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By R. W. Kraft

A comprehensive analysis of the crystallographic and metallographic structure of several Al-CuAl, lamellar eutectic grains solidified under equilibrium conditions has been performed. A consistent pattern was discovered which was interpreted in terms of a detailed atomistic model of an interface describable as: Interface II {111} AL 11 {211} <101>Al <120> ? Several arguments are presented to substantiate the theory. It is compared in detail with another interface model characteristic of the Wid-manstatten precipitate of CuAl2 in A1 at low Cu levels. In addition, a concept is proposed to help explain the structure of the compound CuAl2. It has been shown that the eutectic alloy between A1 and CuA1, can be forced to solidify as substantially parallel lamellae throughout a relatively large volume&apos; by appropriately controlling the solidification parameters of growth rate, thermal gradients, and impurity level and by causing solidification to proceed in a unidirectional fashion from one end of an ingot to the other. A typical ingot solidified in this manner shows three distinct zones along the length of the ingot, Fig. 1. At the head end is a region consisting of many different grains, some of which are elongated slightly in the direction of solidification. After a few centimeters of growth, this polygrained region gradually merges into the second zone which consists of a very few elongated coarse grains. The third zone at the tail end is a region of eutectic colonies caused by segregation of impurities. Microscopic examination of transverse and longitudinal sections of the ingots reveals that during the initial stages of growth (zone I) the lamellar structure is frequently highly distorted and twisted but that it straightens out in zone 11. This characteristic pattern suggests that nucleation of a eutectic grain begins randomly at the head end of the ingot, and that some particular orientation relationship between the phases is more favorable from an energy consideration than others for one reason or another, so that some grains grow and others which are less favorably oriented do not. The favorably oriented or "low energy" grains continue to grow until excess solute rejected at the advancing liquid-solid interface destroys the parallel lamellar structure by forming a cellular rather than a substantially planar interface. When this occurs, the parallel lamellae fan out and eutectic colonies are formed because the lamellae grow perpendicular to the local interface. Questions naturally arise as to the crystallographic nature of the "low energy" grains. What do the grains which persist into zone II have in common? Can this explain the stability of such grains during growth? To answer the first question it is necessary to determine the crystallographic orientation of the lamellae of each phase relative to one another. This has been done for Al-CuAl2 eutectic alloys by two different techniques on specimens prepared in different ways.2&apos;3 The results were different from each other and from a third orientation relationship between A1 and CuA1, reported for overaged A1-Cu alloys.4 The three orientation relationships are summarized below to illustrate their similarities and their differences. (001) ? 11 (001) A1; [l00] ? 11 [l00] Al Eutectic, Ref. 2 (001) 8 1) (001) A1; [1001 ?11 [1101 A1 Eutectic, Ref. 3 (001) ? 11 (001) A1; [l00] ? 11 [310] Al; Widmanstfitten, Ref. 4 It is not surprising that different orientation relationships were found by Ellwood and Bagley,&apos; and Takahashi3 since the solidification conditions were quite different. Nor is it surprising that Mehl, Barrett, and Rhines 4 found still another value since they were studying another type of alloy. Nevertheless, it would be expected that some logical and systematic pattern could be found if all the alloys were at equilibrium since the same two phases are

Jan 1, 1962

By M. S. Klima, P. T. Luckie

Interfacing new or improved unit operations SUBMODULES with the EXECUTIVE of a macro analysis simulator usually requires modification of the input data. For example, particle processing SUBMODULES that are sufficiently general in nature to provide useful predictions require input data for rather narrow size fractions. Such data is not always available for the EXECUTIVE and must therefore be generated by the SUBMODULE. A successful interface to allow incorporation of a new SUBMODULE for comminution and one for classification in a general stream state flowsheet simulator is presented. The general nature of the SUBMODULES, as well as the logic of expanding and contracting the required data input is discussed.

Jan 1, 1983

By M. E. Wadsworth, C. H. Pitt

Nickel corrosion in sulfuric acid solutions at elevated temperatures and oxygen wer-pressures was imestigated. Weight loss was 1inear with time and varied directly with oxygen concentration. Independent variation of the possible active species in solution indicated that the undissociated sulfuric acid molecule plays an important part in the corrosion mechanism. The rate determining step was considered to be the adsorption of oxygen on a site containing adsorbed H2SO4. THE tendency for a metal to go into solution depends on a number of factors some of which are: 1) the position of the metal in the electrochemical series; 2) the type and concentration of corroding species in solution; 3) the concentration of oxygen in solution; 4) the type of film formed at the liquid-metal interface; and 5) the physical state of the metal. The corrosion of a metal in an aqueous solution may be considered to be a heterogeneous reaction that occurs at the liquid-metal interface. The reaction is generally considered to occur as a result of electrochemical potential differences within the system. Little work has been published in the literature concerning the corrosion of pure nickel. A great deal has been publistled dealing with the experimental and theoretical aspects of the over-all corrosion process. Evans,1 Uhlig,&apos; and recently Todt 3 and Tomashoff,4 have published books which review the results of experiments which have been conducted on corrosion, and have developed some of the basic ideas of the more widely accepted theories of corrosion. Friend5 states that. nickel does not readily discharge hydrogen from any of the common nonoxidiz-ing acids and that a supply of some oxidizing agent is necessary for appreciable rates of corrosion. He further notes that at temperatures between atmospheric and close to boiling, corrosion rates tend to vary with concentration, temperature, and aeration in acid concentrations up to 25 pct. Whitman and Russel6 studied the effect of dissolved oxygen on a number of metals in acid solutions and found that oxygen accelerates the rate of corrosion of nickel in sulfuric acid. Flowers and Kelley7 in studying the action of dissolved CO, on electroplated nickel postulated that nickel dissolves as NiHCO3 in the presence of CO, and air. It was found that oxygen was necessary for corrosion to take place and that the rate increased with increasing amounts of oxygen in solution. Flowers and Kelley attributed the oxygen effect to cathodic depolarization. MacGillavry, Rosenbaum, and wensson&apos; determined metal solution potentials of nickel in various electrolytes. They found that nickel has no tendency to corrode in alkaline solutions in the presence or absence of air. In acid solutions in the presence of air, metal solution potential increases in the order of 1/2 v were observed. This increase was attributed to probable chemisorption of oxygen on the nickel surface and the corrosion mechanism suggested was the interaction of H+ ions with the nickel oxide formed at the surface. Delahay9 observed the reduction of oxygen on various metals. A polarograph was used to measure the course of the reaction. With some metals hydrogen peroxide was produced as an intermediate compound. However, nickel was not considered to be a hdrogen peroxide producer. Van Rysselberghe 10,11 and associates attributed the accelerating effect of carbon dioxide on the corrosion process to the presence of percarbonic acid produced in solution reacting with the hydrogen peroxide. The percarbonic acid can be reduced at less negative potentials than hydrogen peroxide and as a result accelerates the reaction. EXPERIMENTAL Since a complete description of the apparatus used can be obtained elsewhere,12&apos;13 no attempt will be made here to describe the equipment other than to note that it consisted essentially of an autoclave unit from which samples could be withdrawn periodically without disturbing the interior state of the autoclave. A titanium autoclave liner was used to protect the autoclave from the solution.

