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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 William M. Boorstein, Robert D. Pehlke

The rates of solution (of hydrogen in liquid pure iron and in several liquid binary iron alloys were meas-ured using a constant volume technique. The rates of absorption and desorption were found to be equal un-der all experimental conditions. increasing concen-trations of S, Si, or Te decrease the rate of hydrogen uptake but additions of Al, B, Cr, Cu, or Ni have no measurable effect up to concentrations normally en-countered in steelmaking practice. No relation ship was found between the effect of an alloying element on the equilibrium solubility of hydrogen in liquid iron and its effect on the solution rate constant. Mathe-rnatical analysis of the data indicates that under the present experimental conditions the rate of reaction of hydrogen with liquid iron is controlled by transport of gas solute atoms in the metal phase. Comparison of the present resuts with data on nitrogen taken un der similar conditions establishes that the hydrody-nurnic conditions which exist near the surface of a metal bath are best approximated mathematically by a surface renewal model for the case of rapid in-ductive stirring and by a boundary layer model for more quiescent melts. HYDROGEN has long been recognized as being a detrimental constituent in steel. If dissolved in the molten metal in excess of its solid solubility, hydro-gen can be evolved during solidification and cause bleeding or porosity in ingots and castings. In the solid metal, lesser amounts play a definite role in causing other defects such as hairline cracks, blisters, and embrittlement. For significant refinements to be made in metallurgical procedures designed to control or eliminate hydrogen from liquid iron or steel dur-ing processing, available equilibrium solubility data must be supplemented with reliable fundamental in-formation pertaining to the kinetic factors involved in the transfer of hydrogen to or from the metal. The scarcity of such information in the literature prompted the present investigation. PREVIOUS RESEARCH Whereas much of the existing data on the solution kinetics of gases such as nitrogen were obtained during the course of thermodynamic investigations, the solu-tion rate of hydrogen has been found too rapid to be accurately determined by conventional solubility meas-urement techniques. Consequently, little work on hy-drogen solution kinetics has been reported in the lit-erature. Carney, Chipman, and crant1 attempted to study the rate of solution and evolution of hydrogen from liquid iron by employing a newly devised sampling method. Although no significant quantitative data could be obtained, it was observed that the rate of solution was approximately equal to the rate of evolution of hy-drogen from the melt. Karnaukov and Morozov2 stud-ied the rate of absorption and Knuppel and Oeters3 the rate of desorption of hydrogen from molten iron by measuring pressure changes with time in a constant volume system. Karnaukov and Morozov determined the hydrogen pressures over their inductively stirred melts with the aid of a McLeod gage and therefore, were forced to work at pressures not in excess of 40 mm of Hg. Their experimental data conformed to a mathematical correlation based on diffusion control: and the rate coefficients calculated on this basis were shown to be independent of the initial absorption pres-sure. These authors reported the solution rate of hy-drogen to be eight-to-ten times higher than they had found for nitrogen in a previous study. They also re-ported that under identical conditions, hydrogen dis-solves somewhat more slowly in iron-columbium alloys than in pure iron. Knuppel and Oeters found that the desorption of hydrogen from pure iron at 1600°C was controlled in all cases investigated by diffusion in the metal bath as long as bubble formation was sup-pressed. This was substantiated by Levin, Kurochkin, and umrikhin4 who studied the kinetics of hydrogen evolution from liquid (technical) iron while applying a vacuum. Salter5 measured the rate of hydrogen ab-sorbed by iron buttons, arc-melted by direct current, as a function of hydrogen partial pressure in a hy-drogen-argon atmosphere. A carrier gas technique was used for analysis of the hydrogen absorbed. The initial rate of absorption was found to increase di-rectly with the square root of the partial pressure of hydrogen. EXPERIMENTAL METHOD Because of the rapid uptake and evolution of hydro-gen by iron-base melts, a constant volume technique was devised in order to obtain meaningful kinetic data over the entire course of the solution process. Apparatus. A schematic view of the experimental apparatus is given in Fig. 1. The hydrogen-liquid iron reaction system consisted of a gas storage bulb con-nected to a meltcontaining reaction chamber through a normally-closed solenoid valve. The gas storage bulb, an inverted 250 ml round-bottomed Pyrex flask was joined to the inlet port of the solenoid valve by a glass-to-metal seal. A more detailed illustration of the reaction chamber is shown in Fig. 2. The design of the Vycor reaction bulb was essentially that de-scribed by Weinstein and Elliott6 with the exception of a shorter, larger diameter gas inlet for this kinetic study. In position, the reaction bulb was closely by an eight-turn coil of water-cooled copper tubing which, when energized by a 400-kc oscillator, provided the inductive heating source. The walls of the bulb were maintained relatively cool by circulating cold water along their outer surface, thus preventing

Jan 1, 1970

By E. Miller, J. M. Eldridge, K. L. Komarek

Aclivilies of magnesium in liquid Alg-Si alloys have been delermined between 5 and 60 at. pcl Si, close to the melling point of Mg2Si, by an improved isopieslic melhod. Silicon specinrens, held in alumina crucibles and graplrile conlainevs of special design, were healed in a letrlpevalure gvadient and equilibrated with mag-nesilcrrl rapor in a closed lilanium system. The ther-madynamic Junctions were calculated and compared with the thermodyuamic properties of the other three mg- Gvoup IVB systems. Lattice paramelers of three Mg2X compounds were measured. The bonding in the Mg2X compounds is largely covalent with small and uarying amounts of metallic and ionic conlvibutions. The Mg-Si phase diagram1 has one congruent melting compound, Mg2Si, of essentially stoichiometric composition, two eutectics, and very limited terminal solid solubilities. Little information is available on the thermodynamic properties of this system. The free energy of formation of Mg2Si has been determined by the Knudsen cell technique2 in the range 572" to 680oC, by the transportation method3 between 858" and 950oC, and by the electromotive-force method4 in the range 400o to 600°C. Kubaschewski and villa5 and caulfield6 have measured the heat of formation of Mg2Si. An electromotive-force study of magnesium-rich liquid alloys was recently published by Sryvalin el al.7 The present investigation was undertaken to complete a general survey of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,a9,Mg-Sn,10,11 mg-Ge,12and Mg-Si. An isopiestic technique, previously developed for similar measurements on liquid Mg-sn11 and Mg-Ge alloys,12 was modified for the Mg-Si system. Specimens of the nonvolatile component, silicon, were contained in dense alumina crucibles placed inside covered graphite crucibles which were heated in a temperature gradient in an evacuated and sealed titanium reaction tube and equilibrated with magnesium vapor of known vapor pressure. The alumina crucibles prevented contact between the highly corrosive liquid Mg-Si alloys and graphite. The graphite cruci- bles effectively preserved the high-temperature equilibrium composition of the liquid alloys containing highly volatile magnesium on termination of the experiments during the quench to room temperature. EXPERIMENTAL PROCEDURE Silicon of semiconductor-grade purity (E. I. du Pont de Nemours and Co., Brevard, N.C.) and 99.99+ pct Mg (Dominion Magnesium Ltd., Toronto, Canada) were used. Graphite crucibles with press-fitted lids were machined from high-density (1.92 g per cu cm) rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The alumina crucibles had a purity of 99.7+ pct (Triangle RR grade, Morganite, Inc., Long Island City, N.Y.). In preliminary runs the liquid alloys were contained in graphite crucibles following the exact procedure developed for the Mg-Ge system.&apos;2 These runs failed due to appreciable reaction between the molten Mg-Si alloys and graphite, and the results have been discarded. The procedure was then modified and the Mg-Si alloys were subsequently held in alumina crucibles. For most of the runs alumina crucibles of known weight and approximately 6.3 mm ID, 12.5 mm height, 1.0 mm wall thickness were loaded with weighed amounts of silicon and encapsuled in tightly covered weighed graphite crucibles 5/16 in. ID, 2 in. helght, 3/32 in. wall thickness). The graphite crucibles were machined from rods which were 85 pct of the theoretical density. These crucibles were therefore sufficiently porous so as to permit magnesium vapor to effuse through the silicon under the experimental conditions of approximately 970O to 1220°C and 1 day equilibration time. However, negligible magnesium was lost from the crucible during the quench due to the slow effusion rate through the pores of the graphite. The inner alumina crucible prevented the liquid alloys from contacting the graphite, and the very tightly fitting graphite crucible lids served to retain any magnesium vaporizing from the alloys inside the crucibles during the quenching step.12 The loaded silicon-alumina-graphite cells were positioned, one above another, on a 16-in.-long titanium thermocouple well and tied securely to the titanium tube with thin molybdenum wires held in grooves around the circumference of the graphite crucibles. A thin (0.005-in.) molybdenum strip prevented contact between the graphite crucibles and the titanium. This assembly was lowered into a titanium reaction tube (la in. ID, 16 in. long, $ in. wall thickness) closed on one end which contained a 11/2-in.-long cylinder of magnesium at the bottom. The inner titanium thermocouple well was positioned eccentrically in the large tube because of the eccentric mounting of the cells on the well. Appropriate modifications of the titanium cap"&apos;12 were made to join the inner and outer titanium

