines, Ltd. In this district so thoroughly searched by an earlier generation of prospectors, any orebody which had remained undiscovered must have little or no surface indication. Consequently, in addition to the basic detailed geological work, the program of exploration included magnetometer and self-potential surveys. Geological bets and geophysical anomalies were tested further, prior to diamond drilling, by a study of copper distribution in tree twigs and/or in the soil. The soil sampling and analytical methods used and some of the results seem of sufficient importance to warrant this paper. The authors had done some plant sampling in this and other districts, using the dithizone neutral-color-end-point method (Warren and Delavault, 1948, 1949; White, 1950),1-3 but they were unfamiliar with its soil application. Finally, after much experimenting in the field, they adopted the methods described here. These methods are not entirely original or defensible on theoretical grounds, but under field conditions of rapid sampling and analysis the results are reliable enough to be of use. Fig. 1, which shows the results of duplicate analyses of duplicate soil samples taken at 50-ft intervals across an anomalous zone, indicates the relative dependability both of the sampling and analytical methods. Sampling and Analytical Equipment A 2-ft piece of 1-in. solid drill steel, one end sharpened to a broad, conical point. The steel is marked at 1 ft from the point. A 2-ft piece of ½-in. black iron pipe, one end filed to a bevelled cutting edge. The pipe is marked at 1 ft 3 in. from the cutting end. A 3-lb hammer. A plastic or rubberized sheet about 18 in. square. Moisture-proof assay pulp envelopes. A 10-mesh seive made from window screen with the paint burnt off. A small assay spatula. A pan balance sensitive to 10 mg. Two ignition trays about 4 in. square, made of sheet iron turned up along the edges. A Coleman two-burner gasoline stove. An asbestos board about 5x8 in., used as a hot plate on the gasoline stove. A circular aluminum rack to hold 8 test tubes while refluxing (design of Almond and Morris). Pyrex Glassware Large refluxing test tubes, 25x200 mm, marked at 40 ml volume. Breakers, 20 ml. Pipettes, 1, 5, and 10-ml capacity. Graduate, 50 ml. Shaking cylinders, 100 ml, glass stoppers. Burette, 25 or 50-ml capacity, with holder. Chemical Supplies 1 N sulphuric acid. Hydroxylamine hydrochloride, solid crystals. Fisher Alkacid test paper. Copper standard solution. Dithizone standard solution 60 mg per liter. Water reasonably free of metals. Soil Sampling Method: The problem of how to take a soil sample is extremely crucial. The method outlined below, adopted after a number of tests, has the advantages of uniform pattern, uniform depth, and uniform size of sample. The area to be tested was marked off by chain and compass lines 100 ft apart, normal to the strike of possible ore deposits. Numbered stakes were set at 50-ft intervals along these lines and a soil sample was taken at each stake in the following manner. The drill steel was driven into the ground normal to the slope of the surface to the marked depth of 1 ft, moved slightly from side to side, then carefully withdrawn. The iron pipe was inserted to the bottom of this hole, tapped down to the marked depth of 1 ft 3 in. and withdrawn; the 3-in. soil plug in the

Jan 1, 1955

By George S. Ansell, John B. Hudson, Stephen A. Koffler

The permeability of hydrogen through the a phase of palladium has been measured by a low pressure permeation technique under conditions such that bulk diffusion was the rate-controlling process. The observed permeability is described by the equation: J = 1.80 x 1O-3 P½exp(-3745)/RT) cc(stp)/sec/cm2/en over a range of hydrogen pressure, P, from 2.9 x 10-5 m Hg to 5.0 x 10-3 cm Hg, and over a temperature range, T, from 300" to 709°K. The fact that the permeability shows a square root dependence on pressure and a reciprocal dependence on thickness was taken as evidence that bulk diffusion, rather than surface reactions, was the rate-controlling process. The permeability data were used in conjunction with the solubility data of Salmon et al., to determine the diffusivity of hydrogen through palludium as: D = 4.94 x 10-3 exp(-5745/RT) cm2/sec There was no influence of sub structural defects observed over the temperature range employed. From the permeability data obtained, coupled with grain size measurements, it was concluded that the ratio of grain boundary diffusivity to bulk diffusivity was less than 105 over the range of temperature investigated. THE diffusive mass transport of hydrogen in the a phase of palladium has been studied previously by numerous investigators.' In spite of the large amount of attention this system has received, there is not good agreement between the results obtained in different investigations.' This is due in part to the fact that the mass transport was surface-limited during some of these studies, rather than being diffusion-controlled3-5 The reason for the disagreement in other cases is not clear. These studies made use of such techniques as rate of absorption from solutions6 and gases,' electrochemical potential,8 time lag,' and permeation10,11 to determine the mass transport behavior. Of these, the gas permeability technique is the only method which allows an easy test to determine if diffusion is the rate-controlling mechanism, thus eliminating the uncertainty regarding the limiting transport processes inherent in the other techniques. The two most recent permeability studies are those of Toda10 and Davis." Toda determined the permeability of hydrogen in the a phase of palladium over the temperature range from 170" to 290°C, and over the pressure range from 36 to 630 mm Hg utilizing a steady-state gas-permeability technique. Toda's result was: J = 1.41 x 10-3 P½ exp(-3220/RT) where J = specific permeability in cc(stp)/sec/cm2/cm, P½ = square root of the inlet pressure in (cm Hg)½, R = Universal gas constant, and T = temperature in deg Kelvin. Davis11 also employed a steady-state gas-permeability technique over the temperature range from 200" to 700°C and over the pressure range from 0.02 to 760 mm Hg. His result for the permeability of hydrogen in the a phase of palladium was: J = 3.15 x 10-3 P½ exp(-A440/RT) In the range of overlapping temperature for these two investigations, the values of the specific permeability calculated from the above two equations differ by a factor of about 1.8. In the present investigation, the permeation of hydrogen in the a phase of palladium was determined over a wide temperature range, 27" to 436oC, and over the pressure range from 2.9 x 10-5 to 5.0 x 10-3 cm Hg. This temperature range overlaps that of the previous investigations of Toda and Davis, but also covers the lower temperature range which has never before been investigated. The lower pressure range used here avoided the interaction between the dissolved hydrogen atoms observed at higher hydrogen concentrations.' MATERIALS The as-received palladium specimens were cold rolled from a casting and were supplied as 5.08 cm discs of 0.508 and 0.762 mm thickness. According to J. Bishop and Company specifications, the composition of the discs was 99.95 pct Pd, the balance being Cu, Ag, Au, and Ir. In order to obtain samples of varying grain size, the as-received discs were then heat treated. Sample 1 was treated for eight minutes in a nitrogen atmosphere at 810°C and then air-cooled. Sample D was heated first to 550°C in helium. The helium atmosphere was then immediately replaced by hydrogen and the temperature was slowly raised to 1220°C and held for 22 hr. The sample was then cooled to 550°C where the hydrogen was replaced by helium and the disc was further furnace-cooled to room temperature. Sample H was given the same heat treatment, only with hydrogen substituted for helium below 550°C. The reason that hydrogen was not used throughout the entire annealing cycle for samples D and H was to prevent the distortion encountered by low-temperature cycling in hydrogen observed by Darling." After these heat treatments were completed, the

