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By G. P. Conard, R. C. Hall, J. F. Libsch

The 50 pct Fe-50 pct Co alloy undergoes a transformation from disorder to an ordered structure of the CsCl type reportedly in the vicinity of 732OC. During this process, the coercive force goes through a maximum, apparently as a result of strains associated with the coherent nucleation and growth reaction. This magnetic alloy also shows a marked increase in the ratio of residual to saturation induction, which is associated with annealing to a high degree of order with the continuous application of a magnetic field. The increase in ratio can be explained on the basis of a decrease in 90' domain boundaries and, perhaps, by an increase in anisotropy resulting from lattice distortion. THE 50 pct Fe-50 pct Co alloy undergoes a disorder-order transformation which has been reported to occur in the vicinity of 732°C1,2 The ordered structure is the CsCl type.' This magnetic alloy also shows a marked increase in the ratio of residual to saturation induction as a result of heat treatment in a magnetic field, sometimes called a response to magnetic anneal.'-' The purpose of this investigation was to study the course of the ordering reaction, the nature of the response to .heat treatment in a magnetic field, and the relation, if any, between ordering and the response. Procedure The method of approach in this investigation was to produce an initial structure as completely disordered as possible and then gradually to order the alloy by isothermal anneals at various temperatures under different conditions of the applied magnetic field. Magnetic, magnetostriction, and X-ray analyses were of primary importance in determining the property and structural changes resulting from the isothermal anneals. Rings of the 50 pct Fe-50 pct Co alloy were prepared from the elemental powders by a powder metallurgy technique, further details of which may be found in ref. 7. The initial structure was produced by annealing the specimens for ½ hr at 1000°C, cooling to and holding for ½ hr at 900°C (in the a range above the ordering temperature), and water quenching. Isothermal anneals were performed at 600°, 675°, 720°, and 740°C. For example, rings were heated to 600°C, held for a predetermined period of time, and cooled by natural cooling at a rate slightly slower than an air cool (average of 20" to 25°C per min). The tests (magnetic, etc.) were made after each heat treatment. All high temperature treatments were performed in a purified hydrogen atmosphere. The treatments at the various temperatures were carried out under one or more conditions of an applied field including 1—no field, 2—field of 20 oersteds applied on cooling only, and 3—field of 20 oersteds applied continuously during heating, holding, and cooling. Magnetic measurements were made using the standard Rowland ring technique8 with a maximum field strength of 100 oersteds. The magnetization curve, induction at 100 oersteds (B.), residual induction (Bt), and coercive force (Hc) were determined. All magnetic analysis data were based on an average of the results from three rings. A strain gage technique9 as used for the measurement of magnetostriction. The X-ray determination of the relative amount of ordered phase present was made on the ring specimen used for magnetic measurement. This was done by the back-reflection method using a rotating specimen (because of the large grain size) with unfiltered CoKa radiation and a 7 hr exposure time. Intensity measurements of the ordered line (300) were made by comparing visually the films so obtained with standard films prepared by exposing for different lengths of time a specimen given a long time anneal (high degree of order). Results In all instances the saturation induction (induction at 100 oersteds) was found to increase slightly with annealing time. This effect was small and appears to be the increase in saturation induction to be expected on ordering.10-13 The residual induction behavior was markedly influenced by the field condition during annealing, Figs. 1, 2. For the condition of no applied field, the ratio of residual to saturation induction remained essentially constant for short annealing times but showed a significant increase at longer times. With increasing annealing temperature, less time was required to produce this increase in the ratio. In the case of the 600°C anneals, the increase did not occur until approximately 20 hr, Fig. I, while on annealing at 740°C the increase was immediate, Fig. 2. Slight decreases in the ratio may be observed at 100 hr for specimens treated at 720°C and at 1 hr for those treated at 740°C. Specimens annealed in a field of 20 oersteds showed a residual to saturation induction ratio consistently higher than that for the specimens annealed without the field. The first anneal with the field (¼ hr) caused an abrupt increase in the ratio at all temperatures; thereafter, the increase in the ratio was generally similar for specimens annealed

Jan 1, 1956

By A. J. Shaler, H. Udin, J. Wulff

In the study of the sintering of meta powders, we have come to the conclusion in this laboratory that further progress requires a more basic understanding of the operating mechanisms. This is emphasized in detail by Shaler. He has shown that a knowledge of the exact value of the surface tension is imperative for a solution of the kinetics of sintering. This force plays a principal role in causing the density of compacts to increase.2 Furthermore, a knowledge of the surface tension of solids is also applicable to other aspects of physical metallurgy. C. S. Smith3 points out the relation between surface and interfacial tension and their function in determining the microstructure and resulting properties of polycrystal-line and polyphase alloys. This paper describes one group of results of an experimental program designed for the study of the surface tension in solid metals. As a by-product of this work, considerable information has been obtained on the rate and nature of the flow of a metal at temperatures approaching the melting point and under extremely low stresses, a field of mechanical behavior heretofore scarcely touched by metallurgists. The importance of this additional information to students of powder metallurgy need not be stressed. Theoretical Considerations Interfacial tension arises from the condition that an excess of energy exists at the interface between two phases. Gibbs proves that this energy is a partial function of the interfacial area; thus: ?F/?s = ? where ?F/?s is the rate of change of free energy of the system with changing surface area, at constant temperature, pressure and composition, and ? is the interfacial tension, or interfacial free energy per unit area. If one of the phases is the pure liquid or solid, and the other the vapor of the substance, ? may properly be termed "surface tension," and is a characteristic of the solid or liquid. The attempt of a body to lower its free energy by decreasing its surface gives rise to a force in the surface which is numerically equal in terms of unit length to the free energy per unit area of the surface. Thus ? may be expressed either in erg-cm-² or in dyne-cm-1. Similarly, surface tension may be determined either by a thermo-dynamic measurement of the surface energy or by a mechanical measurement of the surface force. We have chosen the latter approach. Tammann and Boehme4 determined the surface tension of gold by measuring the amount of shrinkage or extension of thin weighted foil at various temperatures and interpolating to zero strain. The method is of questionable accuracy because of the tendency of foil to form minute tears when heated under tension. Their assumption of F = 2W?, where W is the width of the foil, is unsound, as the foil can decrease its surface area by transverse as well as by longitudinal shrinkage. Although their experimentation was meticulous, the paper does not include details of the sample configuration required for recalculating ? on a correct basis, even if such a calculation were possible. In the experimental procedure chosen here, a series of small weights of increasing magnitude are suspended from a series of line copper wires of uniform cross-section. This array is brought to a temperature at which creep is appreciable under extremely small stress. If the weight overbalances the contracting force of surface tension, the wire stretches; otherwise, it shrinks. The magnitude of the strain is determined by the amount of unbalance, so a plot of strain vs. load should cross the zero strain axis at w = F?. If balance is visualized as a thermodynamic equilibrium, the critical load is readily calculated. At constant temperature, an infinitesimal change in surface energy should be equal to the work done on or by the weight: ds = wdl [A] For a cylinder, s = 2pr2 + 2prl [2] If the volume remains constant, r = vV/pl [31 s = 2vpl+2V/l [4] ds = vpv/l - 2V/l²) dl [5] Substituting [5] into [I] gives for the equilibrium load, w = ?(z/rV- 2V/12) [6] and, again expressing V in terms of r and l, w = pr?(1 - 2r/l [7] Here the end-effect term, 2r/l, is neglected for thin wires in subsequent work. Eq 7 can be confirmed by means of a stress analysis. If the x-axis is chosen along the wire, then the stress is 2pr? - w pr² pr2 [8] A cylinder of diameter dis equivalent to a sphere of radius r, insofar as radial surface tension effects are concerned.³ Thus xv = 2?/d = ?/r = sz [9] For the case of zero strain in the x direction, the strain will also be zero in the y and z directions. Since the wire is under hydrostatic stress, Eq 8 and 9 are