Jan 1, 1968

By Jerome J. English, Gordon W. Powell

An experimental investigation and mathematical analysis of the thermal-dilation behavior of the titanium alloy Ti-7Al-3Cb have shown that the linear dimensional changes associated with the polymorphic transformation need not be isotropic. The absolute magnitude of the linear dimensional change, which may be either positiue or negative, associated with the cr-p transformation is dependent upon the relutzve volumes of different orientations of the transformation product. It is hypothesized that the dilation irregulati-ties that have been observed during the polymorphic transformation of pure, coarse-grained titanium and other titanium-base alloys can be explained in the same manner. When titanium is heated above about 165O°F, the hcp a structure transforms to bcc 0. Thermal-dilatioh measurements have shown that the transformation is accompanied by a decrease in length of 0.16 pct.&apos; Such dilation behavior would be expected because the volume of the hcp unit cell is about 0.3 to 0.4 pct greater than that of the bcc unit cell. A recent investigation2 of the thermal-dilation behavior of an experimental a-p* titanium alloy, Ti- 7A1-3Cb, containing 0.06 wt pct 0 showed that its dilation behavior during the polymorphic transformation differed substantially from that reported for unalloyed titanium. The first time the alloy was cycled through the transformation, the dilation curve closely duplicated that of unalloyed titanium. However, upon repeated cycling through the transformation temperature range, both the magnitude and the sign of the dimensional change associated with the transformation were observed to vary with each cycle. This investigation was undertaken to obtain additional data on the dimensional changes associated with the polymorphic transformation in the Ti-7A1-3Cb alloy and to determine the cause of the dimensional irregularities. After testing, the specimens were examined metallo-graphically. In addition, Laue back-reflection patterns were obtained from selected sections taken perpendicular to the specimen axes to determine the a orientations present in these sections. White radiation from a tungsten target and a 0.1-mm-diam collimator were used to produce the diffraction patterns. RESULTS Dilation Curves. Three types of thermal-dilation curves were obtained when the a-8 titanium alloy was heated and cooled through the transformation temperature range. These three types of curves are illustrated in Fig. 1. The type I curve represents what is considered normal behavior, because the dilation change is what would be expected on the basis of the volumes of the unit cells of a and p. The Type I1 curve is the inverse of Type I. Normal behavior is characterized by an expansion on cooling through the transformation, whereas a contraction takes place in the Type 11 curve. With Type ni behavior, no clearly distinguishable length change occurs during the transformation. No other anomalies that might be indicative of other phase transformations were observed in the dilation curves at lower temperatures. Apparently, the cooling rate was low enough for equilibrium to be reached during the 0 to a transformation. Table I lists the types of dilation curves observed during the polymorphic transformation as a function of the direction of measurement and cycle number. The A1 value was determined by extrapolating the low-temperature (a + 5 pct p) and high-temperature (100 pct p) segments of the dilation curves to a common temperature and measuring the difference in the or-dinates at that temperature, see Fig. 1. The transformation occurs over a temperature range in this alloy, so the magnitude of A1 is not an absolute value but depends on the choice of temperature. A mean temperature, T,, within the transformation temperature range was selected for the measurement. T, on cooling occurred about 100°C lower than T, on heating. The first time each of the three dilation specimens was heated to above the temperature, that is, Cycle 2, normal Type I behavior was observed. In Cycle 3, two deviations from normal behavior occurred. First, during cooling of the longitudinal specimen, a substantially larger expansion, +0.21 pct, was measured as 0 transformed to a compared with +0.03 pct in Cycle 2. Second, the thickness specimen was observed to undergo a contraction instead of the anticipated expansion on cooling. Continued cycling of the three specimens from room temperature to 2500°F produced additional changes in the dilation behavior. These changes did not seem to be related to the fabrication direction of the alloy because the values of a1 for the longitudinal, transverse, and thickness specimens varied unpredictably in magnitude and sign. Furthermore, both the longitudinal and transverse specimens showed all three types of dilation curves at least once during the six cycles that they received. Fig. 2 is a sketch of the transverse specimen after

Jan 1, 1967

By I. H. Silberberg, R. L. Reed, O. K. Kimbler

interfacial films have frequently been observed at interfaces between certain crude oils and water. Several investigators have postulated that the presence of these films should influence the efficiency of oil recovery in water drive or waterflood operations. They may also influence the stability of emulsions which are sometimes a problem in petroleum production, and may be a factor in the fonation of paraffin deposits in oil well tubing and flow lines. This paper presents a technique with which a modified Langmuir film balance may be used to study the compressibility and collapse pressure of these natural interfacial films. Experimental data are presented for several nude oil-water systems. Data developed are used to infer the phase state of the film as a function of such variables as rate of reduction of interfacial area, ionic composition of the subtrate and pH of the subtrate. A film of known physical characteristics is shown to have a sinnificant effect on oil recovery from an unconsolidated sand pack. Possible applications of these results to petroleum production are discussed. INTRODUCTION The use of water to displace petroleum from reservoir rocks is of major importance both as a primary and a secondary recovery process. As water invades the rock, oil is completely displaced from some pores and left as a discontinuous phase in other pores. The manner in which water moves from pore to pore is strongly influenced by capillary forces. In view of the complexity of reservoir fluid systems, there can be little doubt that complicated interactions take place at both the liquid-solid and oil-water interfaces. One of the more interesting, and least understood, of the phenomena which take place at the oil-water interface is the formation of interfacial films. These films are believed to result from the adsorption of high molecular weight polar molecules at the interface.l.2 Presence of such molecules may cause a striking alteration in interfacial tension. When the oil-water interfacial area of certain crudes is rapidly reduced, a thin region (film) about the interface assumes the appearance of a solid membrane, and striations, wrinkles and gross distortions may occur. If such a film is solid, it should greatly alter the interfacial tension normally assumed to exist between the oil and water phases. If the membrane is continuous, a solid phase would separate the oil and water. Interfacial films between crude oil and water were observed in 1949 by Bartell and Niederhausers who commented upon the apparent rigidity of the films and their possible importance in the petroleum industry. Morrell and Egloff4 had earlier attributed the extreme stability of emulsions of sea water in fuel oil to very stable asphaltic films. Numerous investigators have observed rigid films in the course of crude oil-water interfacial tension determinations by the pendent drop method. Several investigators5,6,2 have separated inter-facially active materials from crudes and attempted to characterize them chemically. Reisberg and Doscher,2 using Ventura crude, showed the interfacial tension against water (as measured by the pendent drop method) to be affected by aging, contraction and expansion of the interface, and the pH of the water. These investigators attributed the adhesion of oil to a water-wetted surface and the distortions of flow paths in glass capillaries to the presence of rigid films. Dodd7 has studied the interfacial viscosity of adsorbed films and found them to be non-Newtonian in behavior. Craighead and Harvey8 reported a series of displacements in tubes packed with 60 mesh glass beads. They interpreted the results as indicating an effect of stearic acid films on waterflood recovery and imply that natural films may produce similar results.