Jan 1, 1961

By M. Ahlers, Horace Pops

Slip features and formation of stress-induced mm-tensite have been studied in single crystals of fl phase Cu-Zn alloys in the composition range between 43 and 48 at. pct Zn. A phenomenological analysis is presented in which the glide planes and directions that me associated with the inhomogeneous shear in the martensite phase are predicted from the experimentally determined habit planes and macroscopic shear directions. It is shozun that the resolved shew component of the applied stress on the secondary shew system is a very important factor governing the formation of stress-induced martensite. A comparison is made between martensitic phases that form spontaneously upon cooling and those phases that arise from deformation. THE ß phase in Cu-Zn alloys is unstable and may transform spontaneously by a martensitic transformation1-3 during cooling. Thermoelastic and burst-type spontaneous martensitic phases have been observed3 in the composition range between 38 and 42 at. pct Zn. Martensite forms in alloys containing more than 42 at. pct Zn only by cold work below a temperature denoted as Md.4 Thus, alloys near the equiatomic composition can undergo a stress-induced transformation upon cold work at room temperature. Although data have been obtained concerning the effect of temperature5 and composition4 on the deformation of polycrystalline Cu-Zn alloys, it is rather surprising that few detailed studies6-8 on 6 brass have been conducted for single crystals where the stresses acting on crystallographic planes can be determined. A thorough understanding of transformation mechanisms requires knowledge of the role of stress and plastic strain. With this objective in mind we have made an investigation of the stress-induced rnartensite transformation in single crystals of 0 brass in the composition range between 43 and 48 at. pct Zn. Particular emphasis is given to the morphology and crystallographic features and a comparison is made between stress-induced and spontaneous martensite. I) EXPERIMENTAL PROCEDURE Master alloys having nominal zinc contents of 43, 45, and 48 at. pct were prepared from spectroscop-ically pure metals (>99.999 pct) in sealed quartz tubes under a partial pressure of helium. These alloys were cut into several pieces and converted into small rods by melting in quartz tubes. Subsequently, single crystals were grown from the rods by the Bridgman technique and homogenized for 3 hr at 820°C. Lattice parameter measurements were made from stress- relieved filings. Compositions, as determined from the reported variation of lattice parameter with atomic percent zinc,&apos; indicated a zinc loss of less than approximately 0.25 at. pct. The single crystals were electroturned using a phosphoric acid electrolyte into tensile specimens each with a center section of 1 mm diam and 1 cm gage length. Cylindrical specimens approximately 3 mm in diam and 10 mm long and spark-machined rectangular blocks approximately 3 by 3 by 10 mm were prepared for compression studies. These blocks were stress-relieved and electropolished to eliminate any stresses introduced by spark machining. Crystal orientations were determined to an accuracy of ±2 deg primarily from back-reflection Laue photographs, and sometimes by the rotating single-crystal method. Figs. 1 to 3 show the location of the tension and compression axes within unit stereographic triangles. All specimens were deformed plastically at room temperature using an Instron machine, the crosshead speed being 0.02 or 0.05 cm per min. A hard steel hemisphere was placed at the upper end of the compression samples to achieve uniaxial loading. Trace normals of slip markings and habit planes of strain-induced martensite were determined to an accuracy of ±4 deg from the rectangular blocks by a two-surface analysis and from cylindrical specimens by measuring the angle between the tensile (or compression) axis and the tangent to the surface trace for different rotations about the deformation axis. Slip