Jan 1, 1950

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The microhardness of single crystals of tungsten disilicide has been investigated by the Knoop method. The average random room-temperature hardness of the WSi, matrix was 1350 kg per sq mm. Hardness crnisotropy was noted with respect to plane and indenter orientation as determined by single-crq.stal X-rny studies. Annealing at 1600" and 1800°C decreased the average hardness to 1310 and 1230 kg per sq tnm, respectively, and produced a second phase identified by X-ray diffraction and electron-microprobe analysis to be wSio.7. Ball-impact experiwzents produced rosettes at 850°C. Optical and electron microscopy showed evidence of slip and cross slip and twinning produced by microhardness indentations. Prismatic (100), [001] slip was found and cor~elated with hardness data. THE present study was undertaken to investigate the hardness anisotropy of as-grown and annealed single crystals of tungsten disilicide. The existence of the silicide WSiz in the W-Si system has been well-established and its structure thoroughly investigated zachariasen2 found WSi, to have a tetragonal C type of structure, similar to that of MoSi, with lattice parameters a = 3.212A, Kieffer et al. studied the W-Si system and measured the density and microhardness (at a 100-g load) of both polycrystalline WSi, and WSi,.,. The values found were 9.25 g per cu cm and 1090 kg per sq mm for WSi,, and 12.21 per cu cm and 770 kg per sq mm for WSi0.7, respectively. According to Samsonov et a1.5 the microhardness of polycrystalline WSi2 is 1430 kg per sq mm (at a 120-g load). EXPERIMENTAL The WSi, single-crystal boules investigated in this paper were grown by a Verneuil-type process using an electric arc by the Linde Division of the Union Carbide Corp.6 The largest specimens were 8 mm in diameter by 16 mm long. The crystals had an average density of 9.01 g per cu cm with a tungsten • silicon content of 99.9 wt pct. The major impurities were: 87 ppm O, 41 ppm N. 54 pprn C, 500 ppm Zr, 50 ppm Na, and 50 ppm Mn. The crystals were silicon-poor, the average silicon content being 22.20 pct (stoichiometric value is 23.40 pct), and tungsten-rich, the average tungsten content being 77.70 pct (stoichiometric value is 76.60 pct). As-received single crystals were ground and analyzed by powder X-ray diffraction technique using Cu Ka radiation. Laue and layer line rotation patterns were obtained on cleaved sections of WSi, single crystals. Electron-microprobe traverses of representative crystals were done using a Phillips-AMR electron microanalyzer. Carbon replicas were used to prepare electron micrographs. This work was done with a JEM-6A electron microscope. Prior to the metallographic examination, the specimens were mounted in Lucite and then polished for short times on polishing wheels using 9-, 3-, and 1-p diamond-grade pastes. Finally they were fine-polished with Linde A powder for 24 hr on a Syntron vibratory polisher. The samples were etched with 4H 2 O:1HF:2HNO3, which is a medium fast-acting etchant. The combination 1HF:2HNO3:5 lactic acid is also a satisfactory etchant. Annealing runs for selected specimens were made at 1600" and 1800°C for 3 hr at 1.0 to 3.0 x 10-5 mm Hg. A Brew tantalum resistance furnace with WSi2 powder for setters was used. The WSi2 powder was the same as that used for the crystal growth. Temperatures were measured with a calibrated W, W-26 pct Re thermocouple and a microoptical pyrometer. Powder X-ray diffraction, emission spectrographic, and electron-microprobe analyses were done after the annealing runs. For microhardness measurements a Tukon Microhardness Tester Type FB with a Knoop indenter was used. Although measurements were taken at loads ranging from 25 to 1000 g, the 100-g load was chosen as the standard load. All measurements were taken at room temperature. Only indentations of cracking classes 1 and 2 were considered.' DISCUSSION OF RESULTS Powder X-ray diffraction analysis showed the as-received crystals to be single-phase WSi2. Laue and layer line rotation patterns obtained on cleaved sections of WSi2 single crystals proved them to be tetragonal WS 2 2 The results also indicated that the c axis of the crystal was oriented parallel to the boule or growth axis. Electron-microprobe traverses across the matrix of the as-grown crystals showed them to be homogeneous WSi,. Optical and electron microscopy of etched crystals, however, revealed that they contained minute amounts of the "golden" and the "blue" second phases as opposed to the "white" or WSi2 phase. These two second phases were concentrated in inclusion and etch-pit

Jan 1, 1965

By R. V. Higgins

This paper presents a computer method to obtain the shape factors and equal cell volumes of the channels for any well spacing pattern from a potentiometric model. By using this program the authors have processed the data for the seven-spot, direct line-drive and the staggered line-drive patterns. The data for the five-spot pattern had been previously processed by a noncomputer method and are included for completeness. The shape factors and volumes for the channels are presented in tables for those who want to use them to process data using their own permeability relationships and viscosities of their reservoir oils. The authors have used the data and sets of representative permeability curves to process sample calculationr of waterflood performances. The comparison of the calculated results shows that the influence of well spacing is small. The permeabilities of the reservoir rock to oil and water had a greater influence on oil recovery for a given pore-volume throughput of water than the well spacing pattern. The more water-wet the reservoir rock, the better the possibility of permeabilities which are conducive to good recovery. The viscosity of the reservoir oil also influences the recovery more than the well spacing pattern. The reduction in the percentage recovery of oil with increase in viscosity of the reservoir oils is small when oil viscosities are in the range of 0.1 to 3. Above this range the reductions in recoveries are extensive. Sample comparisons of the time required for different patterns to recover the oil are presented. Results of an example calculation are given to show the effect of the permeability profile on recovery. INTRODUCTION The effect of well spacing pattern on the recovery of oil when flooding with either gas or water has been studied by many investigators. Muskat et al.1 presented an analysis using conductivity, sweep efficiency and unit mobility to the time of breakthrough. Dyes et al.2 used experimental techniques (X-ray shadowgraphs) and different mobility ratios. They presented quantitatively the relationship between mobility and sweep efficiency at and after breakthrough. Hauber3 presented a method to predict waterflood performance for arbitrary well spacing patterns and mobility ratios. Craig et al.,4 using techniques similar to Dyes et al. to determine sweep efficiency for a five-spot pattern, added the use of relative permeability curves at breakthrough and thereafter. Douglas et al.5 sed rela- tive permeabilities and continuously changing saturations throughout the entire five-spot flood pattern. In obtaining their solutions they used finite-difierence equations. Hig-gins and Leighton6,7 also used relative permeabilities and continuously changing saturations throughout the pattern before and after breakthrough. They employed techniques that process a flood-pattern calculation on the computer in about one minute. The methods of Douglas et al. and Higgins and Leighton both checked closely the laboratory results for a wide range of mobility ratios. This paper presents some sample performances calculated by the Higgins and Leighton method that show the effect on recovery of different permeabilities and viscosities using the seven-spot, the line-drive and the staggered line-drive, as well as the fivespot flood pattern. No previous paper has presented these data using different permeability curves and continuously changing saturations throughout the flood patterns. The paper also presents (1) the results and analyses of the flood-pattern prediction, (2) the computer techniques for determining the shape factors and volumes from the potentiometric models for the foregoing flood patterns, and (3) the shape factors and volumes of the channels of the flood pattern in the event reservoir engineers may like to process waterflood calculations using their own permeability curves and reservoir oils. DESCRIPTION OF METHOD VOLUMES AND SHAPE FACTORS The use of channels taken from a potentiometric model (see Fig. 1) to aid in calculating the performances of water floods of nonlinear patterns has been thoroughly explained in the literature.0,7 Therefore, very little theory, discussion, or proof regarding this phase will be repeated in this paper. The computer method presented in this paper to calculate the volumes and the shape factors of the channels of potentiometric models employs the trapezoidal rule for the volumes and the Pythagorean theorem (the hypotenuse equals the square root of the sum of the squares of the two sides of a right triangle) for the shape factors. In calculating the volume of a channel, the area of each cell in the channel is determined and then multiplied by the thickness to obtain the volume. In determining the areas of the cells, trapezoids are constructed whose vertical sides are spaced Ax apart, as shown in Fig. 2. The length of the sides is the difference between an ordinate cut off by the top and bottom of the cell — usually equipo-tentials. The coordinates of the points along an equipo-tential or streamline are obtained by Lagrange's8 equation of interpolation for which the constants are coordinate points at the intersections. Three intersections for con-

Jan 1, 1965

By H. W. Knott, M. H. Mueller

The crystal structures of Ti2Cu, Ti2Ni, Ti4Ni2O, and Ti4Cu20 have been determined using powder specimens examined by X-ray and neutron diffraction. Lattice constants have been determined for all four phases using X-ray powder diffraction films. Atom positional parameters of all four phases have been determined from observed neutron intensities. X-ray diffraction calculated intensity data have been presented also for the phase Ti2Cu to point out the particular suitability of neutron diffraction in this case. Interatomic distances have been determined using the positional parameters obtained from neutron diffraction. ALTHOUGH some investigations of the crystal structures have been made of these four compounds previously,'-13 it was the purpose of the present investigation to expand the previous work in order to locate the various atoms, determine their coordinates, and to confirm or to correct some of the previous work. It was convenient to group these four compounds together since they are related chemicallv and/or structurally. The compound Ti2Cu is tetragonil; and Ti2Ni, Ti4Ni2O, and Ti4CU2O are all large fees of the same space group. Ti2Cu has been previously reported as a fee phase by Laves and Wallbaum;1 and Rostoker2 which was possibly the oxide phase, Ti4Cu20. Joukainen, Grant, and Floe;3 and Trzebiatowski, Berak, and Ramotow-ski4 have also reported a phase of this composition. karlsson5 has reported a small fct phase of the composition Ti3Cu which may be the presently discussed Ti2Cu phase. More recently Ence and Margolin6 have reported a small fct phase for Ti2Cu and the present authors7 together with Nevitt8 have briefly reported it to be a bet related to the fct with a co three times the length of the co of the fct and have also reported that this phase has a very limited composition. Further refinements will be reported which have varied some of the parameters of this bct structure slightly. Ti2Ni has been reported as a fee phase by Laves and wallbaum;1 Duwez and taylor;9 Rostoker;2 Poole and Hume-Rothery;10 and Yurko, Barton, and parr.11 In a later paper Yurko, Barton, and parr12 have given the complete structure of this phase based on an X-ray diffraction study which was independently confirmed with neutron diffraction by Mueller and knott.7 Additional crystal structure information will be given. Ti4Ti2O, Ti4Cu2O, and a number of other compounds including Ti4Fe2O have been reported as fcc phases by Rostoker,2 and more recently Nevitt13 has confirmed the Ti4Ti2O phase. Rostoker,2 however has reported diffraction lines for Ti4Fe2O which do not have all odd or all even indices. These lines, therefore, cannot be observed if this compound has a fee structure. This same error has crept into the diffraction results reported for TiNi2O and Ti4Cu20 in the ASTM powder data which has been credited from Rostoker's data. Complete crystal structures of these two phases will be presented. Although all four of these structures have large unit cells and hence do not lend themselves for completely resolved neutron powder patterns, a sufficient number of individual reflections was observed for solving the structure. They also serve as good examples of some of the advantages to be gained by using both neutron and X-ray diffraction techniques. EXPERIMENTAL PROCEDURE All of the alloys were prepared by arc melting. The starting metals had the following purity: Cu 99.999 pct, Ni 99.83 pct, and Ti 99.92 pct. Oxygen was introduced into the two oxide phases as chemically pure TiO2, with the remainder of the titanium coming from the above mentioned metal. All of the sample buttons were annealed in evacuated Vycor tubes, the two binary phases for 5 days at 700°C and the two oxide phases for 3 days at 900°C. Oxygen analyses were performed on all four phases by two independent laboratories with the following amounts of oxygen present in atomic percent; Ti2Cu-0.06, Ti2Ni-1.03, Ti4Ni2O-13.95, and Ti4Cu20-13.87. The stoichiometric amount for the oxide phases is 14.29 at. pct. Since all of the samples were very brittle they were easily reduced to a powder for diffraction measurements. The lattice constants given in Table I were determined for the four compounds from X-ray diffraction patterns of powder samples exposed to filtered copper radiation using a 114.59 mm diam Debye-Scherrer type camera using the Straumanis loading. None of the patterns showed a detectable amount of a second phase. The lattice constants were obtained from an IBM 704 computer program employing a least squares treatment with systematic correction terms as previously reported.14