Jan 1, 1970

By J. T. Norton, N. J. Grant, A. R. Chaudhuri

MOST of the recent work to establish the mech-anism of creep in metals at high temperatures has utilized aluminum as the experimental material. It was thought desirable to initiate an investigation of a hexagonal close-packed metal, because of the relatively simple slip system, and compare the observed deformation characteristics with those that have been observed for the face-centerd cubic metals. High-purity magnesium was chosen for this purpose, first, because its strength and other mechanical properties are similar to those of aluminum in the same temperature range, and second, because the existing equipment was ideally suited to observe magnesium during creep. It is proposed in this paper to present a pictorial and qualitative account of the changes that high-purity magnesium undergoes during creep at 500°F. The characteristics of deformation of aluminum described below have been observed by various workers and accounts of these may be obtained from the papers of Chang and Grant.'- These characteristics are: slip, subgrain formation, grain boundary sliding and migration, fold formation, deformation bands, and kink bands. It is well known that in a flat magnesium specimen, slip on the basal plane (0001) in the [1120] direction results in the formation of straight bands on the surface of the specimen. Schmid and co-workers' have shown that this system is operative in the temperature range of -185" to 300°C (-300° to 572°F). They have also shown that a second system, slip on the pyramidal planes {1071} or {1012} in the [1120] direction, is operative at temperatures higher than 225°C (437°F). Between 225° and 300°C (437" to 572°F), therefore, deformation by both these systems is expected. Bakarian and Mathewson5 confirmed the occurrence of pyramidal slip on the {1011} plane and found that it resulted in irregular markings on the surfaces of their specimens. Burke and Hibbard6 obtained evidence of pyramidal slip in single crystals of magnesium deformed at room temperature. Bakarian and Mathewson5 suggested that the irregular appearance of these bands was due to slip on both of the pyramidal planes occurring simultaneously but in the same direction, the close angular relationship between the planes making this process possible. Furthermore, since neither of these planes is close enough to the basal plane, slip on the latter does not exhibit the irregular appearance of slip bands resulting from pyramidal slip. Experimental Procedure High-purity magnesium, supplied by the Dow Chemical Co., was used in these experiments. The analysis was as follows: Al, 0.0002 pct; Mn, 0.0018; Fe, 0.0024; Cu, 0.0002; Sn, 0.001; Ca, 0.01; Ni, 0.0003; Zn, 0.01; Pb, 0.0005; Si, 0.001; and Mg, 99.972. The magnesium was supplied in the form of 1/2 in. diam rods. The specimens had an overall length of 21/4 in., the round ends being threaded to fit the specimen holders. The previously round 3/16 in. diam gage section of the specimen had two parallel flats machined on opposite sides for microscopic observation, yielding a test zone having the dimensions of lx3/16x7/64 in. The specimens were electrolytically polished (without prior mechanical polishing of the machined flats), in a solution composed of 375 ml of ortho-phosphoric acid and 625 ml of ethyl alcohol.' The cathode was a stainless steel sheet bent so that the specimen was completely surrounded. The voltage for successful polishing was 1.5 v at 100 to 300 milli-amp current. Electropolishing for about 45 min sufficed to obtain a good metallographic surface on the specimens after they had been machined. The creep tests were performed under constant load, and two types of equipment were used. In the first, designed by Servi and Grant,V he specimens were beam-loaded, and a furnace could be lowered to surround the specimen. As the microstructural changes could not be observed during the course of the test, the tests had to be interrupted periodically by removing the specimen for microscopic examination. The second unit was a high temperature microscopy furnace designed by Chang and Grant.' The furnace was fitted with an optically flat quartz window having area dimensions 1.25x0.5 in., so that the whole test portion could be viewed through it at magnifications up to x240. The metallurgical microscope had three mutually perpendicular axes of motion, and, in addition, it was possible to measure angular displacements by rotation of the eyepiece. It was thus possible to make precise observations of the specimen during creep, and micrographs could be taken by attaching a camera to the eyepiece of the microscope. The average grain size of the specimens that were tested was about 1 to 3 mm. This grain size could