Jan 1, 1969

By Rex B. McLellan, W. A. Oates, William W. Dunn

Vapor transport experiments have been carried out in order to determine the saturation solubility of carbon in cobalt and nickel with respect to graphite over a large temperature range. Some of the uncertainty existing in the thermodynamics of these systems has been removed and accurate estimates of the heat and entropy of solution of carbon in nickel and cobalt have been deduced. The relatitle partial entropies of carbon are considered to be predominantly vibrational in origin. ALTHOUGH the thermodynamic properties of solid solutions of carbon in cobalt and in nickel have been investigated previously, the results of these investigations show a marked lack of agreement amongst themselves. In this investigation simple vapor transport experiments have been undertaken in order to measure the temperature variation of the saturation solubility of carbon in nickel and cobalt with the object of removing to some degree the uncertainties in the thermodynamics of these systems. In the case of the C-Co system, early measurements of the saturation solubility of graphite in Co show results at the same temperature differing by almost an order of magnitude.1-5 Recently Schenck, Frohberg, and Jaspert6 measured the equilibrium between CH4-H2 mixtures and C-Co solid solutions at five temperatures ranging from 850° to 1050°C. Their values of the activity of carbon in the solid solution, deduced from a knowledge of the chemical potential of carbon atoms in the gas, varies linearly with composition at each temperature and the authors concluded that the solutions were Henryan. The saturation solubilities deduced from Schenck, Frohberg, and Jaspert&apos;s measurements are in good agreement with the solubility determined at 1000°C by Rao and Nicholson7 and the value at 1000°C deduced from the measurements of smith8 on the equilibrium between CO/CO2 mixtures and C-Co solutions. The object of this investigation was to check the results of Schenck, Frohberg, and Jaspert and also to extend the range of solubility data to higher temperatures. In the case of the C-Ni system, there is fairly good agreement between the values given by schaefer9 for the saturation solubility of carbon C, in nickel, the value given at 1000°C by Rao and Nicholson,7 and that deduced from Smith&apos;s8 measurements of the equilibrium between C-Ni solutions and CO/CO2 mixtures at 1000°C. The values of C, deduced from Schenck, Frohberg, and Jaspert&apos;s6 measurements of the carbon activity in nickel are also in fairly good agreement. However, there is a large discrepancy between the above set of measurements and those of Lander, Kern, and Beach," who measured the carbon solubility of nickel in equilibrium with graphite by depositing an excess of graphite on the surface of Ni-foils from a gaseous mixture and subsequently diffusing in the carbon. These results are considerably higher than those mentioned above. The determinations6 of carbon activity a, in nickel from the CH4-H2 equilibrium showed that at all the temperatures investigated, the ac-values varied linearly with concentration up to about a, = 0.6 and then began to increase with concentration much more rapidly. On the basis of auxiliary experiments in which C-Ni solutions were equilibrated with graphite, Schenck, Frohberg, and Jaspert concluded that their CH4-H2 solid equilibrations at high values of a, were spurious and a, behaved linearly with composition up to the saturation limit (a, = 1). The short linear extrapolations of Schenck, Frohberg, and Jaspert&apos;s a, data yield values of C, in good agreement with those of Lander, Kern, and Beach." The solubility data for nickel discussed here is presented in Fig. 1 in the form of plots of ln[Cc/(l - 2cc)] vs 1/T. The discrepancies mentioned are clearly seen. In this investigation a vapor transport method is used to measure C, over as wide a temperature range

Jan 1, 1969

By J. B. Cohen

EARLY investigators1-4 reported that additions of beryllium to silver caused embrittlement. The in-termetallic phases which are now known to exist5,&apos; were not known at the time. Solidification appeared to occur by a simple eutectic reation.4,7 (The primary beryllium-rich phase appeared globular, when the liquidus temperature was near the melting point of pure beryllium, and angular when the liquidus was much lower; in discussion of Sloman&apos;s work,4 it was suggested that this difference was due to an intermetallic compound which was not revealed by the polishing technique.) In the investigation reported here, it was found that if the compounds now known to exist were avoided, certain beryllium-silver alloys containing large amounts of the primary beryllium phase possessed sufficient ductility to be cold formed. Alloys containing 14 and 20 at. pct Ag were prepared from vacuum-cast beryllium containing 1.0 to 1.2 pct impurities and silver, 99.99+ pct pure. The elements were melted together by induction in beryllia or alumina crucibles under argon at less than 1 atm pressure. The cooling rate was adjusted by regulating the temperature of the melt and by reducing the power to zero without stopping the water flow in the induction coils, which were in contact with the crucible. Ingots were about 0.75 in. in diam with a grain size of 0.12 to 0.25 in. Microscopic investigation of transverse or longitudinal sections of an ingot cast from a temperature well above its melting point showed that, in general, the compounds did not form, presumably because of rapid cooling; the alloys consisted of beryllium-rich particles in a silver-rich matrix as shown in Fig. 1. A eutectic structure was not observed, probably .due to the low beryllium concentration of the eutectic composition and eutectic divorcement. Within a given grain, the small globules of the primary phase were all oriented in the same direction, as indicated by examination under polarized light; the orientation varied from grain to grain. This suggested that the globules were branches of the same dendrites. If cooling was too slow, a third constituent was observed in the microstructure; because it formed around the primary beryllium-rich globules it was Fig. 1—Ag-Be alloy, 18.6 at. pct Ag, as-cast. Bright field illumination. Etched with an aqueous solution of NH,OH and H2O2. X500. Reduced approximately 21 pct for reproduction. probably the 6 compound. A thin ring around an ingot often contained this constituent. When this compound was present in large quantities, or the silver segregated so that large regions occurred with the beryllium-rich globules in contact, sections from the ingot were brittle. When the compound was initially absent, it was possible to carry out reductions in thickness of 50 pct by cold rolling with only limited edge cracking; failure did not occur until reductions of 80 pct. A typical cross section after cold rolling is shown in Fig. 2. After simple bend tests, microcracks were found; these apparently were difficult to propagate in the two-phase structure, as the specimens continued to behave in a ductile manner after the cracks appeared. Similar cracks would probably be closed during rolling. It is apparent in Fig. 2 however, that the primary beryllium particles undergo extensive plastic deformation. Hardness values of the alloys indicated that some work-hardening occurred during cold working. Fig. 2—Ag-Be alloy, 18.6 at. pct Ag, reduced 83 pct in thickness by cold rolling. Bright field illumination. Etched with an aqueous solution of NH,OH and H2O2. X500. Reduced approximately 21 pct for reproduction.