Jan 1, 1963

By R. G. Davies

The activation energy for steady state creep above -500°C is observed to be independent of the applied stress although it varies from -67 kcal per mole at 2 at. pct Si to -100 kcal per mole at 11 at. pct Si due to changes in crystallographic order. The magnitude of the activation energy, by comparison with Fe-A1 alloys, indicates FeSi type of order in certain alloys. X-ray results confirmed the presence of FeSi type of order. It is proposed that dislocation climb is the rate controlling mechanism for all the alloys. It has been demonstrated that when a diffusion mechanism is the rate controlling process, the formation of a superlattice in brass,1 Fe3A1,2 Ni3Fe,3-5 and Feco6 1) increases the creep resistance, and 2) increases the activation energy for steady state creep. Furthermore, a study of creep in Fe-15 to 20 at. pct A1 alloys7 has revealed that as the alloy composition approaches the long-range order field, there is an increase in the activation energy for steady state creep which is thought to be due to an increase in short range order. Fe-A1 and Fe-Si alloys are similar in that they both form the DO3 superlattice in which aluminum or silicon atoms have only iron atoms as first and second nearest neighbors. There are, however, two important differences between the alloy systems: 1) The superlattice formation at -350°C commences at -10 at. pct si8 as compared to -20 at. pct Al,9 and 2) Fe-A1 alloys form a FeAl (B2 type) super-lattice where aluminum atoms have all iron first nearest neighbors even at 22 at. pct Al, but so far no similar FeSi superlattice has been observed. With the similarity between Fe-A1 and Fe-Si alloys in mind, alloys of iron with 2 to 11 at. pct Si were examined for variations with composition of the activation energy for steady state creep and of creep strength. The temperature range of greatest interest was above 1/2 TM (TM is the absolute melting temperature) where it is usually observed that diffusion is the rate controlling process. A subsidiary X-ray investigation of the Fe-Si system was undertaken in an attempt to define the position of the order-disorder boundary as a function of cooling rate. EXPERIMENTAL DETAILS a) Creep. Specimens whose gage length was 1.5 in. and with a cross-section 0.04 by 0.08 in. were strained in tension by a lever-arm arrangement, and the load was adjusted between each creep test to maintain constant stress. The apparatus and mode of operation have been fully described in a previous publication.7 As each test produced a creep strain of 0.25 pct, the variation in stress during the test was negligible. Creep strain was measured at the end of one of the alloy steel grips by a displacement transducer with the out-of-balance potential being recorded on a variable speed recorder. The full-scale deflection of the recorder could be varied in steps to give limits of sensitivity of between 0.1 and 0.001 pct creep strain. The alloys, Table I, were made available by the Metallurgical Department, National Physical Laboratory (N.P.L.), england,10 and by the Research Department, General Electric Co. (G.E.), Schenectady, N.Y. They were hot worked at -850°C, warm worked at 550° to 650°C, and recrystallized in vacuum at -750°C to give a grain diameter of -0.1 mm. All the alloys had a very low impurity content; those from the N.P.L., for which a complete analysis is available,&apos;&apos; show carbon less than 0.026 pct, manganese less than 0.006 pct, and oxygen plus nitrogen less than 0.0024 pct. b) X-ray Procedure. A General Electric XRD-5 X-ray set with a focussing lithium fluoride mono-chromator in the diffracted beam, and a pulse height analyzer to eliminate harmonic wavelengths of the cobalt radiation, was used to investigate the structure of several very fine grained (grain diameter <.01 mm) Fe-Si alloys after the following heat treatments: 1) Quenched from 700°C, 2) slow cooled from 650°C (-40°C per hr), and 3) very slowly cooled from 400° to 100°C (10°C per hr with a 24 hr anneal every 100°C). The method of obtaining the diffraction pattern over the range of 20 from 15 to 45 deg was to count for at least 100 sec every l/3 deg with a slit subtending 1 deg in 20 at the focus; the probable counting error was less than 2 pct.

Jan 1, 1963

By W. C. Ellis, E. S. Greiner, M. E. Fine

Discontinuous changes of Young&apos;s modulus, internal friction, coefficient of expansion, electrical resistivity, and thermoelectric power are evidence for a transition in chromium near 37OC. Although the X-ray diffraction pattern gives no clue, a difference between the thermal expansivity and the temperature dependence of the lattice parameter suggests a crystal-lographic change. Young&apos;s modulus data disclosed another transition near THE thermal dependence of a number of proper- ties of chromium indicates a transition occurring over a temperature range near room temperature. Bridgman&apos; noted this first from a minimum in the electrical resistivity near 12°C. In a sample of greater purity, Sochtig&apos; observed the minimum at 41 °C. Erfling3 reported an inflection in the thermal expansivity curve at 36°C. These temperature-dependence curves are reversible with no hysteresis being detected. No discontinuity or inflection has been observed in the heat capacity&apos; or the paramagnetic susceptibility.&apos; Likewise, no one has noted a change in crystal symmetry. In the present investigation Young&apos;s modulus, internal friction, coefficient of expansion, electrical resistivity, illustrated in Fig. 1, lattice constant, Fig. 2, thermal electromotive force, Fig. 3, and paramagnetic susceptibility, Fig. 4, were measured over an extended temperature range. The samples were prepared in two ways: (1) By cold pressing a sintered electrolytic powder compact,&apos; and (2) by electroforming from an aqueous solution. The electroformed samples were prepared by R. A. Ehrhardt and G. Bittrich by plating on copper or nickel tubes from an aqueous solution according to the method of Brenner, Burkhead, and Jennings.&apos; The pressed powder samples (method 1) were finally annealed at 1400°C in purified helium: the electroformed samples, packed in powdered chromium, were vacuum-annealed at 1000°C. From the composition of the original powder&apos; the purity of the pressed powder samples is estimated to be 99.8 pct Cr. Spectrochemical analysis furnished by E. K. Jaycox, revealed only slight traces of impurities in the electroformed sample (less than 0.001 pct), neither iron nor nickel being detected. Chromium deposited by this method is reported to contain approximately 0.05 pct 0.- Methods and Data Young&apos;s Modulus: For measurement of Young&apos;s modulus, an annealed, pressed powder sample, 0.114 x0.237x1.845 in., and an electroformed sample, 0.10 in. od, 0.01 in. id, and 1.86 in. long, were prepared. The resonant frequencies of the rod samples in forced longitudinal vibration were measured at a series of temperatures from —192" to 200°C by a method previously de~cribed.6,7 Because the samples were nonferromagnetic, iron- silicon or molybdenum permalloy tips (0.013 in. thick) were soldered to the ends. The softening temperature of the solder limited the temperature of measurement. Young&apos;s modulus, E,, of chromium at temperature, T, may be calculated from the resonant frequency of the composite rod, f,; the thickness of the tips, t; the length of the chromium sample at 25°C, l,.; the density of chromium at 25°C, pc (7.20 g per cc);5 and the thermal expansivity, Al/l25. Modulus differences for two temperatures, ET and E, are accurate to +0.002x10" dynes per cm2. ET = 4PAlc+2tyf Young&apos;s modulus at 25°C, Fig. la, is 28.2~10" dynes per cm&apos; (40.8xlO" si) in wrought chromium (upper curve). The modulus of the electroformed sample is apparently lower due to cracks. From the modulus measurements two transitions were observed: one with a critical temperature at 37°C, the other at —152°C. Internal Friction: The internal friction, 1/Q, was determined from the width, Af, of the strain amplitude-frequency curve at 0.707 times the strain amplitude at resonance;&apos; the internal friction, 1/Q, then equals Af/f. Fig. lb shows a sharp peak in internal friction at 38°C. The internal friction of the electroformed sample had a similar maximum. Thermal Expansion: The expansivity measurements, shown in Fig. 2, covering the temperature range —195" to +400°C were made by D. MacNair in an interferometric dilatometer8 sing a sample consisting of three pyramids 0.25 in. high prepared from wrought electrolytic chromium. Below —120°C the experimental points deviated up to ±2x10 from the drawn expansivity curve in Fig. 2 because of decreased precision of the quartz wedge thermometer at low temperatures. Near 38°C the thermal expansivity curve, Fig. 2, goes through an inflection corresponding to a minimum in the coefficient of expansion, Fig. ld, and a relative volume decrease on heating. Electrical Resistivity: The variation of electrical resistivity with temperature measured by the po-tentiometric method is also shown in Fig. l. The resistivity of the wrought chromium (upper curve) at 20°C is 13.6 microhm-cm; of electroformed chromium (lower curve) 12.8 microhm-cm. The lower value reflects higher purity and agrees closely with a published value." A minimum at 40°C occurs in the resistivity curves of both samples. No conclusive evidence for a transition near — 150°C was observed, but the points, Fig. 1, appear to deviate from a smooth curve between —120" and —160°C.