Jan 1, 1967

By C. A. Stickels

A heat of electrolytic iron, to whzch alunzinutn and nitrogen had been added, was hot-rolled, cold-rolled 90 pct, and recrystallized at temperatures from 500" to 700°C. Primary recrystallization textures appear to arise from competitive growth of two types of nuclei: 1) those having orientations belonging to the "usual" primary recrystallization texture found in riming steel, and 2) those with the {111} (110) ovientation. Development of a (111}(1 10) component in the primary recrystallization texture occurs only over a certain interval of isothermal recrystallizatzon temperatures when the material is supersaturated with respect to the precipitation of AlN. Lowering the degree of supersaturation depresses the temperature interval in which a (111)(110) component occurs. An elongated, &apos;pancake-shaped" recrystallized pain structure and a marked delay in the start of recrystallization were found in all specimens which were supersaturated with respect to A1N precipitation after cold work, regardless of their recrystallization texture. ONE of the consequences of killing low-carbon steel with aluminum is a significant change in recrystallization behavior. About 15 years ago, Solter and eatttiel showed that this behavior was largely controlled by aluminum and nitrogen in the steel. If complete precipitation of A1N was prevented before cold rolling, an increased "recrystallization temperature" was observed in subsequent. annealing, and the recrystal-lized grains were not equiaxed. Leslie et a1.2 studied this phenomenon in some detail and clearly demonstrated the relationship between A1N precipitation, recrystallization kinetics, and the development of "pancake-shaped" grains. It has also been known for some time that aluminum-killed steels, processed to produce elongated "pancake" grains, develop a (11 I}( 110) primary recrystallization texture. This texture has not been found in iron or low-carbon rimming steel as a primary texture4j5 but has been observed following grain growth in electrolytic iron.5 The present work was undertaken to study in more detail the effect of A1N supersaturation on recrystallization textures in iron. LITERATURE REVIEW The deformation texture in heavily rolled iron has been studied in detail by Bennewitz.~ The texture consists primarily of a partial fiber texture about a (110) axis in the rolling direction, designated here as fiber texture A. It includes the range of orienta- tions (111)[110] - (001)[ 110] - (11l)[110]. A weak secondary texture also is present.6 This is a duplex partial fiber texture about two (110) fiber axes located 60 deg from the rolling direction and 30 deg from the sheet normal. The range of this texture, designated here as fiber texture B, about the [101} fiber axis is (112)[110] - near (545)[252] - (211:1[011] *The range given here follows Bennewit~.~ A few pole figures from re-crystallized material indicate a broader range than this.&apos; However, the components which are strongest in the recrystallization texture are in this range.&apos;________________________________________________________ Primary recrystallization textures in unkilled steels can be accounted for by growth of members of fiber texture B present in the deformed metal.5 However, while members of fiber texture B dominate the primary texture, other orientations survive primary recrystallization as well. In particular, some {111}(110) members of fiber texture A must also grow during primary recrystallization, because a well-defined {1ll)( 110) texture develops during subsequent grain growth at 700°C.5 The unusual recrystallization behavior of deformed supersaturated solid solutions has been attributed to: 1) retention of the solute in solution,&apos; 2) formation of coherent, preprecipitation solute clusters prior to and during re~r~stallization,~ and 3) formation of a precipitate prior to and concurrent with recrystallization.&apos;~-&apos;~ When aluminum is supersaturated with iron, the difference in grain boundary mobility between general high-angle boundaries and certain special coincidence site boundaries is apparently eliminated.&apos; In aluminum-killed steels, precipitation of A1N can take place at ordinary subcritical recrystallization temperatures. The rate of precipitation increases with increasing aluminum or nitrogen contents.2&apos;13 There is some doubt, however, as to whether true precipitates form during the time at temperature needed to complete recrystallization. Leslie ef a1.2 found that precipitation in one steel was complete after about 100 min at 700GC, or after about 1000 min at 650GC, as measured by chemical analysis for AlN. Aoki et a1.,13 using internal friction for dissolved nitrogen, showed that a large fraction of the dissolved nitrogen was removed from solution within a few minutes annealing time at temperatures from 400" to 800°C. However , the rate of formation of AlN, as detected bv chemical analvsis. was much slower than the apparent rate of nitrogen removal. Hasebe,&apos;~~ using carbon extraction replicas, has identified A1N precipitates by electron diffraction in a 0.2 C steel, solution-treated at 1300°C and annealed 2 hr at 700°C. Borchers and kim,I6 also using a replication technique, observed precipitates after annealing treatments as short as 2 min at 640°C. However, Leslie et a1.&apos; state that no A1N precipitate can be seen while recrystallization is being inhibited in aluminum-killed steel.

Jan 1, 1967

By Giovanni Barla, Stefan H. Boshkov

This paper examines the application of gelatin mixture models to the study of factors such as gravity effects, tectonic and residual stresses, anisotropy, physical nonlinearity, time-dependent behavior of the rock mass and connectedness of the geologic space. The technique of calibrating gelatin mixtures proposed by Richards and Mark in 1966 is applied to the particular problem considered. Similitude relationships between model and prototype are discussed with reference to the constitutive equations describing the physical behavior of the rock mass. The interaction between two openings in a linearly elastic medium, under conditions of plane strain, is used as an illustrative example with the view to describing the history of stress and deformation changes on the rock medium and lining around a slusher drift while undercuts are made in block caving. The prediction of the displacement, stress field and mode of fracture associated with a given rock structure, its initial stress field, and its physical properties is essential to rock mechanics and ground control. The basic approach is to assume the rock mass to behave as a continuous, homogeneous, and isotropic medium. The classical theory of elasticity is the simplest theory based on such a concept. Specification of the elastic constants, the initial state of stress in the ground, and the boundary conditions on stress and displacement allows one to predict stress and displacement within the body. Subsequently, provided that a criterion which governs rock fracture under various stress conditions has been established, a stability analysis of the rock structure can be performed. A natural extension of the present knowledge consists of removing some of the simplifying assumptions which characterize the analytical solutions based on the classical theory of elasticity. Complex geometry, the significance of tectonic and residual stresses, anisotropy, physical nonlinearity, time-dependent behavior of the rock mass and connectedness of the geologic space are some of the important factors which are neglected in the classical approach. A better insight into the real problem can be attained with either the finite element method of stress analysis or an experimental technique. The former has already been applied with success on several occasion 1-4 and is destined to render great service in the field of rock mechanics and ground control. The latter, which will be considered in this paper, has been used extensively in applications too numerous to be enumerated. Experimental technique involves either prototype testing, if the area to be studied is accessible, or model testing. Two- and three-dimensional photo-elastic analyses are very convenient means of obtaining the stress distribution in models of complex geometry. In general, such analyses are confined to studies of stress fields around openings which are sufficiently far removed from the surface boundary so that the stresses in their neighborhood are practically equal to those produced by an initial uniform stress field; i.e., so that gravitational effects are negligible. There are, however, many rock structures where these effects must be taken into account to attain a more realistic representation of the problem. Surface and near surface rock structures, systems of openings interacting with one another, and structural components loaded only by their own weight are some of the obvious examples. This paper was written to show how factors neglected in the usual analysis based on the classical theory of elasticity, can be taken into account when gelatin mixture models are used inconjunction with photoelastic methods. The interaction between two openings in a linearly elastic medium, under conditions of plane strain, is used as an illustrative example, with a view to describing the history of stress and deformation changes on the rock medium and lining around a slusher drift while undercuts are made in block caving. The birefringence of gelatin mixtures has been known for some time. A series of experiments were carried out by Rossi in 1910,5 but after that very