Jan 1, 1954

By F. G. Jones, R. D. Pehlke, H. E. Gardner

The solubility of nitrogen in liquid Fe-18 pct Cr-8 pct Ni-0. 7 to 2.3 pct A1 alloys has been measured up to the solubility limit for the formation of aluminum nitride in the temperature range 1600° to 1700°C uszng the Sieverts' method. The solubility of nitrogen in 18-8 stainless steel increases with increasing aluminum content. Based on a nitride composition, AlN, the standard free energy of formation of aluminum nitride from the elements dissolved in liquid 18-8 stainless-steel alloys has been determined to be: ?G° = -42,500 + 20. IT in the range from 1600° to 1700° C. EVANS and pehlke1 have measured the equilibrium conditions for the formation of aluminum nitride, AlN, in liquid Fe-A1 alloys. The present study extends that work to the more complex solvent, liquid 18 pct Cr-8 pct Ni (18-8) stainless steel. Recent work by Small and pehlke2 has dealt with the effect of fourth-element additions on the solubility of nitrogen in 18-8 base alloys. They found the effect of aluminum additions, up to 0.74 pct, on the solubility of nitrogen to be small. The present study covered the range from 0.74 to 2.28 pct aluminum, and by extending the composition range may be used to better define the effect of aluminum on the nitrogen solubility in these alloys. EXPERIMENTAL PROCEDURE The Sieverts' method was used to measure the equilibrium solubility of nitrogen gas in liquid 18-8 stainless steel alloys containing 0.74, 1.49, 1.93, and 2.28 pct Al. The solubility was measured as a function of the nitrogen gas pressure at temperatures of 1600°, 1650°, and 1700°C. The apparatus used is the same as described by Small and Pehlke.2 The 100-g melts were made from Ferrovac-E high-purity iron, Crucible Steel Co.; 99.95 pct Cr, Union Carbide Corp.; 99.9 pct Ni, International Nickel Co.; and 99.99+ pct Al, Aluminum Co. of America. The aluminum was charged at the bottom of the crucible, surrounded by nickel and iron. The chromium was packed into the interstices to minimize vapor transport of the aluminum during initial melting. The hot volume of the system, measured for each melt with argon, ranged from 45 to 55 standard cu cm with a temperature coefficient of —8 x 10-3 cu cm per °C. The melt temperature was measured with a Leeds and Northrup disappearing-filament type optical pyrometer sighted vertically downward on the center of the melt surface. The temperature calibration of the system by Small and pehlke2 was assumed. Two problems are involved in determining the solubility product of a solid, metal nitride phase in liquid iron alloys. These are: 1) establishing the point of departure from Henrian behavior at the solubility limit of the metal nitride phase; and 2) determining the composition of the solid nitride which is precipitated. Determination of the solubility product of AlN was made by admitting small amounts of nitrogen into the reaction bulb until the deviation from Sieverts' law was clearly evident in the form of a pressure halt. To obtain the solubility product at several temperatures during one run the following procedure was used: 1) add increments of nitrogen to determine the Sieverts' law line at the lowest desired temperature; 2) continue to add nitrogen to precipitate a small amount of the nitride phase; 3) increase the melt temperature 50°C to dissolve the precipitated nitride; 4) repeat step 2 until either a nitride formed or the system reached ambient pressure; if a nitride formed at 1650°C, the sequence was repeated at 1700°C. The composition of the precipitated phase was checked by an X-ray diffraction pattern obtained from powder scraped from the surface of the solidified 1.93 pct A1 melt. RESULTS AND DISCUSSlON Solubility Measurements. Fig. 1 is a typical nitrogen-absorption curve obtained from measurements on a 1.93 pct A1 alloy. Since the initial absorption of nitrogen follows Sieverts' law the nitrogen solubility is plotted as a function of the square root of the pressure of nitrogen gas in the reaction bulb. The results of the solubility measurements for all alloys studied are summarized in Table I. The slope of the Sieverts' law line for each alloy was determined. Since this is also the solubility of nitrogen at 1 atm pressure of nitrogen gas, the latter designation is used for the data. It should be noted. however, that in most cases the value lies above the solubility limit for AlN. Fig. 2 shows the effect of aluminum on the solubility of nitrogen at this reference pressure and as a function of melt temperature. The solid portions of the lines represent attainable solutions; the dashed regions lie above the limit for precipitation of AlN.