Jan 1, 1952

By David P. Shoemaker, Clara B. Shoemaker

It has been shown for an important class of complex transition intermetallic compounds (a, P, R, 6, and p phases) characterized by "normal" coordination [CN12 (icosahedral), CN14, CN15, CN16/ that interatomic distances nay be calculated to a good approximation as the sum of characteristic atomic radii. Two radii, one for major ligands and one for minor ligmds, are specified for each atom, except in the case of CN12 where only a miaaor-ligand radius is specified. The same appears to be true of transition-metal phases of simpler struc-ture: Laves phases (CN12, CN16), and p-tungsten phases (CN12, CN14). In the case of known examples of the more complex phases, a simple rule is given which specifies these radii. However, only a fraction of the known examples of the simpler phases obey this rule closely. To include the latter phases the rule may be modified by considering the radii as linear functions of the weighted average of the Pauling CN12 radii of the two kinds of atonzs, with the radii weighted according to the over-all chemical composition of the alloy. With very few exceptions interatomic distances for both tlze complex and the simpler transition phases can b$ predicted with this modified rule to within 0.06A. ManY intermetallic compounds are known of composition A,By, in which A is a transition element to the left of the manganese column in the periodic table and B is a transition element in or to the right of it. Frequently the coordination numbers (CN) found in these compounds are CN12 (icosahedral), CN14, CN15, and CN16 (called "normal" coordinations by Frank and Kasperl). Well-known examples are the cubic and hexagonal Laves phases which have CN12 and CN16, and the 0-tungsten (CrsO) phases which have CN12 and CN14. In the more complicated (often ternary) phases, such as the a phase,2 the Beck phases p3 and R~, the 6 phase,5 and the p p atoms occur with CN12, CN14, CN15, and (except for a) CN16; in many cases several crystallographically independent atoms of one particular CN occur in the asymmetric unit. A large number of independent interatomic distances are found in these complicated phases, varying from 20 in the a phase to 94 in the 6 phase. These distances show a large spread; they vary, for example, from 2.358 to 3.278A in the 6 phase. In our analysis of these distances we found that in each of these compounds every atomic position can be characterized by either one or two radii. The CN12 positions are characterized by a single radius, The higher coordinated positions are characterized by two radii, namely: the CN14 positions by 4 in the direction of the twelve "5-coordinated" ligands3 (called &apos;minor" by Frank and Kasperl) and by r:, in the direction of the two "6-coordi-nated" ligands (called "major" by Frank and Kasper); the CN15 positions by r15 for the twelve minor and r:, for the three major ligands; the CN16 positions by rlE for the twelve minor and r:, for the four major ligands. We have expressed the experimentally determined interatomic distances in observational equations as the sums of the appropriate pairs of these characteristic radii and the value of these radii have been determined by the method of least Squares. Despite their wide range, the interatomic distances could then be predicted by the sums of these atomic radii with an average deviation in any one compound of 0.06A or less. The results are summarized in Table I. Inspection of the radii thus obtained shows that in the structures in Table I the radii (in A) are given to a first approximation by the simple relationship: Where CN is the coordination number (12, 14, 15, or 16), and A = 1 for major ligands and = 0 for minor ligands. The interaLomic distances can be predicted within about 0.1A by sums of these atomic radii. Another phase belonging in this group with CN12, 14, 15, and 16 is the y phase & B7, in which A is molybdenum or tungsten and B is iron or cobalt. Recently the M%C phase has been refinedE and the observed distances also agree well with those calculated with Eq. [I]. (In the original determination of the structure of W6FeV7 the F$(II)-W(II1) distance was erroneously given as 2.84A, but we have recalculated it fro? the published parameters and found it to b? 2.57i4, in good agreement with the value of 2.6A predicted with Eq. [I.].) Many binary transition alloys are known to crystallize with the simpler structures having "nor-

Jan 1, 1964

By Forrest K. Pence

Bentonite deposits are known to occur in Texas within the Jackson group of formations. This group represents the uppermost Eocene age sediments found in the coastal plain area of Texas. It outcrops across this area of the state in a narrow band of some 4 to 20 miles width. The outcrop pattern roughly parallels the present Gulf of Mexico shore line and is some 100 miles inland from the Texas shore, Fig 1. The principal bentonite deposits are found in the areas where this outcrop pattern cuts across the south-central Texas counties of Karnes, Gonzales, and Fayette. In these deposits, the better quality bentonite is found in the lower or bottom layers of the volcanic ash deposits in which they occur. Some of these better quality benton-ite~ develop very light colors upon firing and therefore justify their being classified as "white firing." The deposits in Karnes and Gonzales Counties apparently occur in commercial quantity, whereas the white firing strata so far uncovered in Fayette County have been too thin to be classified as yet as "commercial." A study of the ceramic properties of the weathered ash in Gonzales and Karnes Counties was reported in 1941.&apos; Commercial development of the deposit in Gonzales County, 7 miles east of Gonzales, Texas. was started earlier by the Max B. Miller Co. for the purpose of marketing the material as a bleaching clay, and this operation has developed to very sizable proportions. In recent years, this company has offered a specially selected grade of the Gonzales material as a suspending agent in glaze slips. The white firing property especially adapts the material to use in white cover coat enamels. The strata in the deposit are practically horizontal and consist from top to bottom of approximately 2 ft of soil overburden, 10 ft of brown bentonite, 2 ft of coarse white bentonite, and 4 ft of waxy white bentonite overlying a he grained sandstone. The & being made in the quarry is approximately one-half mile in length. Only the bottom 4 ft of waxy bentonite is being recovered, the upper layers being stripped and wasted, Fig 2. It may appear somewhat surprising that the very bottom strata appears to have been the one most completely altered. To confirm this, samples from top to bottom of the various strata were studied microscopically by R. F. Shurtz. Professor of Ceramic Engineering, University of Texas. His interpretation is to the effect that the lower part of the seam was deposited at a much earlier date than the top, and that the lower part was chemically altered to a considerable extent before the upper part of the seam was laid down. The conclusion to be derived from these examinations may be stated briefly to he that the alteration in these strata or parts of strata has proceeded independently of the alteration in other parts of the strata during a considerable geological period. The presence of gypsum and iron stain throughout all of the strata indicates that alteration is now proceeding more or less uniformly throughout. It is contended that the alteration of the original ash to montmorillonite is not a result of the presently operating processes. A deposit which occurs approximately 7 miles southeast of Falls City and just south of the village of Casta-howa, has been explored and leased by J. R. Martin, of San Antonio. Mr. Martin has conducted mining and marketing operations in bentonite for a period of many years and asserts that the white firing strata found in this deposit occurs in commercial quantities. His pit, which is shown in Fig 3, exposes 2 ft of soil overburden, approximately 5 ft of white bentonite having coarse texture, and approximately 5 ft of waxy white bentonite which in turn overlies a brown sandy clay. Here, as in the Gonzales deposit, the most completely altered portion is found at the bottom of the seam, as per following report of microscopic examination by Mr. Shurtz. Sample No. 1: This sample was taken from the top stratum which is one foot thick. It is grayish in color and it contains visible fossilized plants. The color is probably the result of fine carbonaceous material in the rock. Under the microscope the sample is seen to consist of glass and feldspar; the amount of glass predominating. Both these substances are slightly altered. No montmorillonite or other clay mineral can be identified definitely; however, the products of the slight alteration mentioned are probably montmorillonite or mineral gel. Sample No. 2: This sample was taken from the stratum second from the top. This stratum is fourteen inches thick. The sample is light gray. It shows numerous veinlets of greenish translucent material ranging from one-eighth inches wide down to the limit of visibility with the unaided eye. It has the smooth, sub-conchoidal fracture characteristic of some bentonites. Microscopically the sample consists mainly of aggregates of clay minerals. The birefringence of the aggregates is lower than would be expected if the