Jan 1, 1961

By R. K. Datta, T. S. Davis

YVO4:EU, excited under 3650A radiation, shows a marked increase in total brightness with in~rease in temperature. At 25°C the response to 3650A radiation is about 48 pct of its maximum response which occurs at about 350°C, Fig. 1. In an attempt to explain the phenomenon, one of the present authors&apos; (R.K.D.) investigated the diffuse reflectance spectra of the phosphor at different temperatures (up to -150°C) and was unable to observe any significant change to which the increased brightness could be reasonably ascribed. Since then diffuse reflectance spectra at elevated temperatures have been obtained in this laboratory using an improved device. A significant decrease in the diffuse reflectance of a phosphor in the ultraviolet region—especially in the longer wavelength region—at -300°C has been observed. The purpose of this note is to describe the device used for high-temperature reflectance measurements and to explain the increased brightness of YVO4:Eu phosphor at elevated temperatures under 3650A excitation. Experimental. YVO4 and YVO4:Eu samples were prepared as previously described.&apos; The elevated-temperature reflectance spectra were obtained with a Cary 14 spectrophotometer equipped with a diffuse reflectance accessory and a ring collector. CaF2 was used as the standard. The cell used

Jan 1, 1969

By R. S. Sinha

A properly designed pre- and post-grouting program aided with coherent construction sequence and adoption of flexible design approach provide a practical combination to solve excavation problems in a hostile rock environment: intensely fractured and sheared. The Pacheco Pumping Plant demonstrates the utility of an engineered grouting program.

Jan 1, 1984

By J. Gordon Parr, M. J. Bibby

In addition to the (bcc) - (cph) transformation at 882°C a second distinct change of slope has been observed on a titanium cooling curve between 905" and 960°C.1,4 Duwez,1 commenting on work by McQuillan,2-4 attributed this arrest to contamination of the specimen with oxygen—a possibility that existed even at the reduced pressure of 10-5 mm Hg at which the experiments were conducted.

Jan 1, 1963

By P. C. Johnson, B. A. Stein

This paper describes a study of the effects of combined heat treatment and explosive loading on the mechanical properties of high-strength steels. nis program investigated two distinct areas: 1) the effect of shock waves, without gross irreversible defmmution, on a 3-Cr steel at various stages of heat treatment; and 2) the effect of rapid deformation (explosive forming) on H-11 and D6-AC steels in the metastable austenitic state. The mechanical properties of these steels were improved, in some cases markedly, as a result of these treatments. ,AUSFORMWG, which requires the plastic deformation of metastable austenite, is a process which can appreciably improve the properties of selected alloy stee1s.l,2 The Ausform process significantly increases the strength of these steels without decreasing their ductility. The properties at high temperatures are also improved through a change in the response of the steels to tempering. Although the mechanism by which ausforming alters the properties of these steels is not fully understood, it appears that the dislocation arrays produced by deformation of the metastable austenite influence the structure of the martensite on subsequent transformation. This, in turn, affects the strength, ductility, and tempering response of the martensite. This research used chemical explosives to deform steels at various stages in their heat treatment in order to improve the properties of these steels. The explosive energy is used in two ways; 1) high-pressure shock waves are propagated through the steel to produce extensive microscopic shear strain without causing a large irreversible change in shape, and 2) explosive energy is used to cause extensive macroscopic plastic strain in the metastable austenitic state (explosive forming). I) AUSFORMING WITH INTENSE SHOCK WAVES The steel used in this phase of the research was an alloy having a nominal composition 0.43 pct C, 3.0 pct Cr, 1.5 pct Ni, and 1.5 pct Si. The steel was subjected to intense shock waves in three conditions: 1) in the metastable austenitic state, 2) in the tempered mar tens itic state, and 3) in the tempered martensitic state after ausforming by conventional techniques. The specimens were in the form of disks 2.75 in. in diam and 5/16 in. thick. These were incorporated into a specimen assembly consisting of two disks pressed into a 5 by 5 by 1 in. block of stainless steel, Fig. 1. Spalling (or scabbing) is confined to the front disk. The specimen is protected from oxidation and decarburization by the surrounding metal. The temperature of the assembly is monitored by a thermocouple inserted into one side of the stainless steel block. The assembly is positioned over an oil reservoir which serves both as a means of catching the disks and as quenching medium for the disks shocked under ausforming conditions. Plane shock waves are introduced into the assembly by a metal driver plate impacting the top surface of the block. The driver plate is accelerated by a chemical explosive sheet supplied by E. I. du Pont de Nemours & Co. All the specimens were subjected to plane shock waves having a peak pressure of approximately 430 kbar. The pressure is that quoted by G. E. Dieter for the plane wave generator used in this work.&apos; The driver plate used was 1/4 in. thick, so that the initial pulse was essentially a l/2-in.-wide square wave. The attenuation of the peak pressure during the subsequent 1/4 in. is estimated to be less than 5 pct. The shock front induces a temperature rise, a portion of which is irreversible. Rough estimates (+25 pct) of this temperature rise have been made for iron shocked at room temperature.4 For a 500-kbar shock wave, the temperature rise in the shock front is about 700°F, and is held for a time of the order of microseconds. The irreversible temperature rise, which remains after the shock wave passes, is about 450°F.4 The disks are quenched to room temperature within a few seconds of the shock treatment. It should be emphasized that the temperature rises given above are estimates for pure iron at room temperature, and are not necessarily true for the tests made in this work. The disks shocked at temperatures in the metastable austenitic range were austenitized in the stainless steel assembly in a furnace protected from the firing area. The assembly was removed from the furnace and placed over the recovery reservoir. The plane wave generator was then positioned and