Jan 1, 1970

By T. E. Davidson, A. P. Lee

It is known from the early work of Bridgman that the two lowest-pressure transitions (I-II and II-III) are accompanied by substantial and abrupt changes in resistivity and Volume. However, unlike the temperature -induced allotropic transformations observed in such elements as lithium, cobalt, tin, and so forth, there is little actually known about many of the characteristics of the pressure-in&ced transitions. This current work involves an examination of the structural and transformation characteristics of the bismuth I-II and II-III transitions under hydrostatic pressures. The relationship of initial structure to the transformation pressure, rate, resistivity change, and resultant structure is discussed. It is shown that the transition pressure and transformation rate are independent of the presence of grain boundaries and associated anisotropy-induced deformation. An observed hysteresis in both the I-II and II-III transitions is shown. BISMUTH is one of the most interesting of the elements exhibiting pressure-induced polymorphs since it undergoes several allotropic transformations at pressures below 90,000 atm. It is known from the early work of bridman1,2 that the two lowest-pressure transitions (1-11 and 11-111) are accompanied by substantial and abrupt changes in resistance and volume. However, unlike the temperature-induced allotropic transformations observed in such elements as lithium, cobalt, tin, and so forth, there is little actually known about many of the characteristics of these pressure-induced transitions. It is the purpose of this work to examine some of the structural and transformation characteristics of the bismuth 1-11 and 11-111 transitions under hydrostatic pressures. Another interesting characteristic of bismuth is that, in its polycrystalline form, hydrostatic pressures of sufficient magnitude will induce severe progressive plastic deformation in the region of the grain boundaries.3 This deformation, which has also been observed in several other metals, is attributed to the high degree of anisotropy in the linear compressibility of bismuth, resulting in shear stresses in the grain boundaries when it is exposed to hydrostatic pressure. Most thermally induced allotropic transformations in metals, whether of the diffusionless ather-ma1 (martensitic) or isothermal nucleation and growth types, are dependent upon structure and prior history,4 viz., grain boundaries, deformation, and so forth. One logically wonders then whether the transformation characteristics of the pressure-induced polymorphs in bismuth might also depend upon initial structure, particularly with respect to the presence of grain boundaries and associated plastic deformation. In this investigation, the role of grain boundaries and plastic deformation on the characteristics of the bismuth I-II and 11-111 transitions will be established. The rather unique residual microstruc-tural changes associated with these transitions will be presented and discussed. The occurrence of a measurable hysteresis in both the I-II and 11-111 transitions will be demonstrated. The type of transformation mechanism based on the observed transformation rate will be discussed. EXPERIMENTAL PROCEDURE A) Apparatus. The hydrostatic pressure system utilized in this investigation is similar to that previously reported by Bridgman&apos; and Birch and Robertson,5 and has been previously described.3 For the purpose of this work, the pressure medium utilized was a 1:l mixture of pentane and isopentane. Pressure measurement was by means of a manganin coil in conjunction with a Foxboro Recorder. The manganin coil was mounted in the bottom closure and inserted inside the pressure cavity. Based on calibration against a controlled clearance piston gage at approximately 10,000 atm, the estimated error in the pressure measurement was +2 pct. Assuming the nonlinearity in the pressure coefficient of resistivity between 10,000 and 28,000 atm to be not greater than 1 pct, then the estimated error in the range of the I-II and 11-111 transitions was +3 pct. B) specimen Material and Preparation. The bismuth utilized throughout this investigation was of

Jan 1, 1964

By L. W. Holm, A. K. Csaszar

A series of laboratory experiments was conducted in which oil was displaced from a porous medium by water-driven slugs of alcohols or similar solvents. The solvents used were soluble to some degree in both oil and water and covered the range of solubilities from complete solubility in oil to complete solubility in water. Displacement experiments were conducted on 2-and 3%-in. in diameter consolidated cores and 1-and 2-in. in diameter unconsolidated sand packs. The cores and sand packs ranged in length from 1 to 30 ft, and they were saturated with brine and crude or refined oils. The solvents used included ethyl alcohol, isopropyl alcohol (IPA), tertiary butyl alcohol (TBAI, secondary butyl alcohol (SBA), n-amyl alcohol (NAA), methyl ethyl ketone, acetone and others. It was found that all of the oil present in a porous medium could be miscibly displaced by injecting a slug of mutual solvent and driving it with water. The oil-recovery efficiency was dependent upon (1) the relative solubilities of the solvent in oil and water, and (2) the distance traversed by the flood. For complete oil recovery from cores, a smaller amount of a preferentially oil-soluble solvent was required, compared to the amount of preferentially water-soluble solvent needed. The size of the solvent slug required varied inversely with the linear flooding-path length raised to the 0.65 power. Water-driven dual solvent combinations (an oil-soluble solvent slug followed by a water-soluble solvent slug) were found to effect complete oil recovery with less total solvent than any single solvent used. In these dual-solvent displacement experiments, the slug size required varied inversely with length raised to the 0.55 power. Based upon the experimental results, a theory was developed to describe the displacement of oil and water by mutual solvents, and equations are presented to predict the production history in a linear system. These equations take into account the properties of the solvents and the porous medium. INTRODUCTION Oil-recovery processes which utilize displacing fluids that are miscible with the reservoir fluids have been studied extensively in recent years. Because of the poor contact efficiency and high pressure requirements of the LPG-gas displacement process there has been considerable interest in the alcohol-water process, and a number of studies have been made on the recovery of oil through the use of solvents which are mutually soluble in oil and water. An investigation by Sievert, Dew and Conleyl indicated that the use of mutual solvents would be limited because the presence of water in a porous medium would cause a phase break in the leading edge of the displacing solvent. Their study also showed that, in consolidated cores containing. only oil, the displacement of oil by a water-driven mutual-solvent slug of tertiary butyl alcohol (TBA) was affected by the viscosity ratios of the fluids involved. Gatlin and slobod3 concluded that an isopropyl alcohol (IPA) slug acts as a miscible piston, completely displacing both oil and water until the alcohol content of the mixing zone falls below the concentration necessary to maintain miscibility. Their study was conducted on uniform unconsolidated sand packs. They concluded further that IPA could be used effectively to recover oil from a watered-out sand. In a paper by Taber, Gamath and Reed4 relating an investigation on sandstone cores, it was stated that the displacement of oil by mutual solvents, particularly IPA, was not a miscible displacement and that no improvement in efficiency could be expected with increase in flooding-path length. However, their analytical analysis of the displacement mechanism using TBA is, in fact, one which indicates that the displacement is controlled by miscible mixing. They suggested that the lack of improvement in efficiency with flooding - path

By F. Gordon Smith

ALTHOUGH several geological indicators of the critical type are known, including quartz inversions and decomposition of hydrous minerals such as serpentine, there are very few of the general type. Solid solutions are excepted, but the limitations of use are very restricted and interpretations are sometimes ambiguous. General methods for determining temperature and pressure conditions during the crystallization of minerals would have considerable scientific and economic value. It is not the purpose of this paper to discuss the various methods of geological thermometry and barometry, but to present one general method, applicable to all minerals, and to describe what progress has been made in the methods of measurement. The general method, in brief, is a study of the stress conditions in and around various types of foreign inclusions which are trapped in minerals during growth. The method depends upon the fact that any homogeneous gas, liquid, or solid will in general have coefficients of thermal expansion and volume compressibility different from those of any given mineral. Therefore stress must develop in and around all types of inclusions in minerals if the temperature or the pressure, or both, are changed from the conditions which prevailed during the growth of the mineral. The methods of measurement consist of determinations of the temperature-pressure conditions of fit of the inclusions in the host mineral. The types of inclusions in minerals are: I—gas, or liquid plus vapor, when observed at room temperature, due to crystallization under pneumatolytic conditions; 2—liquid, or liquid plus vapor when observed at room temperature, due to crystallization under hydrothermal conditions; 3—glassy solid, or devitrified glass, due to crystallization under magmatic or high temperature metamorphic conditions, in a siliceous liquid; and 4—crystals, due to overgrowth of other minerals crystallizing simultaneously or of other minerals which crystallized previously. A survey of the literature shows that much valuable earlier work on inclusions, especially that car- ried out in England in the last century, has dropped out of current knowledge. The following is a brief summary of the significant contributions to the problem up to the present day. Davy in 1822 asserted that fluid inclusions in minerals consist of an aqueous solution of salts and a gas bubble, the whole being either at lower or higher pressure than atmospheric.&apos; At intervals from 1823 to 1862, Brewster contributed information concerning other types of inclusion consisting of 1—aqueous solution, a much more expansible liquid, and a gas; 2—aqueous solution, salt crystals, and a gas; and 3—the very expansible liquid and a gas. The very expansible liquid fills the gas space between 20" and 30°C. Compression strain effects were seen around inclusions in diamond, topaz, and other minerals.&apos;-" Sorby in 1858 and 1869 further advanced the study begun by Davy, stating that fluid inclusions represent a sample of the mother liquor of crystallization and that the degree of filling of aqueous inclusions at room temperature defines the temperature-pressure relations during formation of the host. The degree of filling may be measured by determining the minimum temperature of filling of the inclusion by the liquid phase. The very expansible liquid in some fluid inclusions is liquid carbon dioxide. The temperature at which salt crystals in fluid inclusions completely dissolve in the fluid is the minimum temperature of formation. Inclusions of glass or devitrified glass indicate crystallization from a melt. Inclusions of crystals in minerals are often centers of strain, which may be seen by optical effects or by radial tension cracks. Sorby realized that an analysis of stress-strain relations about inclusions could be used to provide precise data on the temperature of crystallization, but the matter was never pursued.&apos; , Hartley (1876, 1877),".&apos;" Hawes (1881)," Wright (1881),&apos;V ohnsen (1920),I3 and Holden (1925)"