Jan 1, 1969

By J. F. Elliott

PRESENT knowledge of the usual metallurgical slags indicates that they are, for the most part, rather complex in behavior and as yet there is no ready means for describing, in a simple manner, the behavior of any one of them. One of the best known slag systems is the iron oxide-silica-lime ternary which is the basic "solvent" in a number of important metallurgical refining operations, the basic open hearth being one of the most important. In this operation, the slag dissolves such components as sulphur, phosphorus, manganese oxide, and magnesia. Considerable study of this slag system and the behavior of these additions has been carried out in the past by a number of authors, as has been summarized in several critical reviews.','2 However, except for determination of the activity of iron oxide, only a limited amount of effort has been directed towards developing, from these data, an understanding of the general behavior of the basic solvent. Reported here are the results from a series of calculations based on data from the literature which permit a semiquantitative evaluation of the activities of iron oxide, silica, and lime (plus magnesia) in the ternary system at 1600°C. The preliminary results, which were reported briefly at a symposium held by AIME in 1953, have been revised and are completed. The steps in the calculation are as follows:* I—establish the activity curves and the curve of the excess molar free energy of mixing at 1600°C for each of the binary systems, 2—construct the activity surface of iron oxide for the ternary from the data on the binary systems and information available in the literature for the ternary area, 3—determine the surface of excess molar free energy of mixing for the ternary system from the activity surface of iron oxide and from the molar curves obtained for the binary system, and 4—differentiate the ternary surface of the molar excess free energy of mixing to obtain the ternary surfaces for the logarithm of the activity coefficients for silica and lime (log rslo, and log rc.~). Si0,-Fe,O: Schuhmann and Ensio have measured the activity of iron oxide in simple iron oxide-silica slags when in equilibrium with y iron. Their data recalculated to 1600°C are shown in Fig. 1. Also included is a point representing a measurement by Gokcen and Chipmana of the activity of iron oxide at 1600°C at the point of saturation with solid silica. For convenience and in accordance with other treatments,' the calculations are based on the hypothetical component, FelO, which is obtained by converting all the analyzed iron in the slag to FeO. In spite of Schuhmann and Ensio's conclusion that the activity of iron oxide in the system does not vary with temperature over the experimental range of 1258" to 1407"C, the data are corrected to 1600°C assuming that temperature does have an effect. It was felt to be most reasonable to assume that the term log rr.10 is a linear function of the reciprocal of the temperature. Reyu has indicated that an effect of temperature on the activities in this system is to be expected from the Schuhmann and Ensio data. In essence, the correction consists of multiplying the experimental value of log rf,,o by the ratio of the experimental temperature in Kelvin to 1873°K. The magnitude of the correction is not large, being approximately 11.5 pct of the experimental value of log rve10. A very minor correction was necessary to compensate for the fact that the slags were in equilibrium with y iron in the experiment, while at steel-making temperatures they would be in equilibrium with liquid iron. Data for the correction were obtained from Darken and Gurry. The standard states established are pure liquid iron oxide (FelO) in equilibrium with pure liquid iron (with the appropriate amount of oxygen in solution) and pure liquid silica. The method of plotting in Fig. 1 is convenient for the calculation of the activity of liquid silica and permits a reasonable extrapolation for the activity of Fe,O in the ranges where no experimental data are available. The uncertainty in the extrapolation to infinity at one terminal where Nvelo = 1 for the usual Gibbs-Duhem integration is reduced considerably by this method. The region of two coexisting liquid phases is estimated to range from 1.8 to 41.7 mol pct Fe,O. The nature of the activity curve for the single-phase region indicates that the activity of iron oxide across the two-phase region is very close to 0.39. Computation of the function log ~F,,o/(1— NF,,o)' for this region (dashed line) in conjunction with the curve through the adjusted experimental data indicate the best probable value of 0.382 for alPe,o in the two-phase area. The line from 0 to 0.018 Nf~~o is obtained by assuming that the component follows Henry's law. In this range, the value for log rveto is 2.59. Appropriate mathematical manipulation of the plotted linet yields the activity curves for the The curve AF", the excess molar free energy of mixing (actual minus ideal), as shown in Fig. 3 is also computed from Fig. 1. This curve is required for subsequent calculations. CaO-Fe,O: The phase diagram for the lime-iron oxide system when in equilibrium with liquid iron is not well known but there appears to be no intermediate compound present. This fact as well as the activity values for Fe,O extrapolated to the CaO-Fe,O binary from Taylor and Chipman' tend to indicate somewhat negative deviations from ideality for the activity curves for the two components. Strong indication of this is evident in Fig. 1 where are plotted the points computed from the estimated activities of Fe,O for the binary system.' It appears that the best line through the data is a horizontal straight line. Because of the general indication of the slight negative departure from ideality, the line is extrapolated horizontally to NF~,o = 0. It is con-

Jan 1, 1956

By C. Feng, W. E. Krul

A study was made of the development of texture and the anisotropy in plastic flow of Ti-8Al-1Mo-1V alloy. Based on Pole figure determinations, the shifting of texture induced by rolling at approximately 400°C was found to be due primarily to slip rotation for the major Portion of the material. Grain boundary shear is believed to be an important factor. The anisotropy of the textured alloy was examined in terms of the variations of yield stress under tension and the ratio of bi -axial strain increments µp, in the temperature range 25" to 290°C. The results were related to Hill&apos;s theory on plastic anisotropy. The Schmid factors of (1100)[1120], (1101)[1120/, and (1101)[1120] slip systems were analyzed and found to be compatible with the observed anisotropy. Cross-slip between these planes was proposed as a possible deformation mode. In a number of published articles, considerable interest has been directed to the possible achievement of texture hardening in hcp metals. Following Backofen, Hosford, and Burke,&apos; this phenomenon was related to the yield criteria of the material and was expressed in terms of the biaxial strain ratio, r = d?w/d?l. The higher the value of r, the greater is the expected potential for texture hardening under certain loading conditions. For a given material, r varies with direction. Such variation can be traced to the anisotropy in plastic flow and can be explained within the framework of the various modes of deformation. Hatch2 found that a high r value coincides with a texture whereby the (0001) pole is closely aligned with the surface normal for sheet materials, Based on the analysis of the slip on the {1010}, {1011}, and (0001) planes, Lee and Backofen3 and Avery, Hosford, and Backofen4 concluded that the resistance to thinning is reduced by the operation of the (0001) <1120> slip system; with this reasoning they were able to explain the low r values (i.e., r « 1) observed in magnesium alloy sheets in the rolling direction and in commercially pure titanium in the transverse direction. The general equation, dealing with plastic flow in a polycrystalline aggregate has been used to correlate the plastic anisotropy and texture. In this expression, T and s are shear and normal stresses, and dri and d? are shear and normal strain increments, respectively. Assuming that five slip systems are operative within each grain and applying the principle of maximum work,5,6 one can determine the m value among the available systems. On this basis, Hosford7 and Chin, Nesbitt, and Williams&apos; were able to correlate m with yield stress under plane-strain compression, and Svensson9 was able to predict the variation of yield stress in textured aluminum. These workers made their analyses from materials in which slip operation is known to be associated with plastic flow. Questions remain regarding the derivation of Hill&apos;s theory on plastic anisotropy,10,11 since it was formulated on von Mises&apos; yield criterion.&apos;&apos; Its ability to deal with other forms of deformation has been in doubt.13 Others have discussed the validity of Hill&apos;s quadratic equation relating strain and yield stress.14&apos;15 For hcp titanium, deformation by various modes of slip and twinning operations has been reported.16-20 If all possible modes of deformation operate and contribute substantially to the plastic flow, it is difficult to imagine how the quadratic expression can suitably describe the anisotropic plastic flow of titanium alloys. Backofen and Hosford15 considered that Hill&apos;s is a macroscopic theory and implied that the major mode of deformation by slip mechanism will adequately describe anisotropy of the material. In the present investigation, slip operation will be shown to play the major role in the development of sheet texture induced by rolling of a commercial titanium alloy. Although twinning and other modes of deformation may also operate, their operation is believed to be secondary. The anisotropic properties of the sheet, which can be expressed in terms of directional variation of r, µp = -d?w/d?l and the yield stress will be shown to be governed primarily by slip operation. MATERIALS AND EXPERIMENTAL TECHNIQUES The titanium alloy chosen for the present investigation had a nominal composition of 8 wt pct Al, 1 wt pct Mo, 1 wt pct V, and 0.1 wt pct interstitial impurities. Sheets varying between 0.1 and 0.15 in. thickness were used. The alloy was received in a condition which was prepared by rolling at 900°C and annealing at 700°C. Subsequently, the sheets were subjected to further reduction in thickness by rolling at 400°C. A total reduction in thickness of 65 to 70 pct was obtained by a series of quick passes in a rolling mill with intermediate reheating. Further reduction in thickness was not possible due to cracking developed at the edges of the sheets. X-ray measurements were conducted in a Siemens and a Norelco unit to determine the texture of the sheets. Reflection techniques were used exclusively with CuK, radiation and a nickel filter. The loss of X-ray intensity due to geometric defocusing was calibrated with a technique described previously." The (0001), (1010), and (1071) pole figures were plotted from 0 to 80 deg, and to present the texture elements quantitatively, inverse pole figures were constructed following the technique described by Jetter, McHargue, and Williams.22 Tensile experiments were carried out at 25", 175",