Jan 1, 1950

By Joseph R. Stephens

Deformation substructures of&apos; polycrystalline tungsten, W-2, 9, and 24 pct Re, and W-3 pct Ta were studied by tra?zsrnission electron microscopy. The stress-strain curve for unalloyed tungsten showed gradual yielding followed by work-hardening. Electron nzicrographs indicated a gradual increase in dislocation density with increase in strain up to 5.0 pct. Dislocations, although frequently jogged, were straight over moderate distances and were in a randorn array. Stress-strain curves for alloy specimens of W-2 and 9 pct Re and W-3 pct Ta exhibited a drop in stress at yielding followed by only slight work-hardening. Electron micrographs of these specimens after strains of 0.05, 0.1, and 0.5 pct revealed no change in dislocation substructure from the unstrained specimens. After 2.0 pct strain, the three alloys exhibited dense networks. W-3 pct Ta was characterized by straight, frequently jogged dislocations comparable with the dislocation structure in unalloyed tungsten after a similar amount of strain. In contrast, W-2 pct Re exhibited dislocations that contained widely spaced jogs, while W-9 pct Re had developed a cell structure after the relatively srnall strain of 2.0 pct. The W-24 pct Re alloy contained a few dislocations after 0.1 pct strain, while after 0.5 pct strain twins were evident. Dislocation slip bands apparently preceded the twins. The stress-strain curve for the alloy indicated that twinning commenced after approximately 0.25 pet strain. These results indicate that the primary effect of low rhenium concentrations (2 and 9 pct) in tungsten is to increase dislocation multiplication after macroyielding by reducing the Peierls-Nabarro force (lattice resistance to dislocation motion). The dislocation bands that precede twins in W-24 pct Re may be caused by localized internal stresses resulting fro a metastable structure, for example, clustering of rhenium atoms. The effect of high rhenium additions (22 a 65 pet* Rproperties of tungsten. Klopp, Witzke, and Raffo5 reported bend transition temperatures as low as -100°F (200°K) for dilute electron-beam-melted W-Re alloys tested in the worked condition. Recrystalliza-tion increased the bend transition temperature, but alloys with 2 to 4 pct Re were still markedly superior to unalloyed tungsten. Fractographic examinations of tungsten and W- 3 pct Re and W- 5 pct Re alloys by Gilbert 6 revealed that these low rhenium alloys showed a greater tendency toward cleavage failure than did tungsten. Garfinkle 7 showed that rhenium additions, up to 9 pct, to (100) oriented tungsten single crystals increased the proportional limit stress and decreased the flow stress and the rate of work-hardening. In addition, while deformation in unalloyed (100) oriented crystals apparently involved both (110)100) and (112) slip, crystals with rhenium contents of 5 andpct or more deformed primarily by (112) slip. The mechanism by which high and low rhenium additions affect the mechanical properties of tungsten is still not well-established. The present investigation was undertaken to determine by transmission electron microscopy the effects of low rhenium additions, 2 and 9 pct, and a high rhenium addition, 24 pct, on dislocation substructure in the early stages of deformation of polycrystalline electron-beam-melted tungsten. Unalloyed tungsten and a W- 3 pct Ta alloy were included for comparison. EXPERIMENTAL PROCEDURES Materials. Triple electron-beam-melted tungsten, W-2, 9, and 24 pct Re, and W- pet Ta were used for this investigation. Chemical analyses of the cast ingots are given in Table I. A description of the starting metal powders and melting and fabrication pro-cedures for unalloyed tungsten and the W-Re alloys is reported.5 The W-3 pet Ta alloy was processed in a similar manner. Compression specimens measuring 0.300 in. (7.6 mm) in length by 0.130 in. (3.3 mm) in diam were machined from swaged rods. All alloy specimens were annealed in a vacuum of 8 x 10- 6 Torr (10&apos;2iVper sq m) for 1 hr at 3600°F (2255°K). The recrystallized grain size ranged from 0.06 to 0.08 mm diam for the alloy specimens. Unalloyed tungsten was annealed at 2400° F (1589°K) for 1 hr to produce a recrystallized grain diameter of approximately 0.12 mm. Specimens were electropolished in a 2 pet NaOH solution to a diameter of 0.125 in. (3.18 mm) to remove surface notches resulting from grinding and to improve reproducibility of t data. The ends o the compression specimens were ground flat, parallel to each other, and perpendicular to the longitudinal axes with 4/0 emery paper. Compression Tests. The compressive stress-strain apparatus used for compression tests is described in detail by Stearns and Gotsky.9 Room-temperature compression tests were conducted at a crosshead speed of 0.01 in. per min (0.25 mm per min).

Jan 1, 1969

By H. Conrad, V. V. Damiano, G. J. London

A method is described for producing single crystals of high-purity beryllium, Be-4.37pct Cu, and Be-5.24 pct Ni. These crystals were prepared for testing in compression parallel to the [0001] by orienting and lapping to within ±3&apos; of arc of the (0001). Microstrain testing apparatus is described along with c axis compression results for ingot purity beryllium, twelve-zone-pass material, and the above-mentioned alloys. Results show no measurable plasticity for the ingot purity material from -196" to 400°C, although some surface traces of (1122) slip was observed at 200°C and above. The twelve-zone-pass material shows substantial microstrain plasticity at 220°C with slip on (1122). Both alloys show significant plasticity at room temperature and above with slip also on (1122) planes. THE two slip systems which normally operate during the plastic deformation of beryllium in the vicinity of room temperature are:&apos; basal slip (0001)(1120) and prism slip . Pyramidal slip with a vector inclined to the basal plane has been reported for elevated temperatures,&apos;-a but occurs near room temperature only at very high stresses.~ A summary of the available data on the effect of temperature on the critical resolved shear stress for slip on these systems has been compiled by Conrad and Perlmutter.~ It has been postulated6&apos;7 that one of the principal factors contributing to the brittleness of poly crystalline beryllium at temperatures below about 200°C is the difficulty of operating pyramidal slip with a vector inclined to the basal plane. Hence, detailed information on the operation of such a slip system is important to understanding the brittleness of beryllium. The operation of pyramidal slip with a vector inclined to the basal plane is best accomplished in beryllium by compressing single crystals in a direction parallel to the c axis. In such a test the resolved macroscopic shear strzss on the basal and prism planes is zero and (1012) twinning which is favored by tension along the c axis does not occur. Hence, in c axis compression of beryllium the normal deformation modes are inhibited and the operation of pyramidal slip with a vector inclined to the basal plane is favored. In the present investigation, c axis compression tests were performed on beryllium single crystal as a function of temperature (77" to 700°K), purity (commercial and twelve zone pass), and alloy content (4.37 wt pct Cu and 5.24 wt pct Ni). Presented here is a description of the test techniques employed and the gross mechanical behavior observed. A detailed analysis of the slip traces developed on the surfaces of the deformed specimens during these tests and the results of electron transmission studies of the deformed crystals are given in a separate paper.B PROCEDURE 1) Materials and Preparation. Single crystals about 1 in. diam were prepared of the following materials: commercial-purity beryllium, high-purity beryllium, and two beryllium alloys, one with 4.37 wt pct Cu and the other with 5.24 wt pct Ni. The commercial-purity single crystals were obtained by cutting specimens from large-grained ingot of Pechiney SR material, which is approximately 99.98 pct pure. The high-purity crystals were prepared by floating-zone refining (twelve passes) a rod (7 in. by 1 in, diam) of Pechiney SR grade cast and extruded beryllium. Although an absolute chemical analysis of the zone-refined material was not established, mass spectro-graphic analysis, emission spectrographic analysis, and y activation analysis indicated that it contained in atomic fractions about 5 to 10 ppm each of carbon and oxygen, 1 to 5 ppm each of nickel and iron, and about 1 to 2 ppm of copper, with the remaining residual impurities being less than 1 ppm. Further indication of the purity of this material is provided by the critical resolved shear stress for basal slip, which was approximately 300 psi. The starting material for the alloy single crystals was 1-in.-diam floating-zone-refined (six passes) rod of Pechiney SR grade beryllium. Two such rods were wrapped respectively with sufficient weight of wire of high-purity copper (99.999 pct) or nickel (99.999 pct) to yield a 5 wt pct alloy. A seventh floating-zone pass was then applied to each of the rods to accomplish the initial alloying and an eighth pass for homogenization. Analytical samples were taken from regions of the rod immediately adjacent to where the mechanical test specimens were cut; these indicated 4.37 wt pct Cu and 5.24 wt pct Ni. 2) Crystal Orientation. To avoid the occurrence of basal slip during c axis compression testing, it is necessary to load the crystals as nearly parallel to the c axis as possible. Preliminary c axis compression tests indicated that plastic flow and/or fracture occurred at stresses of the order of 300,000 psi; hence on the basis of a critical resolved shear stress for basal slip of 300 to 400 psi, the maximum crystal misorientation permitted is about 4 to 5&apos; of arc. Since this accuracy cannot be obtained using the usual back-

Jan 1, 1969

By C. G. Dunn

According to a recently suggested effect of silicon on the re recrystallization textures of high-purity Fe-Si alloys with (111)[112] type rolling textures, the recrystallization texture for a rolled (110)[001] oriented iron crystal probably should be entirely different from that of a (110)[001] oriented 3 pct Si-Fe crystal. Comparative studies of iron and 3 pct Si-Fe crystals, however, show that both have (110)[Ool] recrystallization textures when the rolling textures are the (111)[112] type after reductions in thickness of about 70 pct. Qualitatively the results from the iron crystal are like those of polycrystalline high-purity 3 pct Si-Fe and not like polycrys-talline high-purity iron. The large effect previously noted probably involves unknown impurities or processing variables rather than silicon itself. Some problems on experimental and analytical procedure for a spherical X-ray specimen, which was machined from a laminated composite of sheet specimens, are treated in the Appendix. A possible strong effect of silicon on the textures produced in cold-rolled high-purity Fe-Si (HPFe-Si) alloys during primary recrystallization and normal grain growth was suggested in a recent paper.&apos; All the textures were far from the random-orientation type, but that of iron, or of Fe-Si alloys of low silicon composition, was entirely different from the texture of 3 pct Si-Fe. The same effect was noted for the textures obtained prior to normal grain growth, i.e., for primary recrystallization.2 It is the main purpose of the present paper to provide some clarification of this silicon effect. All the HPFe-Si alloys from zero to 3 pct Si, which were rolled by two or more stages separated by anneals, developed (111)[112] type rolling textures.2 Thus, there was no effect of silicon on the rolling textures. Earlier, Gensamer and Mehl3 also found no effect of silicon on the rolling textures of Fe-Si alloys; they obtained the Kurdjum.ow and Sachs (K-S) rolling texture for iron,4 which is characterized as the three ideal components: (100)[011], (112)[li0], and (111)[112]. There is a difference between the HPFe-Si multiple-stage rolling texture and the K-S single-stage rolling texture, but this is a variable processing effect. Of interest here is the fact that the recrystallization textures from (111) [llZ] type rolling textures were different depending on the amount of silicon in the alloy. There was a relatively strong (110) [001] component in the recrystallization texture of HP 3 pct Si-Fe5,8,2 but no such component in HP 0.6 pct Si-Fe, for example; the recrystallization texture for the latter was two (111) [110] type components and a (111) fiber component 1,2 Several publications have shown that a strong (110) [001] recrystallization texture is derivable from a (111) [112] type rolling texture for 3 pct Si-Fe crystals reduced in thickness by about 70 pct.7-10 Furthermore it appears that the strongest of these (110) [001] recrystallization textures occurred when the orientation of the crystal prior to rolling was (110) [001].7 Barrett and evensoon11 found that the rolling texture of a (110)[001] oriented iron crystal was (111) [llj]. Accordingly, it seemed desirable to determine whether a (110) [001] oriented iron crystal, upon rolling and annealing, would behave like the 3 pct Si-Fe crystal (or the polycrystalline HP 3 pct Si-Fe) and thus produce a (110) [001] recrystallization texture contrary to the suggested silicon effect, or would behave like the polycry stalline HP iron or HP 0.6 pct Si-Fe and thus produce (lll) [110] type components in agreement with a silicon effect. Briefly, the idea here involves the use of more precisely defined textures to obtain if possible better control of important variables that affect the recrystallization process. PROCEDURE A (110) oriented crystal of Ferrovac "E" iron (99.9 pct pure) was prepared in sheet form 0.080 in. thick with the [001] direction parallel to the long dimension of the specimen.&apos;&apos; This crystal was etched to 0.073 in. thickness (to remove some small included grains) and then was cold rolled in a 6-in.-diam mill to a final thickness of 0.022 in. The rolling was unidirectional except for an inadvertent reversal at 0.061 in. thickness. At this thickness, and also at 0.040 in., the rolling was interrupted for transmission Laue photographs. Molybdenum Ka-radiation filtered with zirconium was used in a transmission method1&apos; to obtain the cold-rolled (110) pole figure. The sample was a 0.002-in.-thick section taken from the central region of the 0.022-in.-thick cold-rolled crystal. For the primary recrystallization study, cold-rolled samples were etched from 0.022 to 0.021 in. thick and annealed in hydrogen at 850°C. Primary recrystallization to a fine-grained structure, Fig. 1, was obtained in a 5-min anneal. Eleven sheets after