Jan 1, 1953

By F. Gordon Smith

ALTHOUGH several geological indicators of the critical type are known, including quartz inversions and decomposition of hydrous minerals such as serpentine, there are very few of the general type. Solid solutions are excepted, but the limitations of use are very restricted and interpretations are sometimes ambiguous. General methods for determining temperature and pressure conditions during the crystallization of minerals would have considerable scientific and economic value. It is not the purpose of this paper to discuss the various methods of geological thermometry and barometry, but to present one general method, applicable to all minerals, and to describe what progress has been made in the methods of measurement. The general method, in brief, is a study of the stress conditions in and around various types of foreign inclusions which are trapped in minerals during growth. The method depends upon the fact that any homogeneous gas, liquid, or solid will in general have coefficients of thermal expansion and volume compressibility different from those of any given mineral. Therefore stress must develop in and around all types of inclusions in minerals if the temperature or the pressure, or both, are changed from the conditions which prevailed during the growth of the mineral. The methods of measurement consist of determinations of the temperature-pressure conditions of fit of the inclusions in the host mineral. The types of inclusions in minerals are: I—gas, or liquid plus vapor, when observed at room temperature, due to crystallization under pneumatolytic conditions; 2—liquid, or liquid plus vapor when observed at room temperature, due to crystallization under hydrothermal conditions; 3—glassy solid, or devitrified glass, due to crystallization under magmatic or high temperature metamorphic conditions, in a siliceous liquid; and 4—crystals, due to overgrowth of other minerals crystallizing simultaneously or of other minerals which crystallized previously. A survey of the literature shows that much valuable earlier work on inclusions, especially that car- ried out in England in the last century, has dropped out of current knowledge. The following is a brief summary of the significant contributions to the problem up to the present day. Davy in 1822 asserted that fluid inclusions in minerals consist of an aqueous solution of salts and a gas bubble, the whole being either at lower or higher pressure than atmospheric.&apos; At intervals from 1823 to 1862, Brewster contributed information concerning other types of inclusion consisting of 1—aqueous solution, a much more expansible liquid, and a gas; 2—aqueous solution, salt crystals, and a gas; and 3—the very expansible liquid and a gas. The very expansible liquid fills the gas space between 20" and 30°C. Compression strain effects were seen around inclusions in diamond, topaz, and other minerals.&apos;-" Sorby in 1858 and 1869 further advanced the study begun by Davy, stating that fluid inclusions represent a sample of the mother liquor of crystallization and that the degree of filling of aqueous inclusions at room temperature defines the temperature-pressure relations during formation of the host. The degree of filling may be measured by determining the minimum temperature of filling of the inclusion by the liquid phase. The very expansible liquid in some fluid inclusions is liquid carbon dioxide. The temperature at which salt crystals in fluid inclusions completely dissolve in the fluid is the minimum temperature of formation. Inclusions of glass or devitrified glass indicate crystallization from a melt. Inclusions of crystals in minerals are often centers of strain, which may be seen by optical effects or by radial tension cracks. Sorby realized that an analysis of stress-strain relations about inclusions could be used to provide precise data on the temperature of crystallization, but the matter was never pursued.&apos; , Hartley (1876, 1877),".&apos;" Hawes (1881)," Wright (1881),&apos;V ohnsen (1920),I3 and Holden (1925)"

Jan 1, 1953

By Jaakko Kajamaa

Neutron diffraction was applied to determine sheet textures by the transmission method. Cold-rolled and recrystallized copper sheets were investigated. The amount of cube texture was determined for three compositions, in which the phosphorus content was, respectively, 0, 0.005, and 0.03 wt pct. The heat treatment was in every case 8 sec at 650°C. In the two latter cases the cube texture was prevented. In addition a comparison with the X-ray diffraction transmission method was made with the 96 pct cold-rolled copper sheet. Outer parts of both (111) pole figures can be considered to be rather identical. This is seen from the fact that the intensity ratio ITD/120" was 0.45 for neutron diffraction and 0.40 for X-ray diffraction. Differences between the methods were discussed in detail. Features peculiar to neutron and X-ray diffraction in texture studies were listed and compared. In this work neutron diffraction was applied to determine sheet textures. Specifically, it was desired to ascertain whether this method can be used to reveal differences when compared to other methods. In addition, the amount of the cube texture in copper sheets was determined as a function of phosphorus content. Previous applications of neutron diffraction to texture problems include the following: nickel wires,&apos; wire of some bcc metals,&apos; and uranium bars.3 In the neutron diffraction technique the greatest difference is in the sample—its method of production and its volume. A sample needs no treatment and its volume is roughly 105 times larger than the volume of an X-ray diffraction sample. The cold-rolled sheet was investigated both by neutron diffraction and by X-ray diffraction, because it is expected that, due to large number of defects, possible differences in the results of the two methods would be revealed. It is a well-known fact that X-ray lines show broadening when cold-worked. Analysis has shown that this is based chiefly on small crystalline size, micro-stresses, and/or faults.4&apos;5 Neutrons are sensitive to the above-mentioned disturbing factors as well, but circumstances in diffraction are different from the X-ray case. Because the sample represents a larger volume, the result is an average over that volume. In addition, it can be assumed that the sample has preserved its original structure, because it needs no special preparation. The particular limitation of neutrons is the relatively low neutron intensity available from nuclear reactors. This decreases the resolution as compared to the X-ray diffraction methods. Furthermore, absorption mainly reduces diffracted X-ray intensity, while multiple scattering effects, i.e., secondary extinction, disturb neutron diffraction. SO neutrons and X-rays behave in a different way when interacting with matter. As in other structural investigations, one can utilize this difference in texture studies as well. One cold-rolled and three recrystallization textures in copper sheets were investigated by neutron diffraction. The samples were produced at the Outokumpu copper factory to the specifications shown in Table I. The paper is divided into five parts. The first deals with the theory of the measurement. In the second, experimental procedures are described. Results are presented in the third part. Both cold-rolled and re-crystallized samples are studied. Discussion is in the fourth part, and finally in the fifth part some conclusions are drawn. 1) THEORETICAL CONSIDERATIONS Properties peculiar to neutron diffraction are the following: a) the scattering length varies greatly between one element and another; b) many of the elements do not absorb neutrons appreciably. In this connection it is of primary interest to know the interaction of neutrons with lattice imperfections. As with X-rays this problem leads to diffraction analysis of deformed and recrystallized metals. From the physical point of view the main difference is that neutrons are scattered by nuclei (magnetic scattering is not considered here), whereas X-rays are scattered by electrons. The features peculiar to neutron and X-ray diffraction methods in texture studies are listed in Table 11. Pole figures are an important tool in performing structural analysis of deformed or recrystallized metal. Present texture research technology requires pole figures which are as precise as possible. The choice between these two methods depends on the technical information which is required. The X-ray diffraction transmission technique may give results which are not necessarily representative of the average physical state of the sample. Although foil samples normally contain enough crystallites for diffraction, they may not necessarily represent the whole structure. An example of this problem is the frequently observed difference between the "surface" and the "inside" texture of a sample. The production of foil samples may disturb the original structure of the parent material. The selection and orientation of the foil from the sample is quite arbitrary. Normally, a highly deformed piece of metal has several texture components. Different components are deformed in a slightly different manner. This is a re-

Jan 1, 1969

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&apos; 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&apos; 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&apos; 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.&apos;.&apos; 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 J. T. Norton, N. J. Grant, A. M. Gervais