Jan 1, 1970

By P. N. Richards, M. K. Ormay

Commercially hot-rolled low-carbon steel strip may have one of two basic types of orientation texture, depending upon the amount of a iron which was present during the finishing passes. The changes in these textures with varying amounts of cold reduction up to 95 pct have been determined for the sheet surface plane and for parallel planes down to the mid-plane. The development of cold reduction textures has been reassessed on the basis of (200), (222). and (110) stereographic pole figures and pole density or inverse pole figure values. In agreement with the literature, it is shown that the textures can be described in terms of partial fiber textures but alternative descriptions are given for one of the fiber textures, in order to more closely correlate with experimental data. One partial fiber texture consists of orientations of the type (hkk)[011] extending from (100)[011] to {322}(011) in agreement with the literature. At moderate amounts of cold reduction, a second partial fiber texture forms with a <331> fiber axis inclined 20 deg to the sheet normal and a range of orientations centered on one close to (1 11)[112] and reaching to (232)[101] or (322)[011]. An alternative description involves a (111) fiber axis parallel to the sheet normal but capable of rotation about the rolling direction with rotation about the fiber axis. ORIENTATIONS developed in low-carbon steel strip after cold reduction are of commercial importance because they control, in part, the final preferred orientations after subsequent annealing. The method of control however is not understood completely. Some preliminary work indicated that the cold-reduced orientations and the subsequent annealing textures of commercial low-carbon steel were dependent on the orientations present in the material before cold reduction, that is, those present in the hot-rolled strip but, to date, the effects of initial orientations have not been extensively investigated. For this reason, much of the information given in the literature on development of preferred orientation is difficult to assess as details of initial texture and processing conditions are often inadequate or are altered by a subsequent heat treatment such as normalizing.&apos; It is known2 that anomalous results for near surface orientations may be obtained if lubrication during cold rolling is not adequate but whether lubricant was used during the experiments has not always been given, nor has the exact depth below the surface at which determinations have been made. A comprehensive review of cold rolling textures has been made recently by Dillamore and Roberts&apos; and more restricted recent reviews are due to stickels4 and Abe.5 Based largely on the experimental work of Bennewitz,1 reviewers have accepted that the preferred orientations produced on cold reducing low-carbon steel can be described in terms of two partial fiber textures as follows: Partial Fiber Texture A which has a (011) direction in the rolling direction and includes orientations within the spread from (211)[011] through (100)[Oll] to (211)[011.]; there is some controversy as to whether it extends as far as the orientation (111)[011]. As Dillamore6 has observed, the extent of this partial fiber texture depends on the intensity levels selected. Partial Fiber -texture B which has a (011) direction located 60 den from the rolling direction in the plane containing the rolling direction and the sheet normal. There are two directions which satisfy these conditions and orientations in this partial fiber texture extend from (21l)[0ll] through (554)[225] to (121)[101]. The orientations {211}(011) are members of both partial fiber textures A and B and it can be noted that a variant of {554)<225> is within 6 deg of a variant of {111}(112). Barrett7 had postulated earlier that, in addition to orientations which would fall into partial fiber texture A, a true fiber texture with a (111) direction in the sheet normal was present after heavy cold reduction. This fiber texture would include orientations such as {111}(011) and {111}(112). Later investigators, notably Bennewitz,&apos; have discounted this, mostly on the ground that the partial fiber textures A and B, as described above, contain all the strong orientations that have been observed. However in other work it has been reported2 that (222) pole density or inverse pole figure values show a continuing increase with increasing reduction by cold rolling and give values considerably greater than for any other low indices plane. Thus it could be inferred that a (111) fiber texture as described by Barrett would be one which becomes more dominant with increasing cold reduction, whereas Bennewitz&apos; concluded that components such as {554)(225) in partial fiber texture B began to decrease in intensity at high reductions. Following Bennewitz, one would expect a decreasing (222) pole density value (parallel to the sheet normal) with increasing cold reduction. Because fiber textures consist of grains with a range of orientations that have one axis in common, it has been inferred that during deformation the crystal orientations rotate about the fiber axis&apos;74 and that the orientations of crystals that at one stage belong to one fiber texture can rotate on further cold reduction into the other fiber texture through an orientation in which the two fiber textures intersect.&apos; For example,