Jan 1, 1963

By K. T. Aust

It is proposed that the intergranular corrosion of austenitic stainless steels is associated with the presence of continuous grain houndary paths of either second phase, or solute segregate resulting from solute-vacancy interactions. Experimental observations of structural changes and crrosion behavior of different types of austenitic stainless steel provide support for this poposal. On the basis of this model, it is shown that the intergranular -corrosion susceptibility of austenitic stainless steels in nitric-dic hromate solution may be substantially reduced either by suitable heat treatments or by impurity control. AUSTENITIC stainless steels, such as Type 304, generally have excellent corrosion resistant properties when properly solution heat-treated and used at temperatures where carbide precipitation is slow. However, several corrosion environments have been found which produce intergranular corrosion of solu-tion-treated stainless steels, that is, those steels with no detectable carbide precipitation.&apos;&apos;2 Of the various corrosion environments, the most widely used test solution has been the boiling nitric-dichromate solution. In these acid solutions, stainless steels have been found to be susceptible to intergranular attack despite the addition of carbide-forming elements such as titanium or columbium, or despite lowering of the carbon content or use of high-temperature solution treatments. Studies of the electrochemical mechanism of corrosion attack have been made by several worke1s3&apos;4 who found that oxidizing ions such as crt6 depolarize the cathodic reactions and consequently raise the open-circuit potential of stainless steel immersed in nitric acids. As a result of this, the anodic reaction is accelerated. The reason for the localization of anodic activity at the grain boundaries, and resulting intergranular corrosion, has not been conclusively determined. Several workers, e.g., Streicher,3 and Coriou et al.,4 have suggested that the strain energy associated with grain boundaries provides the driving force for the accelerated intergranular corrosion. This argument would predict that alloys of high purity would still be susceptible to intergranular attack. However, work by chaudron5 and by ArmijO,6 has shown that high-purity alloys are immune to attack, in disagreement with this argument. An alternative suggestion is that chemical concentration differences exist between grains and grain boundaries, that is, impurity segregation at boundaries, and that these chemical differences provide the driving force for localized attack. It is this impurity segregation which can lead to accelerated dissolution of grain boundaries when the alloy is exposed to a suitable corrodant. This mechanism would predict the immunity of high-purity alloys to inter-granular attack, which is in agreement with experi-mental observations. In the present paper, some recent studies on inter-granular corrosion of austenitic stainless steels which were conducted by coworkers and myself will be re-tibility A simple model will be described in which it is proposed that the intergranular corrosion of aus-tenitic stainless steel is associated with the presence of continuous grain boundary paths of either second phase or solute-segregated regions.* On the basis of this model, it is suggested that the intergranular corrosion rate can be markedly reduced by the formation of a discontinuous second phase at the grain boundaries if the discontinuous second phase incorporates the major part of the segregating solute, drained from the grain boundary region. Results are presented of corrosion tests and electron microscopic studies of different types of austenitic stainless steel after various heat treatments which provide experimental support for this model. Finally, a solute clustering mechanism, based on a solute-vacancy interaction, is shown to be consistent with the results obtained for inter-granular corrosion of solution-treated austenitic stainless steels. EXPERIMENTAL Corrosion tests using weight loss measurements were made on sheet specimens, which were lightly electropolished, washed, and immersed in boiling (115°C) 5 N HN03 containing 4 g crt+6 per liter added as potassium dichromate. Studies in which the inter-granular penetration depth was measured both by electrical resistance and metallographic methods have shown an empirical correlation between the rate of intergranular penetration and the weight loss per unit time for identically treated specimens of stainless steel." As a result, although all the corrosion data reported here are in terms of simple weight loss measurements, these data are considered to reflect primarily the rate of intergranular dissolution. Fig. 1 shows a typical result of intergranular attack of a solution-treated Type 304 stainless steel after 4 hr in a boiling nitric-dichromate solution. The wide grain boundary grooving at the surface, and the attack at incoherent twin boundaries, are evident; very little corrosion attack is seen at the coherent twin boundaries. INTERGRANULAR CORROSION MODEL

Jan 1, 1970

By Robert G. Van Nostrand, John H. Henkel

TRANSIENT potentials obtained in resistivity prospecting can be separated into two classes. The first is electromagnetic, has a comparatively short time constant, and increases in relative amplitude as the electrode separation is increased. These electromagnetic transient potentials, of which an excellent theoretical treatment is given by Yost: are the result of changes in the current and can be classed as differentiated signals. The second class is electrochemical, has a comparatively long time constant, and decreases in relative amplitude as the electrode separation is increased. The electrochemical signals are generated by the current flow itself and can be classed as integrated signals. The transient potentials due to electrochemical factors are the subject of this article. The phenomenon is referred to as induced polarization. Schlumberger" was the first worker to observe induced polarization, but he was unsuccessful in attempts to apply the principles of induced polarization in electrochemical prospecting. Other workers, notably Bleil; have studied polarization and in some cases pointed out its possibilities, but no theory has been presented that describes polarization and its time dependence adequately. It is the purpose of this discussion to present the essence of a theory to geo-physicists and to show that it leads to results consistent with experimental evidence. The theory on which this analysis is based has existed in electrochemical circles since 1910."