An investigation of the creep deformation of coarse grained specimens of high purity aluminum in the temperature range 800&apos; to 1150°F, permitted the formulation of a theory explaining the formation of kink bands. The X-ray Laue back-reflection technique was used in conjunction with metallographic studies to determine the crystallographic elements involved in kinking and to measure the rotations of the bands. THAT metals deform by the formation of kink bands was first shown by Orowan1 in 1942. He manually compressed cadmium single-crystal wires, the basal planes of which were parallel to the wire axis and to the direction of compression. He found that kink bands formed quite suddenly. Similar experiments were performed by Hess and Barrett2 on zinc with a hydraulic testing machine to permit slower more careful compression. They observed that kink bands formed progressively with increasing compression. Recently Washburn and Parker3 observed the formation of kink bands in zinc single-crystal specimens during tension creep experiments. Each of these authors observed the formation of kink bands but did not make a complete analyses of the crystallographic relationships. In addition to these studies on hexagonal metals, extensive investigations of kink bands formed during deformation of aluminum in tension at room temperature have been reported. Two types of deformation bands have been observed during the deformation of aluminum at room temperature. These are: 1—kink bands: these exhibit a sharp curvature of the lattice along certain surfaces, and 2—bands formed by secondary slip along certain regions. As has already been shown by Honeycombe,4 it is important to point out the difference characterizing the two types of deformation bands. In the first case. for moderate deformation, only one system of slip planes normally is active; in the second case, however, two slip systems are active in the deformation bands. The latter have a rumpled surface because of the action of the two slip systems. In the present work only the first type of band was studied and to avoid any confusion the term kink band will be used exclusively in the discussion which follows. Honeycombe&apos; observed that very narrow kink bands (width, 0.01 mm) formed along the (110) planes during the deformation of high purity aluminum at room temperature. He observed narrower ones in commercially pure aluminum and found also that their width decreased with decreasing temperatures. Chen and Mathewson5 reported the formation of kink bands during tensile testing of single crystals of high purity aluminum at room temperature and pointed out that some rotation occurred about a [211] direction. The influence of the bending moment on the formation of kink bands was illustrated by the experiments of Rohm and Kochendorferl0 who used a Polanyi apparatus to obtain pure shear during tensile testing of high purity aluminum single crystals. Under such conditions only one slip system was active and no kink bands were observed; consequently, no noticeable asterism was detected after deformation. The influence of the bending moment will be discussed later. Calnan8 gave a detailed account of the work performed on kink bands obtained during deformation of aluminum at room temperature. Because no explanation of the process of kink band formation in creep was given in the previous investigations and because some of the above observations are vital to the following discussion the brief review of the literature has been given. It is proposed in the present work to provide an explanation of kink band formation during creep deformation at elevated temperatures. Results and Discussion Kink bands were observed to form during tensile creep testing of high purity (99.995 pct) aluminum specimens, having a very large grain size, in the temperature range 800" to 1150°F. These observations were made in grains which occupied the whole cross section of the specimen. The specimens were originally round (diameter, 0.187 in.; gage length, 1 in.) and had parallel flats milled to permit easier metallographic and X-ray observations. The final

Jan 1, 1954

By Irwin R. Higgins

CONTENTS A. Introduction B. System Description C. Uranium Pilot Plant Programs D. Summary INTRODUCTION The Chem-Seps Continuous Countercurrent Ion Exchange (CCIX) contactor was first conceived of in 1951 at the Oak Ridge National Laboratory. In the 27 years that have passed, there has been a steady stream of pilot plant process development studies on a variety of processes far too numerous to mention. These have been in the area of water and waste treatment, chemical processing, ore leach treatment, and many others. Many successful production systems have been installed and operated in a variety of applications. A few of these are described herein together with a description of the system and its operational characteristics. SYSTEM DESCRIPTION Chem-Seps Continuous Countercurrent Ion Exchange* is a single loop in which various sections are separated by valves to isolate the sections performing different functions simultaneously. (Refer to Figure 1). To explain the working of a typical unit, let us use a simple configuration used in water softening or demineralization. The resin is moved in small increments by the hydraulic ram action. All solution flows are countercurrent to the flow of resin. The contaminants are removed in the process cycle and the resin is moved in the pulse cycle. A controller in the effluent stream from the treatment section senses the proper limit permissible in the effluent. In the process cycle, the influent enters through a set of distributors, moves downward and leaves through a set of collectors. Simultaneously the regenerant enters through valve RE and leaves through valve WA. The rinse enters through valve RI and its duration is controlled by an interface controller. In the process cycle, valves B, C, and D are closed, isolating all the sections. The duration of the process cycle is 4-10 minutes depending on the contaminants to be removed and is controlled either by a timer if the contaminants are fixed, or a controller in the effluent stream, if the contaminants fluctuate at short intervals. Valve A is open and resin is dropped to the pulse section simultaneously with the removal of contaminants in the treatment section, regeneration of loaded resin in the strip section, and rinsing of regenerated resin in the rinse section. As the resin drops through the valve A, it is backwashed to remove the suspended solids or resin fines. Removal of these fine particles is important to avoid the unnecessary pressure drop in the bed and plugging of the distributors. At the end of process cycle, all flows going into the unit and out of unit are automatically shut off. The valve A closes and valves B, C, and D open in proper sequence. A slug of water enters through valve PU, a predetermined incremental volume of resin moves into the regeneration section, an equal volume of regenerated and rinsed resin enters the bottom of the treatment section, and an equal volume of the loaded resin leaves the top of the treatment section and goes into the resin reservoir section. (The resin movement is plug flow with the Reynold&apos;s number being in the laminar region of the curve, and no fluidization occurs during the pulse cycle.) The total time required for proper sequencing of valves and the movement of resin is 20-30 seconds. At the end of this period, the valves B, C, and D close and valve A opens. The solution valves open and normal steady state operation begins. All valves are interlocked and properly sequenced. The resin movement is precisely controlled by sonic devices. Special Features of Chem-Seps CIIX "Downflow"*: The raw feed in the treatment section moves downward and the resin moves upward in the treatment section. The "downflow" of feed overcomes the handicap encountered in "upflow" systems. The "upflow" of feed requires a certain minimum flux during process cycle to lift the bed and keep it

Jan 1, 1979

By R. G. Knickerbocker, W. E. Brown, G. J. Vahrenkamp, M. M. Fine

THE results of a research and development laboratory and pilot-plant mineral-dressing investigation by the Bureau of Mines of the complex copper-lead-cobalt-nickel ores of southeast Missouri are reported in this paper. This investigation, in cooperation with the National Lead Co., showed that separate concentrates of lead, copper, and cobalt-nickel could be made by fine grinding and flotation. An industrial plant built subsequently by the St. Louis Smelting and Refining Div. near Fredericktown, Madison County, Mo., produced such concentrates during the war years. Present commercial production at the mill is limited to lead and copper concentrates, but research to permit economic utilization of the cobalt and nickel values is continuing. The complex sulphide deposits near Frederick-town in Madison County, Mo., have an operating history that dates back to the years preceding the Civil War. Perhaps these operations can best be summarized in terms of output which are given by Tyler: "Previous to 1900, the Mine la Motte Co. shipped cobalt ore to Swansea and in 1903 produced 120,000 pounds of oxide in a Missouri plant. Another cobalt refinery erected in 1906 by the North America Lead Co. at Fredericktown, Mo., operated intermittently until 1910. In 1909 it produced 83,384 pounds of cobalt oxide, 328,403 pounds of nickel, 8,314 tons of nickel-cobalt concentrates, 600 tons of copper concentrates, and 1,353 tons of lead concentrates. This plant was purchased at a forced sale in 1915 by the Missouri Cobalt Co., which produced a certain amount of oxide in 1918 and in 1920 recovered 102,410 pounds of cobalt oxide and cobalt hydrate, valued at $262,810." According to Buehler,2 "The ore, which consists of a complex mixture of the sulphides of cobalt, nickel, copper, lead, and iron, occurs at the contact of the pre-Cambrian porphyry and the overlying Lamotte sandstone and Bonneterre dolomite." The source of most of the cobalt and nickel is siegenite, a member of the linnaetite series of minerals. Its composition is variable, and although the chemical formula may be given as (CoNi),S,, it usually contains both iron and copper. The siegenite is characterized in this instance by an intimate association with chalcopyrite, and to a lesser extent with iron sulphides. Galena, on the other hand, while dis- seminated throughout the ore, is not closely bound to other constituents. Gangue is composed essentially of dolomite and quartz. Petrographic examination showed that fair liberation of sulphides and gangue could be attained at — 100 mesh. Complete liberation of micronsize inclusions, particularly of sulphides in each other would not have been possible at —400 mesh. Beneficiation Studies Many samples of the southeast Missouri ore were tested, but most of the work was confined to five samples of churn drill cuttings weighing 15 tons. The samples were reportedly representative of five sections of the deposit and were tested individually and as a composite. Only the results of the tests on the composite, which contained 1.28 pct lead, 2.03 pct copper, 1.06 pct nickel, 0.87 pct cobalt, 3.57 pct iron, 15.4 pct lime, and 23.9 pct silica, are presented in this report. In view of the rather complex and intimate association in the mineralogical composition of the ore, flotation was the logical choice in the selection of a beneficiation process. Other mineral dressing unit operations were considered as an adjunct to flotation, but none were beneficial. Many tests were made on these samples to determine the flotation characteristics of the mineral siegenite. As a result of this work, it was noted the siegenite was intermediate in floatability between chalcopyrite and galena on one extreme and iron sulphides on the other. The difference in floatability between siegenite and the iron sulphides was not very great and, in general, the same reagents that depressed pyrite and marcasite would also, in slightly larger quantities, depress siegenite. This tendency for siegenite