Jan 1, 1970

By Hsun Hu, B. B. Ruth

The rates of migration of high-angle boundaries in zone-refined aluminum crystals rolled 20 to 70 pct in the (110)[i12/ orientation were studied. Following a recovery anneal at an appropriate temperature to stabilize the polygonized structure, boundary migration rates of artificially nucleated grains were measwed isothermally at several temperatures. Results indicate that the rate of boundary migration depends strongly on the amount of deformation and on the cell size of the polygonized matrix, and is related to the driving free energy by a power function. The degree of anisotropy in growth 0.f the re crystallized grains nn&apos;th preferred mientation is independent of deformation; the migration rates of the fast-moving and the slow-moping boundary segments of a gowing grain differ by as much as one order of magnitude. The actir\ation energy fm a grain boundary migration, although nearly the same for both the fast-moving and the slow-moving boundaries for a given deformalion, decreases from 45 to 30 kcal per mole with an increase in deformation from 20 to 70 pct reduction. Re crstallization by the growth of the artificially nucleated grains results in preferred orientation. The Percentuge of&apos; grains favorably oriented for growth increases with increasing deformation. None of these grains corresponds to the ideal Kronberg-Wilson orientation relationship. The observed growth aniso-tropy is discussed in terms of boundary structure. The boundary velocity as a function of the cell inter -facial area, or the driving free energy, is discussed in the light of current theories of boundary migration. It is well established that recrystallization with re-orientation occurs by the migration of high-angle boundaries of strain-free grains. The driving force for this process is provided by the free energy stored in the metal during deformation. A quantitative study of the effect of varying driving force on grain boundary migration in deformed metals has not been possible heretofore, primarily because of: 1) concurrent recovery steadily decreasing the available driving free energy for boundary migration, &apos;-3 and 2) in-homogeneity of strain in the deformed metal.4 Aust and Rutter3 studied grain boundary migration in striated single crystals of zone-refined lead. Although the driving free energy in such crystals remains unaltered during annealing, this method does not provide a range of driving free energies over which measurements of grain boundary migration can be made. In the present investigation, the rates of migration of high-angle boundaries in deformed aluminum zone- refined single crystals were studied at various temperatures, after deformation ranging from 20 to 70 pct reduction by rolling at -78°C in the (ll0)[i12] orientation. The boundary migration rates along different crystallographic directions were determined under steady-state conditions, i.e., in the absence of competing recovery processes or impingement of recrystallized grains growing into the deformed single crystal matrix. Simultaneous recovery was eliminated by suitable anneals prior to the boundary migration measurements. The recrystallized grains, which grew a ni so tropically into the homogeneously polygonized matrix, developed flat boundary segments during early stages of growth. These boundary segments subsequently migrated along a direction approximately normal to the boundary plane into the matrix rystal. Increasing deformation over the range employed was estimated to increase the driving free energy for boundary migration by about five times. The kinetics of the boundary migration process, examined under these conditions, indicate that the boundary velocity is greatly affected by a small change of the driving free energy in the matrix crystals. These results were examined in the light of the current theories of grain boundary migration. EXPERIMENTAL PROCEDURES Single crystal strips (9 by 1 by 0.125 in.) of zone-refined aluminum, were seed-grown by the Bridgman method in a high-purity graphite mold (<lo ppm ash) at 1 in. per hr. Precautions were taken to minimize contamination of the metal during crystal preparation and subsequent handling. Spectrographic analysis of the metallic impurities in the grown crystals is Qven in Table I. The crystals were rolled in the (110)[112] orientation at -78°C to various reductions in thickness, ranging from 20 to 70 pct, in 10 pct increments. The desired reduction was achieved by many rolling passes, each being no more than 0.002 in. To minimize surface friction, the crystal was rolled between two thin layers of teflon. For those crystals rolled more than 40 pct, it was necessary to remove the disturbed surface layers by electropolishing at -5" to -10°C at an intermediate stage of rolling. The edges of deformed crystals were removed by a jeweler&apos;s saw while submerged in alcohol at -78° C to obtain samples of about ? by i in. The distorted metal at the cut edges and the surface layers were then removed by electropolishing, with removal of a minimum of 0.004 in. from each surface. The thickness of the crystals prior to rolling was chosen so that the final thickness was 0.025 in. for all samples. These deformed single crystals were each prean-nealed for 1 hr at an appropriate temperature in the range of 130" to 280°C, depending upon the amount of deformation. The purpose of this preannealing was to