Jan 1, 1963

By L. F. Bryant, J. P. Hirth, R. Speiser

The surface, gain boundary, and twin boundary energies, as well as the surface diffusion coefficient, of cobalt were determined from tests at 1354°C in pure hydrogen. A value of 1970 ergs per sq cm was calculated for the surface energy, using the zero creep method. It was possible to measure the creep strains at room temperature because the phase transformation was accompanied by negligible irreversible strain and no kinking. Established techniques based on interference microscopy were used to obtain values for the other three properties. The gain boundary and twin boundary energies were 650 ad 12.7 ergs per sq cm, respectively, while a value of 2.75 x l0 sq cm per sec was determined for the surface dufusion coefficient. In the course of a general study of cobalt and cobalt-base alloys, information was required about the surface energy of cobalt. Hence, the present program was undertaken to measure the interfacial free energy, or, briefly, the surface energy, of the solid-vapor interface of cobalt. The microcreep method was selected for this measurement because other surface properties could also be determined from the accompanying thermal grooving at grain boundaries and twin boundaries. A brief summary of the methods for determining the various surface properties follows. At very high temperatures and under applied stresses too small to initiate slip, small-diameter wires will change in length by the process of diffu-sional creep described by Herring.1 The wires acquire the familiar bamboo structure and increase or decrease in length in direct proportion to the net force on the specimen. For a specimen experiencing a zero creep rate, the applied load, wo, necessary to offset the effects of the surface energy, y,, and grain boundary energy, y b, is given by the relation: where r is the wire radius and n is the number of grains per unit length of wire. The first results obtained from wire specimens were reported by Udin, Shaler, and Wulff.&apos; udin3 later corrected these results for the effect of grain boundary energy. The grain boundary energy is determined from measurements of the dihedral angle 8 of the groove which develops by thermal etching at the grain boundary-free surface junction. For an equilibrium configuration: Measurements of the angle 8 can be made on the creep specimens4&apos;5 or on sheet material, as was done in this investigation by a method employing interference microscopy.= If the vapor pressure is low, the rate at which grain boundary grooves widen is determined primarily by surface diffusion and, to a lesser extent, by bulk diffusion. The surface diffusion coefficient, D,, is obtained from interferometric measurements of the groove width as a function of the annealing time, t. As predicted by Mullins~ and verified by experiment, the distance, w,, between the maxima of the humps formed on either side of the grain boundary increases in proportion to if grooving proceeds by surface diffusion alone. For this case: where fl is the atomic volume and n is the number of atoms per square centimeter of surface. When volume diffusion also contributes to the widening, the surface diffusion contribution can be extracted from the data by the method described by Mullins and shewmon.8 Where a pair of twin boundaries intersects a free surface, a groove with an included angle of A + B (using the groove figure and notations of Robertson and shewmong) forms by thermal etching at one twin boundary-free surface junction. If the "torque terms", i.e., the terms in the Herring10 equations describing the orientation dependence of the surface energy, are sufficiently large, an "inverted groove" with an included angle of 360 deg-A&apos;-B&apos; develops at the other intersection. The angles A + B and A&apos; + B&apos; are measured interferometrically. When the angle, , between the twinning plane and the macroscopic surface plane is near 90 deg, the twin boundary energy is calculated from the relation: 1) EXPERIMENTAL TECHNIQUES Five-mil-diam wire containing 56 parts per million impurities was used for making ten creep specimens. These specimens had about 15 mm gage lengths with appended loops of wire and carried loads (the specimen weight below the midpoint of the gage length) ranging from 3.7 to 149.8 mg. The wires were hung inside a can made from 99.6 pct pure cobalt sheet. Beneath the wires were placed small specimens of 20-mil-thick, 99.9982 pct pure cobalt sheet from which the relative twin boundary and grain boundary energies and the surface diffusion coefficient were measured. All the specimens were annealed at a temperature of 1354" i 3°C which is 92 pct of the absolute melting point of cobalt. The furnace atmosphere was 99.9 pct pure hydrogen that was purified further by a Deoxo catalytic unit, magnesium perchlorate, and a liquid-nitrogen cold trap. As a precautionary measure the gas was then passed through titanium alloy turnings which were heated to 280" to 420°C and replaced after every test period. The hydrogen was maintained at a

Jan 1, 1969

By W. M. Robertson

The formation of grain boundary grooves on surfaces of poly crystalline samples of cobalt and iron immersed in liquid lead has been studied. The grooves form by volume diffusion of the solutes cobalt and iron in the liquid. The diffusion coefficients of the solutes in liquid lead are derived from the measured rate of grooving. The diffusion coefficients are described by the relation D = Do exp (-Q/RT), with, for cobalt, Do = 4.6 x 10-4 sq cm per sec and Q = 5300 ± 800 cal per mole, and for iron, DO = 4.9 x 10-3 sq cm per sec and Q = 10,500 ± 1500 cal per mole. LIQUID metal-solid metal interactions occur at solid-liquid interfaces. Interfacial energy provides a driving force to change the morphology of the interface. Mullins1,2 has derived expressions for the kinetics of interface morphology changes driven by capillarity. These expressions can be applied to an isothermal system of a solid in equilibrium with a liquid saturated with the solid. Surface profile changes can occur by volume diffusion of the solute in the liquid, by volume self-diffusion in the solid, and by interfacial diffusion at the liquid-solid interface. A groove will form at the intersection of a grain boundary with a solid-liquid interface, reducing the total interfacial free energy of the system. The solid-liquid interfacial energy ? must be greater than half the grain boundary energy of the solid ?6 for Mullins&apos; calculations to apply. If ? is less than ?b/2, then the liquid penetrates the boundaries, separating the grains rather than forming grooves. Boundary penetration did not occur in the work described here. where CO is the equilibrium volume concentration of the solid in the liquid, Dv the volume diffusion coefficient of the solid in the liquid, ? the interfacial free energy of the solid-liquid interface, O the atomic volume of the solid crystal, k Boltzmann&apos;s constant and T the absolute temperature. Eqs. [1] and [2 ] also apply to grooving by volume self-diffusion in the solid,1 with CoODv = D Self, where DSelf is the volume self-diffusion coefficient of the solid. For a grooving mechanism of interfacial diffusion at the solid-liquid interface, the groove width is given by2 where CS is the interfacial concentration of the diffusing species, and DS is the interfacial diffusion coefficient. Eqs. [1] and [3] can be used to determine the mechanism of groove growth. A t1/3 dependence of the growth indicates volume diffusion and t1/4 indicates interfacial diffusion. In some cases, volume diffusion and interfacial diffusion both can contribute substantially to the grooving process, causing the time dependence to be intermediate between t 1/3 and t1/4.3 For these cases, the relative contributions of the two processes can be separated.4 However, in many cases, one process will be dominant, and the data can be analyzed on the basis of Eq. [1] or Eq. [3] alone. The time dependences for volume diffusion in a liquid and volume self-diffusion in a solid are the same. However, the self-diffusion contribution of the solid is usually negligible compared to volume diffusion in the liquid. After the grooving mechanism has been determined, Eq. [1] or Eq. [3 ] yields the kinetic parameter A or B. The kinetic parameter can be used to calculate values for the unknown quantities in the product CD?. Usually C is known or can be estimated. If ? is known, then D can be calculated. In a measurement of grain boundary grooving of copper in liquid lead,&apos; the time dependence indicated volume diffusion in the liquid. The quantities Co, Dv, and ? were obtained from the literature, giving excellent agreement between the observed values of A and the values calculated from Eq. [2 ].5 In a study of the grooving of several refractory metals in liquid tin and liquid silver, A1len6 educed that grooves formed by volume diffusion in the liquid. In a study of nickel in a nickel sulfide melt, Steidel, Li, and spencer7 found volume diffusion grooving kinetics. Both Dv and ? were unknown, so they could not obtain either one separately, though they did obtain a reasonable value for the temperature dependence of the product Dv ?. Several methods have been used to obtain surface profiles. It can be done by sectioning through the interface7 or by chemically removing the liquid from the solid surface after solidification of the liquid.6 However, if the liquid dewets the solid on removing the solid from the melt, then the interface can be observed directly. This method was used previously&apos; and was utilized also in the present study. EXPERIMENTAL PROCEDURE Lead of 99.999 pct purity was obtained from American Smelting and Refining Co. Cobalt sheet was obtained from Sherritt-Gordon Mines, Ltd., with a nominal purity of 99.9 pct, the principal impurities being nickel, iron, copper, carbon, and sulfur. The sheet was