Jan 1, 1958

By Larry G. Hayes

Development of the Bowers-Campbell zinc deposit, located in the Shenandoah Valley two miles northwest of Timberville, Va., was commenced in 1956 by the Tri-State Zinc Co. The occurrence of lead-zinc mineralization in this area has been known for many years, but the first serious exploration program was initiated in 1951 by the geologic staff of Tri-State Zinc Co. Ordovician dolomites. The deposit is approximately 700 ft long, 100 ft wide, and 475 ft thick. Its projected plan has an elongated ovoid shape, where- as the profile appears boot-shaped with the upper portion outcropping. Vertical cross sections show the lense as having been thrust-faulted along certain bedding planes. The movement along these bedding thrusts varies greatly and in one case, has offset the deposit so as to divide it into an upper and lower orebody. The breccia lense strikes parallel to the N 34" E strike of enclosing strata.

Jan 9, 1960

By Oliver Bowles

WHILE vast quantities of limestone and dolomite are used in metallurgy, the estimated production in 1926 being 23,860,000 tons, there are many problems connected with their use which have not received adequate study. The literature of metallurgy is notably lacking in comprehensive discussions of fluxing or furnace stone. Approximately 900 lb. of limestone is used for every long ton of pig iron produced in the blast furnace, but this important constituent of the charge receives little attention compared with the intensive study that has been applied to ores and fuels, the other important constituents of the charge. In an effort to elucidate some of the doubtful points, the writer has made a wide review of metallurgical literature, and has had the disappointing experience of finding not more than a paragraph or two on metallurgical stone for each two or three thousand pages of literature reviewed. Furthermore, the limited information supplied is in some instances contradictory and even absurd. For example, a correspondent in a reputable metallurgical magazine classifies magnesia and silica together as impurities in flux "that must be melted and run off as slag." From the furnace operator&apos;s viewpoint it is desirable that as complete knowledge as possible be obtained concerning the effects of chemical composition and physical character of the stone on its action in the furnace and on the quality of the metal produced. A better knowledge of these features is advantageous also to the quarry operator in that it enables him to work more intelligently in producing stone that will best satisfy the metallurgists&apos; requirements. The following pages comprise a brief compilation of data now available. Much of the information is well established and probably acceptable to most metallurgists. On some points there is room for debate, and the chief purpose in presenting a paper at this time is to arouse discussion which will throw more light on controversial points and thus assist the author in preparing a more comprehensive and accurate dis¬cussion of metallurgical limestone problems.

Jan 1, 1928

By M. E. Wadsworth, R. D. Groves, B. W. Madsen

Experimental results obtained from large-scale (7 ton), long-term (500 days) leaching of low-tenor copper sulfide ores were interpreted by a geometric model involving the movement of a reaction zone through the ore fragments. The postulated leaching mechanism involved mixed kinetics and included diffusion of the reacting species through the host rock and a chemical reaction at the surface of the mineral particles. Ore properties which were considered were Ore particle size and shape, grade of ore, and mineral content. Excellent agreement between the mixed kinetic model and the laboratory leaching results was obtained when -1/2-in. ore particles were not included in the leach. Also, a satisfactory prediction of copper recovery from +1/2-in. ore with a different particle size distribution was made; however, it was necessary to modify the shape factor in the model. Prediction of copper recovery from an ore sample which included the -1/2-in. fine fraction and leaching for 460 days was 56.5%, and the recovery from leaching was 47.0%. The presence of fines caused solution channeling and a deficiency of oxygen which inhibited the leaching rate. Also, compaction of fines around coarser particles interfered with circulation around the ore particles, and bulk solution transport probably was a rate controlling factor.