Jan 1, 1970

By R. W. Carpenter, J. C. Ogle

It is possible, by using pack-rolling instead of conventional rolling, to reduce a number of metals to thicknesses of 2µm or less. Such thinfoils are generally made at room temperature without intermediate annealing. In addition, pack-rolled foils fail by developing pinholes at thicknesses near 2µm instead of developing the shear cracks usually observed in cold-rolled ductile metals. This paper presents the results of a general investigation of the deformation substructure and texture developed in copper and iron pack -rolled from 130 to about 2µm thickness. Electron microscopy showed that in both metals a fine (0.2 to 0.5?µ m) deformation subgrain structure formed during pack-rolling; in neither case was this substructure grossly different from substructures formed during conventional rolling. The deformation texture formed in pack-rolled iron was quite similar to usual bcc textures; however, in the case of copper, the cube texture was stable during pack-rolling and the normal copper deformation texture was unstable. It is shown analytically that the constraining pack induced a large hydrostatic pressure in the foils during pack-rolling. The pinhole failure mechanism is attributed to the presence of the large hydrostatic pressure during pack-rolling; this strongly suppressed the growth of shear cracks. The stability of the cube texture in copper is also probably due to the unusuul stress distribution developed during pack-rolling. EXPERIMENTS at several laboratories have shown that very thin foils of the common structural metals and many of the rare earths can be made by "pack-rolling". 1-3 The technique was originally developed to make specimens for nuclear scattering experiments and foils for X-ray filters. It is also useful for making experimental laminar metallic composite bodies and foils thin enough for direct examination by ultra-high voltage electron microscopy without the need for special thinning techniques. Pack-rolling in the present context means a three-layer pack, with the material to be rolled into foil comprising the center layer. The outer two layers, which constrain the foil during reduction, are ordinarily austenitic stainless steel. Typically, a 130 µm (0.005 in.) metal strip can be reduced to a final thickness of 2 µm or less by this process. This is accomplished at room temperature, without intermediate annealing. It has been observed that foils produced by this process do not exhibit at any stage of their reduction the severe work-hardening found in strip rolled by conventional cold-rolling methods. Neither is the failure characteristic the same."&apos; Conventionally cold-rolled ductile metal strip fails by developing shear cracks on planes whose normals nearly bisect the angle between the rolling direction and normal to the rolling plane; these are planes of maximum shear stress. In pack-rolling this mechanism has not been observed; failure occurs by the formation of pinholes on the foil surface (penetrating the foil). If pack-rolling is continued the hole density increases. These differences in behavior imply the existence of appreciably different substructure in pack-rolled foils compared to substructure in conventionally rolled material, or perhaps that the geometry of pack-rolling has an effect on the foil behavior. This paper describes an investigation of deformation substructure and texture in some specimens of pack-rolled copper and iron, and some considerations of the stress distribution in the foils during rolling that result from the geometry of pack-rolling. EXPERIMENTAL DETAILS Three different materials were used for pack-rolling in the present work: soft copper sheet (99.8 pct Cu, 0.03 pct 0, electrolytic tough pitch) and two types of iron, Ferrovac E* and Armco iron. Each was "Crucible Stccl Co. initially in the form of 130 µm annealed strip with grain size ranges of approximately 10 to 40 µm. The initial texture of the copper (determined as noted below) was the normally observed cube type (001)[100]; there was evidence of a small amount of material in the cube-twin orientation reported by Beck and Hu.4 The initial texture of the Ferrovac E was similar to that reported for recrystallized iron by Kurdjumov and sachs,5 who list the principal orientations as {111}<112>, {001}<110> 15degfrom RD and a weak component {112}(110) 15 deg from RD. The starting texture of the Armco iron was not determined. Pack-Rolling Procedure. A four-high mill was used for all specimens. The work roll and backing roll diameters were 1.625 and 5.25 in., respectively. The peripheral roll speed of the work rolls was about 2.5 in. per sec. All foils were initially reduced from 130 to 100 µm by conventional straight rolling and then inserted into a pack, without any intermediate annealing, for further reduction. The pack consisted of an 0.033 in. (838 µm) thick 3 by 6 in. polished sheet of austenitic stainless steel, folded to make a 3 by 3 in. jacket. After folding, the jacket was given a small reduction to close the fold tightly before insertion of the foil. During pack-rolling a constant change in roll spacing was made every third pass. The roll-spacing change corresponded to a 5 pct reduction in thickness for a new pack. This approached a 10 pct reduction when the pack had decreased to about half its original thickness. At this point the deformed pack was discarded and a new one

Jan 1, 1970

By C. T. Wei, A. Kelly

USING a recently developed X-ray method, reported by Schulz,2 it is possible to make a rapid survey of the perfection of a single crystal at a particular surface. This technique has the advantage of allowing a large surface of a specimen to be examined by taking a single photograph and it compares well with other X-ray methods in regard to sensitivity of detection of small angle boundaries. During the course of a survey of the perfection of large crystals of aluminum produced by a number of methods, an examination has been made of a number of single crystals produced from the melt using a soft mold (levigated alumina)." Crystals grown by this method are known, from an X-ray study carried out by Noggle and Koehler,3 to contain regions where they are highly perfect. In the present work, it has been possible to obtain photographs showing directly the distribution of low angle boundaries at a particular surface of these crystals. single crystals were grown from the melt using the modified Bridgman method with a speed of furnace travel of -1 mm per min. These were about 1/10 in. thick, 1 in. wide, and several inches long. The metal was 99.99 pct pure aluminum supplied by the Aluminum co. of America. The crystals were examined by placing them at an angle of about 25° to the X-ray beam issuing from a fine focus X-ray tube of the type described by Ehrenberg and Spear4 and constructed by A. Kelly at the University of Illinois. A photographic film was placed SO as to record the X-ray reflection from the lattice planes most nearly parallel to the crystal surface. The size of the focal spot on the X-ray tube was between 25 and 40 u, and the distance from the X-ray tube focus to the specimen (approximately equal to the specimen to film distance) was -15 cm. White X-radiation was used from a tungsten target with not more than 35 kv in order to reduce the penetration of the X-rays into the specimen. Exposure times were approximately 1 hr with tube currents between 150 and 250 microamp. The type of photograph obtained from these crystals is illustrated in Fig. 1, which shows a number of overlapping reflections from the same crystal. The large uniform central reflection is traversed by sets of horizontal white and dark lines. These two sets run mainly parallel to one another. Lines of one color are wavy in nature and often branch and run together. Large areas of the crystal surface show no evidence of these lines whatsoever. The lines are interpreted as being due to low angle boundaries in the crystal, separating regions which are tilted with respect to one another. A white line is formed when the relative tilt forms a ridge at the interface and a black line is found when a valley is formed. In a number of cases, the lines stop and start within the area of the reflection and often run into the reflection from the edge, corresponding to a low angle boundary starting from the edge of the crystal. The prominent lines run roughly parallel to the direction of growth of the crystal although narrow bands can run in a direction perpendicular to this; see Fig. 2. Although they may change their appearance slightly, the lines tend to occur in the slightly,Same place in the X-ray image and to maintain their rough parallelism when the crystals are reduced in thickness by etching. Thus the low angle boundaries can occur at any depth within the crystal. The appearance of the lines is unaffected by subjecting the crystal to rapid temperature changes, such as plunging into liquid nitrogen or rapid quenching from 620°C. From the width of the lines on the x-ray reflection, values can be found for the angular misorienta-tion of the two parts of the crystal on either side of a boundary. The values found run from 1&apos; to 10&apos; of arc, but values of UP to 20&apos; have sometimes been found, e.g., the widest lines on Fig. 2. These mis-orientations are much less than those commonly found in crystals possessing a lineage structure. When a number of a and white lines occur, running in a roughly parallel direction across the image of a Crystal, the total misorientation corresponding to lines of one color is approximately equal to that corresponding to lines of the other color. The interpretation of the lines as due to low angle boundaries has been checked in a number of ways. Photographs taken with different specimen-to-film distances distinguish lines due to low angle boundaries from effects due to surface relief of the specimen. Normal Laue back-reflection photographs, taken with the beam irradiating an area of the surface showing a number of the lines, show white lines running through each Laue spot. Black lines are set to see by this method. X-ray photographs were also taken, using the set-up described by Lam-one et al.5 when the beam straddles regions giving rise to lines in the Schulz pattern, split reflections are observed within the Bragg spot. The misorienta-tions calculated from the separation of these reflections and that found from the widths of the lines on the schulz technique patterns show good agreement. An exposure was made with Lambot technique of an area of the crystal showing no evidence of low angle