Jan 1, 1969

By W. A. Backofen, R. L. Fleischer

Single crystal, bicrystal, and polycrystal tensile tests of aluminum at 4.2°K, 77°K, and 300°K have been used to examine the role of grain boundaries in the deformation process. Results indicate that a grain boundary may affect the extent and slope of easy glide. The stage II hardening rate, on the other hand, is independent of the presence or absence of grain boundaries. This conclusion allows the size of the region of multiple slip caused by an incompatible grain boundary to be determined. For the size of bicyystal sample used in this study, multiple slip occurs in about half of the cross section. PREVIOUS studies of the stress-strain characteristics of bicrystals of face-centered-cubic metals have been limited to aluminuml-5 at room temperature. Recent results, however, indicate that the stress-strain curves of single crystals of such metals may be separated into at least three stages6 in which different deformation processes are occurring7 provided testing is done at sufficiently low temperatures.&apos; Since for aluminum a well-defined stage II develops only below room temperature, previous studies have not been able to relate effects of grain boundaries to all of the three stages of deformation. It is therefore to be expected that low-temperature deformation of aluminum single crystals and bicrystals should clarify the effects of grain boundaries on the different processes of deformation. EXPERIMENTAL PROCEDURE Single crystals and bicrystals were grown from the melt by the standard techniqueg with aluminum reported by Alcoa to be 99.993 pct pure. Ridges in the boat were used to guide the grain boundary during growth, assuring that the boundary would bisect the sample.10 The rate of furnace motion during growth was 1.0 cm per hr. During growth zone purification resulted, as evidenced by the ability of the first material to freeze to recrystallize at room temperature following severe deformation. Samples were approximately 4.4 X 6.6 mm in cross section and 103.5 mm in length between grips. Samples were annealed at 635" i 5°C for 40 hr and furnace cooled over a 7-hr period. They were then electropolished in a solution of 5 parts methanol to 1 part perchloric acid at a current density of 15 amp per sq dm for about 30 min at temperatures below 0°C. Tensile testing was performed at 295" (room temperature), 77" (sample in liquid nitrogen), and 4.2"K (sample in liquid helium) on the hard-type machine indicated schematically in Fig. 1. The machine con- sists basically of a tube surrounding a rod; one end of the sample is attached to each member, and the rod is pulled up the tube to extend the sample. The rod is rigidly mounted and is moved vertically by a system described by asinski." The pulling force is measured continuously by an electrical strain gage load cell, and the relative displacement of the tube and rod is also recorded continuously by a soft cantilever beam with electrical strain gages. Maximum stress and strain sensitivities were ±2g per sq mm and * 3-10-5. In all tests the strain rate was approximately 5.10-5 per sec. The thin wires in the tensile apparatus introduce softness, which may be corrected for, however, by measuring load vs displacement with the sample replaced by an elastic member. For loads greater than 15 kg the spring constant is 1.875.106 g per cm. The flexible wires also served to reduce substantially the large shearing forces which may arise in the case of grips having horizontal rigidity.&apos;&apos; As in any gripping system, however, bending moments will arise in the course of deformation by single slip. Engineering stress, s = (load)/(original cross-sectional area), and strain, E = (increase in length)/ (original length), are used for stress-strain curves unless otherwise indicated. Tables list resolved shear stress, T=mo and shear strain ? = dm, where m is the usual Schmid resolved shear stress factor for the primary slip system at the start of deformation. The first group of samples to be described forms an isoaxial set, all of the crystals making up the single crystals or bicrystals having the same tensile axis, the orientation of which is indicated by the cross in Fig. 2. For this orientation the primary slip plane and slip direction make angles of 45 deg with the tensile axis and the Schmid factor m has its maximum possible value of 0.5. Rotations about the tensile axis are indexed by means of an angle 0 between the small-area surface of the samples and the projection of the primary slip direction onto the cross section, as defined in Fig. 3. In single crystals, values of 0 were 0 and 90 deg, while in bicrystals 0 values were (0 deg, 180 deg), (90 deg, 270 deg), and (0 deg, 90 deg) as indicated in Fig. 4.

Jan 1, 1961

By R. G. Aspden

The cold rolling and annealing textures were studied for 3 pct Si-Fe grains initially (001) [hkl]. A concentration of (001) [loo] primaries were observed only in the annealing textures of crystals initially having [loo] within 8 deg of the rolling direction. Eke annealing textures of the (001) [I101 cold rolling textures were sensitive to the initial orientation of the grains. Single crystal data were used to explain the formation of (001) [loo] in poly-crystalline malerial. CUBE texture formation in 3 pet Si-Fe sheet occurs during the final high temperature anneal. Its formation is dependent on the proper distribution of (001) plane primaries with reference to the rolling direction&apos; and on the growth of these primaries by secondary recrystallization. The selective driving force for these primaries with (001) within 7 deg of rolling plane is derived from the difference in surface energy between the annealing atmosphere and the crystallographic planes exposed at the surface of the sheet.&apos;-= The alignment of [loo] directions of (001) secondaries with the rolling direction is required for optimum magnetic characteristics7 and is dependent on processing.&apos; A high degree of alignment has been observed when the final cold rolled texture has a strong (111) [ll2] type component3 and the normal grain growth texture prior to secondary recrystallization has components with a [loo] parallel to the rolling direction and planes from (001) to (110) parallel to the rolling plane.1,3,8,9 Generally, this (001) component is much weaker than the (110) component. The growth rate of (001) plane primaries to secondaries has been found to be independent of the orientation of the primaries with reference to the rolling direction, i.e., the secondaries have the same degree of alignment of [loo] directions with the rolling direction as the (001) primaries.&apos; Hence, the rolling and annealing textures of individual grains or single crystals are of interest in understanding the development of the (001) [loo] secondary recrystallization texture. (001) components have been observed in the annealing textures of cold rolled grains initially having a [loo] parallel to the rolling direction and an (001) rotated up to 30 deg from the rolling plane. Crystals initially near the (001) [loo] orientation when rolled under the influence of constraints imposed by neighboring grains form deformation bands and ro- tate in both directions toward (001) <110>.10,11 Deformation bands have been reported also for crystals initially with an (001) within 1 deg of the rolling plane and a [loo] within 1 deg of the rolling direction when rolled as a free single crystal.12 These crystals have weak recrystallization textures and contain near an (001) [loo] component.10-12 When near (001) [loo] crystals are rolled as free single crystals no deformation bands form and the crystals rotate by a single rotation toward (001) [110]. Recrystallization after a 70 pct cold reduction yielded near an (001) [loo] component13 and after a 90 pct cold reduction an (001) [I201 component." Crystals initially near (210) [001] had a texture after a reduction of 70 and 84 pct which was similar to the (111) [li2] but rotated 10 to 15 deg in the transverse direction. These crystals recrystallize to (210) [OOl] or (410) [001] and contain an (001) [loo] component.10,13 An (001) component has not been detected in the normal grain growth textures of other single crystals. Crystals initially having orientations between (110) [001] and (111) [ll2] have a cold rolled texture of principally (111) [ll2] .10>16 Other crystals with a [I101 parallel to the cross direction rotate to (111) [112] and/or (001) [110] stable end orientations. Crystals initially having from (001) [110] to (111) [lie] retain this orientation after cold rolling.15 The cold rolled textures having [I101 directions parallel to the rolling direction had components in the annealing textures related to the deformation textures by 25 to 30 deg rotations about common (1 10) poles. Cold rolled textures of the (111) (112) type recrys-tallized to (120) [001] or (110) [00l]. The purpose of the present work was to further the understanding of the alignment of [loo] directions of (001) secondaries with the rolling direction. The cold rolling and annealing textures of grains initially (001) [hkl] were studied. These data were applied to the formation of (001) [loo] by secondary recrystallization. PROCEDURES AND EXPERIMENTAL TECHNIQUES The (001) poles near the sheet normal and rolling direction are given in Fig. 1 for the 10 grains studied. Each of these grains was located in the center of a polycrystalline specimen approximately 25 mm wide and 50 mm long. The lower case lettered grains, a through dl were about 1.2 mm in diam and near the (001) [loo] orientation. Specimens containing these grains were from a commercial 3 pct Si-Fe alloy with the principle orientation of (110) [001] as obtained by impurity inhibition of growth with manganese sulfide inclusions.17,18 Upper case lettered grains, A through F, were about 6 mm in diam and had (001) planes near the rolling plane and [hkl] di-