Jan 1, 1952

By J. W. Galpin, R. H. Allen

Controlled pre-grouting is a technique developed during a period of more than ten Years experience, in an effort to produce safer, drier and more economical mine shaft sinking. The technique involves a knowledge Of hydro-mechanics, both static and dynamic, and a series of specially formulated grout mixtures to obtain several desired results through precontrolled setting time. In general, the following procedures have been used to secure the best results in controlled pre-grouting: I. Before drilling is commenced, One Of two decisions is made: one procedure, a modified form of the Francois method, is to stage drill and grout, that is, drill a limited portion of the hole, then grout and redrill that section which has been grouted, progressing in stages until the required depth is reached. We prefer this method because no casing Or grouting packers are required in the bore hole. This eliminates the risk of losing them in the bore hole due to packer failure, which might result in the expense of drilling a new grout hole. Another feature Of this approach is that smaller drill holes may be effectively used, further reducing the costs. One drawback, however, is that because of the open and small size hole, it is impractical to attempt water draw-down tests. The second alternative is to drill the bore hole, (generally NX size), to the re-quire~ depth. he casing and grouting packer are placed in the bore hole at the lowest packer setting. A small, portable, power driven, swabbing device is used in the grouting casing to test the packer and remove mud or cuttings from the bore hole below the packer. The hydrostatic level is recorded and a close estimate or test is made of the quantity of water at each packer setting. Grouting progresses upward in a series of packer settings to the surface. Occasionally, casing is inserted in the bot-tom of the bore hole from within the mine, and water pressure and volume can be obtained in this manner. This is usually dangerous because of the unknown quantity of water. 2. The grouting, mining and geological engineers at the drill location make a detailed examination of the cores and also locate proper and firm grouting packer locations. A competent driller,s opinion should be given due consideration as to the character and condition of the bore hole. 3. Several samples of formation water

Jan 1, 1949

By B. C. Allen

The interface energies of chronzium, molybdenunz. hugsten, and their solid-solution alloys Cv-35Re, MO-33Re, and UJ-25Re were studied at 0.6 to 1.0 of the absolllte liquidus ter)zpe,vature using fiz&apos;e )izethods. Liquid surface tension, yv , was deter mined clsing the pendant-drop and drop-weight methods. Results are, respectizlely, 1700, 2370, and 2480 +100 dynes per ct for the rhernium -containing alloys and essentially the same as tlwse reported for liquid chro)riln, trolybdenum, and tungsten. Average solid slrjace energy, rsv< xias ))zeasured using tlre fiber-extetlsion method. The ratio of ysS, the acerage high-angle grain-boundary energy, to ySV cclas jolnd fronz grain-bolzdary grooue angles fort)zed at the surface in an inert atrfizosphere. Absolllte iute?:face energies were deterawined using ?nultip/rase equilibria involzing suitable liquids of known surface tension (tin, silver). Interpretation of the experimented results in view of pvobable tenzperatzcre, orientation, and purity effects giz,e the follouling approximations in ergs per sq ctn: ysv (i2lo. Mo-33Re) - 2100, ySS (Mo, Mo-33Re) - 800, rr (defornzation twins in MO-33Re at 1200"C) - 800. ysV (Cr. Cr-35Re) - 2400. YSS (CY, Cr-35Re) - 1000. Probably Ylv- YSV- 2500 for tungsten and W-25Re, giving yss (It&apos;, W-25Re) - 900. The interface energies of solid and liqid ch?&apos;omiu?.z, nolybdenu?rr, and tungsten are not geatly aff&apos;ected by rhenium and therefore are not a ttlajor factor in the ductili zing rhenium effect in Croup VI-A metals. THE interface energies of the refractory Group VI-A metals, chromium, molybdenum, and tungsten, are not well-established. The objective of this investigation was to study the liquid surface tension, solid surface energy, and grain-boundary energy of these metals and compare them to those found for the bcc solid-solution alloys, Cr-35e,&apos; 0-33e,&apos; and -25e. Five techniques were used to measure interface energies in high-purity polycrystal rod, wire, and sheet at 0.6 to 1.0 of the absolute liquidus temperature. The alloys were chosen to see if there was any connection between interface-energy behavior and the ductilizing rhenium effecL4j5 EXPERIMENTAL WORK Materials. A description of the materials used is presented in Table I. Chromium rod was prepared by arc melting iodide process crystals supplied by Chromallo Cor., hot extruding, and warm swaging to 0.63-cm-diam rod.6 The sheet was prepared by rolling as-extruded rod to 95 pct reduction in area from a hydrogen furnace at 800" to 900°C and surface grinding off 0.02 cm from each face. Cr-35Re rod was prepared by arc melting sintered rhenium powder and iodide chromium crystals, warm rod rolling to 50 pct reduction in area in cans, and swaging to 60 pct reduction in area at 1100" to 1200°C. Some of the rod was warm-rolled to sheet and then surface-ground. Portions of swaged chromium and Cr-35Re were further reduced by swaging and drawing to 0.013-cm-diam wire by the General Electric Co. Mo-33Re and W-25Re rod, sheet, and wire were provided by Chase Brass and Copper Co. The molybdenum sheet consisted of two lots, both essentially the same except for the carbon content. Liquid Surface Tension. The liquid surface tension of Cr-35Re, Mo-33Re, and W-25Re was measured by a combination of pendant-drop and drop-weight methods using techniques already decribed." Following out-gassing, molten drops were formed on the ends of centerless-ground Mo-33Re and W-25Re rods by electron bombardment at 5 x 106 mm. Similar drops were formed on outgassed Cr-35Re rods by induction heating under 1 atm of 99.995 pct Ar. Solid Surface Energy. Solid surface energy was measured by conducting microcreep experiments on molybdenum, Mo-33Re, chromium, and Cr-35Re wires at 2350°, 2306, 1550°, and 180O°C, respectively. In preparation, gage marks -2.5 cm apart and -0.001 cm deep were circumferentially scribed on the wire with a razor blade. Weights of the wire material were then attached. Five to seven reasonably straight wires were hung in a container made out of the wire material. The free end was placed through a small hole in the removable top and secured by bending a small portion 90 deg. The containers not only tended to provide vapor-solid equilibrium for the wires but also protected them from gaseous impurities. They were nominally 2.5 cm in diam by 5 cm high and were made from extruded chromium rod, Cr-35Re arc casting, molybdenum bar stock, or welded Mo-33Re sheet. After deg re as ing, the assembly was outgassed at a relatively low temperature to 2 x 10"5 mm and then recrystallized 2 to 8 hr at the creep temperature in a rhenium-element resistance furnace. The static argon atmosphere was gettered by tantalum radiation shielding. Specimen temperature was measured optically to 25"C using calibration with known melting points and blackbody conditions. The wires generally developed a stable bamboo-type structure according to Fig, l(b), (c), and (d) and retained their gage marks [upper portion of Fig. l(d)]. One or two of the weights were clipped off to provide a low load for the creep anneal. To minimize the possibility of bending or breakage, the wires remained attached to the top of the annealing container which was held to keep the wires vertical. The distance between gage marks was