Jan 1, 1976

By J. E. Campbell, G. D. Calkins, N. M. Ewbank, M. Pobereskin, A. Wesner

GRINDING for size reduction affects the economics of many processes and products. It is essential as the first step in many industrial processes and is also a finishing step for materials with properties depending on particle size, such as talc, cement, and silica sand. Intermediate and fine grinding are vital operations in the U. S. cement industry, which is producing more than 250 million bbl of cement per year.&apos; Wear of the grinding media is a large part of the grinding operation cost. Problems encountered in grinding cement are so complex that evaluation of efficiency and economy of grinding media is difficult.2 It has been especially difficult to evaluate the relative effectiveness of different types of balls because there are no good testing techniques. Many other industrial operations can be evaluated on a laboratory scale with reasonable accuracy. This does not hold true for evaluation of grinding balls. The consistent results obtained in a laboratory test under a given set of conditions are not always borne out in field application. Rough evaluations of the effectiveness of various compositions and types of grinding balls have been made in the field by using a full charge of one type in a mill and comparing the production record with another run using another type of ball. This method is time-consuming and not very precise, as the second run may not have been carried out under identical conditions. Laboratory-scale tests, on the other hand, have yielded inconclusive results, and many investigators have turned their attention to the development of a field testing technique. Field testing small sample lots of grinding balls has been impractical because it is difficult to identify and recover the test specimens from the grinding mill, and individual groups of balls that have undergone different heat treatments can not be separated.".4 To overcome these difficulties, previous investigators have identified the balls by distinctive marks, notches, and drilled holes, but this procedure has three serious drawbacks: 1) Grinding characteristics and quality of the steel balls may be affected. 2) Physical markings may be worn away in the grinding process, especially during a prolonged run. 3) Recovery from the bulk of the charge will be extremely difficult because the markings are hard to see and may be masked by a coating of the product. To circumvent these difficulties, a radioactive-tracer technique was proposed for recovery and separation of steel grinding balls and subsequent evaluation of the various compositions of the balls. The proposed technique involved five basic operations: 1) Thermal-neutron irradiation activation5 of each group of test grinding balls to a different level of specific radioactivity. 2) Addition of groups of radioactive steel-ball specimens into a ball tube mill. 3) Recovery of radioactive steel-ball specimens from the bulk of the mill charge. 4) Separation of the various groups by their specific radioactivity. 5) Evaluation of actual grinding ball wear. Before any physical tests were performed, required neutron irradiation intensity and time were calculated. Probable composition of the steels to be used was ascertained. An examination was made of the radioactive nuclides8 to be formed which would contribute measurably to the radiation level immediately after irradiation and during the test operation. The radioisotopes formed, their types of radiation, and their half lives are listed in Table I. Of these radioisotopes only iron-59 and chromium-51 were significant for the actual wear test. The intensity of radiation that could be detected by a Geiger counter when the test was completed was the basis for the minimum activation level established. The intensity of radiaton that could be safely handled at the beginning of the test was the basis for the maximum activation level, although this was not considered a major problem. Ten groups of grinding balls of various composition and/or surface or heat treatment were to be tested. One group was designated for the minimum irradiation time. The remaining groups were designated for irradiation periods that increased by increments of 33 pct from that of each preceding group. This difference was considered enough for separation and identification of the groups by comparison of specific activity. Potential Hazards: Possible radiation hazards that might be encountered during this experiment were evaluated for the three important phases: 1) the radiation hazard of placing balls and removing them from the mill, 2) contamination of the product cement by radioactive material worn from the balls, and 3) contamination of the steel by the radioactive balls left in the mill. The radiation intensity expected from the whole group of radioactive balls was calculated to be 250 milliroentgen per hr at 1 ft. This meant the balls would require special shielded packaging and warning labels on the shipping containers. In a radiation field of 250 mr per hr a man can work for 1 hr without exceeding maximum permissible weekly exposure. Since the balls could be dumped into the mill in a matter of seconds, relatively little radiation exposure was anticipated at this stage of the operation. If the weight loss in the balls was 7.7 pct per month and the cement feed through the mill was

Jan 1, 1958

By W. Rostoker, H. Nichols

It has been demonstrated in previous work1&apos;2 that wetting of aluminum alloys by liquid mercury can cause fracture to occur with substantial suppression of prior plastic flow. This has been interpreted as the action of a critical liquid species in reducing the cohesive strength of a stressed solid at sites of potential crack nucleation. In this way the critical transverse stress for fracture nucleation is reached at much lower stresses than is normally the case. The stresses for both fracture nucleation and fracture propagation are depressed by the same mechanism. In so doing the plastic-energy component of fracture energy is reduced to a level which is of the same order of magnitude as the surface, interfacial, or cleavage energy. Recent work2 has illustrated the influence of dispersed precipitates, cold work, and combinations of these on brittle fracture associated with plastic strains of the microyield order of magnitude. This has been rationalized in terms of the contribution of internal microstress fields to the stress magnifications at points of obstruction of active slip bands in a stressed metal. The presently reported studies on an Al-4-1/2 pct Mg alloy amplify this subject by introducing thermal-mechanical conditions which can produce strain aging. As amply demonstrated by Phillips, Swain, and borall, the tensile behavior of aluminum alloys containing magnesium reveals a yield-point elongation and successive discontinuous elongations over the whole plastic-strain range. This gives a stepped or serrated character to the stress-strain diagram. The yield-point elongation is not temperature-dependent. On the other hand, the discontinuous extensions in the plastic-strain range are gradually suppressed by lower temperatures of testing. At -78"C, only the yield-point elongation persists. The yield-point elongation itself can be suppressed by rapid quenching to room temperature from an annealing temperature of 500°C. The argument presented by Phillips et 1. and Cottre114 is that the yield-point elongation derives from surmounting at a critical stress the restraint to slip by grain boundaries which have been reinforced by appreciable magnesium-atom segregation. The serrated character of the plastic-strain range is the result of rapid strain aging during the test. This is made possible by the inevitable proximity of magnesium atoms to any dislocation line. In the Al-4-1/2 pct Mg alloy there is one magnesium atom for every twenty-two aluminum atoms and, with a coordination number of 12, a magnesium atom is on the average only about two atomic distances from any given lattice site. Rapid strain aging is therefore a reasonable expectation. A study of mercury embrittlement of the Al-4-1/2 pct Mg alloy (commercial designation 5083) provides an opportunity to relate the interplay of grain size, grain boundary restraint to slip and strain aging in the brittle-fracture process. One lot of commercial sheet material of 0.125-in. thickness was used for all of the tests. The specimen shape and test procedures used were the same as those described in a previous publication.2 A range of grain sizes between 0.0057 and 0.0125 mm was produced by various combinations of plastic prestrain and annealing. The coarsest grain was somewhat elongated in shape. In this case the measurement was taken in the direction transverse to the axis of tension as more meaningful to a brittle-fracture process. In the annealed condition, specimens wetted with mercury failed with zero permanent elongation at stresses slightly below the normal yield point, i.e., stresses at 0.05 to 0.2 pct strain. Since this occurs before yield-point elongation can begin, fracture derives from slip contained within individual grains and restrained from propagating across grain boundaries. No significant difference in wetted fracture stress was observed between specimens which had been water-quenched or furnace-cooled from the annealing temperatures. This signifies that the degree of magnesium segregation at grain boundaries