Jan 1, 1956

By G. E. Johnson

E. D. HYMAN*—How much sorting of scrap is done ? G. E. JOHNSON (author&apos;s reply)—We do practically no sorting. We charge "run of mine" scrap to the furnace. The unmeltables, mostly iron, are in such demand today that there is no difficulty in disposing of them. It may soon be desirable to sort out from the unmeltables as much of the brass as possible. J. J. BRUGMAN†—We have somewhat similar problems in the secondary aluminum business. What is your method of removing the unmelted material from the furnaces? Why have you such an apparently small space in which to charge your materials? Do you find that you have to seal that opening, or can you have it open and continuously charge at one end and pull out the other ? G. E. JOHNSON—Our means of melting scrap is efficient only to the extent that we use the waste heat from the vaporizing chamber to do the job. It is a batch process. We open the charge door and place the scrap on the hearth by hand shoveling. The door is then closed during the melting down period. After the melting is complete, the opposite door is opened and the unmeltables are raked out. The doors are approximately 3½ X 4½ ft and are not sealed during the process only closed. They are nominally tight. Some metal is oxidized in the process. We have visualized a means of conveying the materials through this melting unit with the metals that are melted trickling out during its travel. T. H. WELDON‡—Mr. Johnson, in line with the last question, is it necessary to seal the furnace between the melting down and the vaporizing unit, or have you got an inverted syphon in the bottom of the chamber? G. E. JOHNSON—That was one of the first things we encountered. We had to have a sealed opening, and it is a molten metal seal. You have indirectly asked me another question, which was: "Do you have to seal up the melting unit?" I would say we should exclude as much air as possible, although we are not too efficient in doing that. We allow the melting unit doors to be open when we charge and when we remove unmeltables. You can readily see that that would lead to the idea of having a controlled atmosphere in the melting unit, and I think this would do a more efficient job of melting the scrap. T. H. WELDON—How often do you charge the furnace? G. E. JOHNSON—We charge the melting unit, and rake out the unmeltables, about every hour. H. R. HANLEY*—Are any provisions made for controlling the rate of oxidation for the production of various size particles for certain characteristics of the zinc oxide product? G. E. JOHNSON—Yes, there are many. You are getting pretty much into the fine points of zinc oxide manufacture. Some of us still think we have something to learn about that. In general, this muffle furnace as I have described it to you produces a rounded particle of zinc oxide which is generally formed by a rapid oxidation of the zinc vapor, followed by rapid cooling. We have gone to the other extreme in some of our experiments. We have changed the furnace to produce a type of zinc oxide, such as we thought was peculiar to American process zinc oxide, by controlling the temperature at the point of oxidation and maintaining that temperature for a much longer period of time than we do when we make the rounded shape. There are other relationships that this furnace readily provides. One of the important factors is the ratio of air to zinc vapors. We can vary that by varying the air supply to the baghouse, or vary the rate at which we are vaporizing the zinc by the simple expedient of regulating the temperature over the carborundum arch. We have a number of variables that permit us to produce all of the grades of French process zinc oxide from lead-free up through the highest grades of seal oxides. There are many controls that we can apply to the operation. What I have said is but a brief condensation. K. MORGAN*—Can Mr. Johnson give us some idea of the fuel consumption of the furnace ? How much oil does he use per ton of zinc distilled? I am also interested to know what sort of heat transmission he gets through the arch? What is the thickness of the tiles used to construct the arch? Some time ago we built a small furnace for a different purpose, using a carborundum arch, and we found that the reflectivity of the molten zinc surface was so great we had to use a very high arch temperature. We found we made an improvement by having a layer of carbon on the surface of the zinc. Has Mr. Johnson had any experience on these points ? Does he make any sort of insolu-bles which he leaves in the furnace which he cannot tap out ? G. E. JOHNSON—I believe your first question was the fuel consumption. If I recall, somewhere in this paper there is a test that I quote. I believe we used 800 gal in a given period of time. Offhand I cannot translate that into tons of metal. I might also state that we have this understanding; that the carborundum arch, as the temperature becomes higher, becomes more efficient in heat transmission. As a matter of fact, I believe it is at about 2600°F or higher that the highest efficiency of heat transmission becomes available. We have calculations that I cannot quote from memory which indicate that the carborundum arch does a really very fine job for this type of furnace. Another point that we had considered was the fact that this furnace could be readily constructed so as to furnish an ideal source of heat for waste heat boilers. If a carborundum arch was used over the melting unit, we would have no zinc vapors in the gases at all— just clean combustion gases from which we would have removed some of the heat. L. P. DAVIDSON†— The insolubles

Jan 1, 1950