Jan 1, 1967

By Kun Li, Alex Simkovich

The rate of dissolution of alumina in carbon-saturated liquid iron has been studied experimentally in a system where alumina was in the form of a cylindrical rod immersed in an iron bath contained in a graphite crucible. Data obtained consisted of the concentrations of aluminum in the melt as a function of time. In the case of static experiments, the data are shown to agree with theoretical prdictions based on the diffusion of aluminum.. The rate of dissolution was greatly increased by the rotation of the alumina rod. It is concluded that the diffusion of aluminum from the alumina/metal interface is the rate-controlling step. In the past, thermodynamic investigations of systems encountered in ferrous process metallurgy have received widespread attention. More recently, considerable work has been devoted to the study of kinetics associated with these systems in an effort to determine their rate controlling mechanisms. The alumina-iron system is of great importance in ferrous metallurgy. Yet information concerning kinetics of reaction in this system is seriously limited. The present study was made in order to establish the rate-controlling step for dissolution of solid alumina in liquid iron. LITERATURE REVIEW A number of papers concerning dissolution of solid metals in liquid metals have been reported in the literat~re. Generally, for these simple systems, dissolution is controlled by mass transfer of the dissolving species. Complex systems involving dissolution of solid metal carbides and oxides in liquid metals and slags have been studied to a much lesser extent. Skolnick5,6 reported on the reaction between liquid cobalt and poly-crystalline cylinders of tungsten carbide, in which the cylinders were dissolved while being rotated about their longitudinal axes at various speeds and temperatures. As a result of unexpected preferential grain boundary attack by the liquid cobalt, large errors in the measured dissolution rates occurred because of loss of tungsten carbide grains to the liquid cobalt. Nevertheless, it was possible to establish that the liquid Co-W carbide reaction was not controlled by mass transfer. In a similar approach, cooper7 was able to show that artificial sapphire rods, (alumina single crystals) dissolving in lime-alumina-silica slags obeyed a mechanism of mass transfer control. Here, again, the rods were rotated at various speeds and temperatures, and the process was followed as a function of these variables. Forster and Knacke8 took a practical approach to reaction between slags and refractories. By blowing argon through refractory cylinders of silica, silli-manite, or dolomite and directing the gas to rise along the slag-refractory interface, it was possible to increase the rate of mass transfer. Although the method was admittedly crude, it nevertheless permitted an evaluation of the relative stabilities of refractories with respect to slag attack. Data were interpreted on the basis of mass transfer control. EXPERIMENTAL TECHNIQUE Apparatus. An illustration of the apparatus used in this study is shown in Fig. 1. The furnace consisted of a Morganite recrystallized alumina tube wound with a molybdenum coil. A secondary molybdenum heater was mounted around the upper half of the primary coil to aid in controlling the thermal gradient within the furnace. The primary heater tube was 3 in. in ID and 30 in. long. A reducing mixture of 95 pct N and 5 pct H was maintained around the heating elements. Thermal insulation was provided by alumina powder. The chamber within the primary combustion tube contained a boron nitride block near the top to assist in controlling the thermal gradient to the furnace and also to provide a bearing surface for the rotating graphite shaft. The outside diameter of the graphite shaft was $ in. A separate threaded graphite specimen holder was screwed into the end of the shaft. The holder contained a tapered hole drilled into the end to guide the oxide specimens as they were pressed into it for mounting. Additional guidance for the rotating graphite shaft was furnished by a water-cooled bronze bushing attached to the top of the furnace. A steel clamp was fastened to the upper end of the graphite shaft and rested on a thrust bearing; the shaft and clamp were driven by a dc motor through a set of gears. Two O-rings located immediately above the bronze bushing maintained a gas-tight seal about the graphite shaft. The lower half of the alumina tube housed the crucible and charge, which were placed on a 3/4-in. diam movable alumina support tube. With this arrangement, charges could be inserted into or removed from the furnace while the hot zone was maintained at or above 1000°C. To control the temperature of the furnace, the thermocouple was mounted inside the support tube and in contact with the crucible bottom. Stray electric fields in the furnace were of sufficient intensity to cause erratic indications by the thermocouple. By enclosing the thermocouple protection tube in a molybdenum sheath and grounding this shield, the problem was eliminated. Output of the thermocouple went to an automatic continuous balance controller. Procedure. A typical run was as follows. First, electrolytic iron was premelted in graphite crucibles and cast into graphite molds with the same configura-

Jan 1, 1970

By G. R. Speich

The interlarnmelm spacing, growth rate, and degree of segregation that accompany cellular precipitation in four Fe-Zn alloys containing 9.7, 15.2, 23.5, and 30.5 at. pct Zn have been determined in the temperature range 400" to 600°C. The chemical free-energy change for the reaction was calculated from the available thermodynamic data and the known compositions of the phases. The fraction of the chemical free-energy change for equilibrium segregation that is converted into interfacial free energy decreases from 0.43 to 0.08 as the magnitude of this free-energy change increases from 35 to 270 cal per mole. At constant temperature the cellular growth rate is proportional to the cube of the dissipated free energy. At 600°C newly 100 pct of the equilibrium segregation is achieved during cellulm precipitation whereas at 400°C only 85 pct of the equilibrium segregation is attained. During cellular growth, mass transport of zinc occurs by grain boundary diffusion; excess zinc remaining in the a! phase after the completion of growth is removed slowly by volume diffusion. A modified Cahn theory of cellular precipitation predicts the observed interlamellar spacing within a factor of two. In cellular precipitation reactions such as pearlite formation or discontinuous precipitation, the basic problem is to predict the variation of growth rate G, interlamellar spacing S, and degree of segregation P with composition and temperature. To accomplish this we need three independent equations relating these quantities. One of these equations comes from the diffusion solution. To obtain two additional independent equations, some assumptions must be made. cahnl has suggested recently that two plausible assumptions are 1) that growth rate is proportional to the dissipated free energy and 2) that the spacing which occurs is that which maximizes the dissipated free energy. According to the first assumption, this spacing also maximizes the growth rate and the rate of decrease of free energy per unit area of cell boundary. The present work was undertaken to test these assumptions. To test the first assumption it is necessary to study a cellular reaction over a wide range of supersatura-tions to establish a relationship between G and the dissipated free energy at constant temperature. This is possible only in discontinuous precipitation reactions since in pearlite reactions constituents other than pearlite form if the composition of the parent phase deviates even slightly from the eutectoid composition. The Fe-Zn system was chosen for study because 1) discontinuous precipitation proceeds to completion over a wide temperature and concentration range, 2) the degree of segregation within the cell can be measured by lattice parameter measurements,2 and 3) the thermodynamics of this system have recently been determined by Wriedt.3 In this system the cells consisting d alternate lamellae of a and r phases form from supercooled iron-rich a phase. The a phase within the cells is bcc as is the original a phase, cia, but has a different orientation and a slightly lower zinc content than the original a phase. The r phase has a zinc content of about 70 at. pct and a crystal structure isomor-phous with T brass. EXPERIMENTAL PROCEDURE Four Fe-Zn alloys with 9.7, 15.2, 23.5, and 30.5 at. pct Zn were prepared from carbonyl-iron powder (400 mesh, 99.8 wt pct Fe) and zinc powder (200 mesh, 99.99 wt pct Zn). The powders were ball-milled together and cold-pressed under 60,000 psi to discs $ in. thick by $ in. diam. The cold-pressed discs of the alloys with 9.7 and 15.2 at. pct Zn were sealed in evacuated silica capsules and heated slowly to 1100°C over a period of 1 week (3 days at 600°C, then 3 days at 80O°C, then 1 day at 1100°C). The alloys with 23.5 and 30.5 at. pct Zn were treated similarly except that the final homogenization temperatures were 1000" and 85O°C, respectively, to prevent melting. The alloys were quenched in iced brine from the final homogenization temperature. Specimens of each alloy were subsequently aged in salt pots at temperatures of 400°, 450°, 500°, 550°, 600°, and 650°C for times that varied from a few minutes to several hundred hours. At a late stage of this work, an alloy containing 11.2 at. pct Zn was prepared by vapor-impregnation of iron foil with zinc vapor at 890°C. This alloy proved useful for electron microscope studies because it was free of porosity. The homogenization and aging conditions were based on the recent Fe-Zn phase diagram of Stadelmaier and Bridgers4 rather than the earlier diagram of ansen.5 They consist of a homogenization heat treatment in the homogeneous a field followed by an aging treatment in the two-phase a + r field. The aged specimens were metallographically polished and etched in 2 pct nital and the radius of the largest cell in the microstructure determined. This radius plotted vs time gave a straight line whose slope is the boundary migration rate or growth rate G of the cell. To determine the interlamellar spacing, specimens were examined by surface-replica and thin-section electron microscope techniques. Because of the irregular nature of the lamellae within the cell, the average interlamellar spacing S .of the cell was measured by the method of Cahn and Hagel,6 where S is defined by:

Jan 1, 1969