Jan 1, 1964

By N. K. Chen, R. Maddin

Columbium single crystals were deformed in tension and compression. Reorientation by X-rays and stereographic projections of slip traces indicate that plane of slip may be considered as (110). The plastic behavior is shown to be quite similar to the deformation of molybdenum single crystals. STUDIES on the crystallography of the deformation process in body-centered cubic metals have been renewed recently with investigations of iron single crystals1-" and molybdenum single crystals.4 It is now apparent that too many exceptions to the rationalization based upon the ratio of absolute testing temperature to absolute melting point by Andrade5 exist to permit more serious discussion of this type of analysis. The considerations of resolved shear stress utilizing only planes of the type {ll0}, {112), and {123)³,6 permit analysis of the deformation only on the basis of those three types of planes. The suggestions made by Elam7 and by Greninger8 in which the slip process is envisioned as a composite slip on two nonparallel {110) planes can be illustrated schematically in Fig. 1. It may be seen that an unresolved trace on any plane containing a <111> direction may be accomplished by varying the number of atoms participating in the composite process. By further varying the number of atoms in each plane but keeping the ratio of participating atoms constant, jogs could be obtained in the traces and hence wavy slip lines could be produced. Vogel and Brick&apos; studied the behavior of a iron single crystals in which they suggest that the plane of glide is "non-crystallographic" and may be predicted from the intersection between the great circle joining the slip direction and specimen axis with the great circle whose zone axis is the slip direction. In a more recent investigation on iron single crystals, Steijn and Brick" suggest that the slip mechanism may be considered as made up of a type of composite slip occurring on {110} and {112} planes. Evidence for a possible composite nature of the slip process has been presented for the case of molybdenum in the form of analysis of asterism and specimen axis rotation." Definite proof of a composite slip process must, however, await good electron microscopic resolution of the individual traces making up the unresolved optical trace used in determining the acting slip plane. The present investigation was undertaken to study the behavior of columbium single crystals not only in tension but also in compression since the specimen axis migration should indicate the plane or planes of glide in the same manner that the specimen axis migration in tension indicates the direction of glide. The orientations of eleven crystals investigated are shown in Fig. 2. Specific orientations are missing (those in the vicinity of [Ill] and [001] and consequently the effect of orientation on the crystallography of deformation could not be considered. Experimental Procedure The 1/8 in. rods (7 in. long) were subjected to an axial tension in vacuo while at temperatures in the vicinity of 2000°C for 2 to 4 hr. This treatment resulted in large cylindrical grains (about ½ in. long) occupying the entire cross section. A number of these rods were used for the tension studies by observing the behavior of the individual grains. For the compression studies, single crystals approximately % in. long by 1/8 in. in diameter were cut from the rods; the ends were ground parallel. All specimens were polished electrolytically in a solution of 15 cc HF(48 pct) and 85 cc H2SO4 (concentrated) using a platinum cathode, a current density of 0.04 amp per sq cm and a temperature between 25" and 60°C.10 Orientations were obtained using a Laue back-reflection method (3 cm film to specimen distance) with a ½ mm collimator 9 cm long. For the compression specimens, a reference mark was scratched on one of the compression sur-

Jan 1, 1954

By L. K. Jetter, C. J. McHargue

DEVELOPMENT of preferred orientation in uranium is of interest because of the strongly anisotropic properties of the orthorhombic crystal structure. Harris&apos; reported inverse pole figures for rolled uranium rods which showed <010> and <410>* to be parallel to the rolling direction after On 0.19-in. spherical X-ray diffraction specimens taken from the center of the middle section of each rod, pole distribution data were obtained by the spectrometric method described previously.4 The specimen was rotated rapidly about the axis coinciding with the rod axis in order that a large number of grains could be scanned and was rotated slowly about an axis perpendicular to the rod axis. The variation in the diffracted X-ray intensity was recorded as a function of the latter motion (angle 4). Fiber-axis distribution charts (inverse pole figures) were prepared by the method described by Setter, McHargue, and Williams." After having been corrected for background radiation, the pole distribution data (I vs ?) were normalized. A normalizing factor for each plane has been shown to be Iranaom = f I sin 4 ? 4 and was obtained by graphical integration from the data for that plane plotted as I sin ? vs ?. The axis-distribution charts deduced from the normalized pole densities are shown in Figs. 1 to 3. On these charts, the contours indicate angular positions of equal normalized axis density,

Jan 1, 1958

By R. F. Favreau, G. E. Larocque

The objective of the study is development of an analytic process based on rock and explosive properties which allows the prediction of the stress distributions and fracture zone around explosive charges. A computer program has been written for this purpose, using a finite difference approximation to the momentum equation, to describe the motion of the surrounding rock by step-wise integration. Its application provides ground motion data such as stress components, displacement and particle velocity as a function of position and time with respect to a spherical charge. The effect of tensile and shear failure on these ground motion parameters can be included. The analytic procedure contained within this program has been used to predict peak stress as a function of distance in rock for rock-explosive combinations for which field data exists to determine peak stress levels directly. Two methods have been used for the spherical charge which in the analysis replaces the actual cylindrical charges: instantaneous application of peak pressure to a charge having a radius equivalent in contained volume to a charge having a length to diameter ratio of 1, and gradual pressure build up to peak pressure with a charge radius equivalent in contained volume to the total charge used in the field test. The agreement with field data would appear best with the latter treatment. The peak stresses obtained are in closer agreement with field measured peak-stress and a better approximation to field stress wave duration exists in the case of gradual pressure build up. One of the assumptions made in the analysis is that, in the case of cylindrical charges, the explosion pressure rather than the detonation pressure of an explosive establishes the peak stresses in the

Jan 1, 1971