Jan 1, 1963

By W. J. Helfrich, R. A. Dodd

Binary aluminum solid-solution alloys containing various amounts of silver, magnesium, and zinc were prepared by careful directional solidification, and the hydrostatic and X-ray densities were compared. With the exception of the Al(Ag) alloys, the X-ray densities were consistently greater than the hydrostatic measurements, in agreement with earlier observations by Ellwood. In contrast to Ell-wood&apos;s interpretation in terms of vacant lattice sites associated with Brillouin zone effects, a tentative explanation based on the existence of solidification microshrinkage was favored. This hypothesis was confirmed by an examination of Al(Zn) alloys prepared by vapor diffusion of zinc into aluminum. The hydrostatic and X-ray densities were now in very close agreement, and it was concluded that the filling of Brillouin zones in aluminum solid-solution alloys does not necessarily result in the formation of defect structures containing an excess of vacant lattice sites. ThE existence of defect structures of the vacancy type in alloys in which the excess vacancies have an electronic rather than a thermal or mechanical, and so forth, origin is well recognized. Examples of incomplete lattices of this type are to be found in the Ni-Al,1-3 Fe-Ni-A1,4 c~-Ni-Al,5 Fe-Cu-Al,= and Co-A17 systems. These defect structures are of a special kind in that the intermediate phases possess an ordered atomic arrangement or superlattice, and in some instances the vacancy concentration may be unusually large, e.g., at 45.25 at. pet Ni in NiA1, approximately 8.8 pet of the lattice sites are unoccupied. Ellwood8-10 has reported similar defect structures in the aluminum solid solution alloys of the Al-Zn and A1-Mg systems and in alloys of the Au-Ni system." In Al(Zn) the (apparent) vacancy concentration rose, somewhat irregularly, to a maximum of about 2 pet vacant sites at 25 at. pet Zn, while in Al(Mg) the (apparent) vacancy concentration increased continuously to 1.7 pet at 15 at. pet Mg. An explanation in terms of Brillouin zone overlap was attempted, although Pearson12 has pointed out the difficulty of reconciling the observations with zone theory. However, the possibility of the effect being caused by the Fermi surface just touching a plane of energy discontinuity inside a prominent Brillouin zone has, in general, been accepted. In fact, Massal-ski13 has interpreted Ellwood&apos;s8 observations as confirmation of Leigh&apos;s14 theoretically predicted zone overlap occurring at approximately 2.67 electrons per atom. Unfortunately, Massalski was apparently unaware that Ellwood9 had revised his earlier results considerably, and the revised data did not confirm Leigh&apos;s analysis. Ellwood&apos;s clata were reexamined by the present authors who noted a possible correlation between the percentage defects as a function of alloy composition and the temperature interval of solidification measured from the respective equilibrium diagrams. This suggested an explanation in terms of shrinkage porosity rather than vacant lattice sites, and pointed to the desirability of reexamining appropriate alloy systems using: both Ellwood&apos;s method of specimen preparation (casting followed by wrought fabrication) and alternativ&apos;e methods, i.e., diffusion, which might be expected to minimize, or even completely obviate, microporosity. ALLOY PREPARATION 1) Cast Allolys and Aluminum Single Crystals. Al(Ag), Al(Mg;l, and Al(Zn) alloys of various compositions up to 20 at. pet silver, 13.5 at. pet mg, and 30 at. pet Zn were prepared by melting under helium and casting into graphite molds. In the first two systems, the maximum alloying addition was quite close to the limit of solid solubility, but the possibility of transformation to a&apos; during quenching somewhat restricted the suitable Al(Zn) composition range. The alloys were prepared from high-purity aluminum, a lot analysis showing 0.002 wt pet Cu, 0.002 wt pet Fe, and 99.996 wt pet A1 by difference. The silver, magnesium, and zinc were of 99.99+, 99.98+, and 99.998 wt pet respectively. Each composition was analyzed chemically. The as-cast ingots measured 7/16 in. diam and 5 in. length. One in. was removed from the top of the ingot, and the bottom 3 in. was machined to 0.275 in. diam; a point was also machined on the smaller diameter end. The remainder of the original ingot served as a top riser during subsequent remelting and controlled solidification. The machined ingots were now remelted using a Bridgman soft-mold technique to ensure directional solidification and, therefore, a minimum of micro-shrinkage. Alumina powder was used as mold material contained in an alundum thimble, and this crucible was placed in a helium-filled Vycor tube. The assembly was lowered through a suitable temperature gradient at approximately 0.5 in. min-l, and the risered portion of the casting was subsequently removed by sawing.

Jan 1, 1962

By R. L. Bell, T. G. Langdon

A technique was developed- for determining the grain strain, and hence the grain boundary sliding contribution, occurring during the high- temperature creep of a magnesium alloy, from the distortion of a grid photographically printed on the specimen surface. The results were compared with those obtained from measurements of grain shape, both at the surface and interrwlly, and it was concluded that the grain shape technique may substantially underestimate the grain strain and overestimate the sliding contribution due to the tendency for migration to spheroidize the grains. ALTHOUGH a considerable volume of work has been published on the role of grain boundary sliding in high-temperature creep, many of the estimates of Egb (the contribution of grain boundary sliding to the total strain) have been in error due to the use of incorrect formulas or inadequate averaging procedures.&apos; One of the most easy and convenient measurements from which to compute Egb is that of v, the step normal to the surface where a grain boundary is incident. Unfortunately, this parameter is also the one associated with the treatest number of pitfalls. Values of v have been used to calculate Egb from the equation: egb =knrVr [1] where k is a geometrical averaging factor, n is the number of grains per unit length before deformation, v is the average value of v, and the subscript ,r denotes the procedure of averaging along a number of randomly directed lines. If the dependence of sliding on stress were assumed, it would be possible, in principle, to calculate k from the known distribution of angles between boundaries and the surface. This in itself is difficult because the distribution depends on the history of the surface,&apos; but the problem is even further complicated by the fact that v depends on other factors such as the unbalanced pressure from subsurface grains.3 However, the great simplicity of the measurement procedure for v makes it highly desirable that this problem of k determination should be overcome. In the present experiments, this was achieved by the use of an indirect empirical method in which the grain strain, eg, at the surface was determined by the use of a photographically printed grid. The assumption here is that the total strain, et, is simply the sum of that due to grain boundary sliding, egb, and that due to slip or other processes within the grains, eg. SO that: Et = Eg + Egb [2] Thus k is given by: In practice, it is customary to indicate the importance of sliding by expressing it as a percentage of the total creep strain; this quantity is termed y (= 100Egb/Et). The determination of Eg from a printed grid within the grains avoids the difficulties due to boundary migration which should be considered when the grain strain is calculated from measurements of the average grain shape before and after deformation. As first pointed out by Rachinger,4,5 however, this latter technique has the particular advantage that it can also be applied in the interior of a polycrystal. Recently, several workers have produced evidence on a variety of materials6-&apos;&apos; to support the observation, first made by Rachinger on aluminum,4,5 that 7 can be very high, 70 to 100 pct, in the interior, even when the surface value, determined from boundary offsets, is very much lower.10&apos;11 Although there have been criticisms both of the shortcomings of the grain shape technique&apos;&apos; and of the different procedures used to determine y at the surface,&apos; it seemed important to check whether measurements of sliding by grain shape gave values of y which were truly representative of the material. In the present experiments, grain shape measurements were therefore made both at the surface and in the interior for comparison with one another and with the independent measurements of grain strain using the surface grid technique. EXPERIMENTAL TECHNIQUES The material used in this investigation was Magnox AL80, a Mg-0.78 wt pct A1 alloy supplied by Magnesium Elektron Ltd., Manchester. Tensile specimens, about 7 cm in length, were prepared from a 1.27-cm-diam rod, with two parallel longitudinal flat faces each approximately 3 cm in length. The specimens were annealed for 2 hr in an oxygen-free capsule, at temperatures in the range 430° to 540°C, to give varying grain sizes, and, prior to testing, the grain size of each was carefully determined using the linear intercept method. This revealed that the grains were elongated -0.5 to 5 pct in the longitudinal direction. Testing was carried out in Dennison Model T47E machines under constant load at temperatures in the range 150" to 300°C. At temperatures of 200°C and below, tests were conducted in air with the polished flat faces coated with a thin film of silicone oil to prevent oxidation; at higher temperatures, an argon atmosphere was used. To determine v,, each test was interrupted at regular increments of strain and the specimen removed from the machine. At the lower strains, when v, was less than about 1 pm, measurements were taken on a Zeiss Linnik interference microscope;

Jan 1, 1969

By N. A. Gokcen, J. Chipman

Aluminum and oxygen dissolved in liquid iron were brought into equilibrium with pure alumina crucibles and atmospheres of known H2O and H2 contents to study the reactions: 1—Al2O3(s) = 2 Al + 3 0; 2—Al2o3(s) + 3H2(g) = 2Al+ 3H2o(g); and 3—H2(9) +O = H2O(g). Aluminum strongly reduces the activity coefficient of oxygen and similarly oxygen reduces that of aluminum. Values of the product [% All" • [% O]3 are much smaller than those found in previous experimental studies and are of the order of magnitude of the calculated values. ALUMINUM is the strongest deoxidizer commonly A used in steelmaking, but the extent to which it removes dissolved oxygen has been debatable. The relationship between aluminum and oxygen has not been determined reliably not only on account of the usual experimental difficulties at high temperatures but also because of uncertainties in the analyses of very small concentrations of oxygen and aluminum. The earliest experimental attempt of Herty and coworkers&apos; was followed by a more systematic study of Wentrup and Hieber.&apos; These authors added aluminum to liquid iron of high oxygen content in an induction furnace and considered that 10 min was sufficient to remove the deoxidation products from the melt. Parts of the melts thus obtained were poured into a copper mold and analyzed for total aluminum and oxygen (soluble plus insoluble forms), assuming that the insoluble parts were in solution at the temperatures from which samples were taken. It is conceivable that the furnace atmosphere in their experiments, consisting of mainly air at 20 mm Hg pressure, was a serious source of continuous oxidation and therefore that their oxygen concentrations were correspondingly high. Scattering of their data was explained to be well within the maximum inaccuracy of 10°C in the temperature measurements and errors of ±0.002 pct each in the oxygen and total aluminum analyses. Maximum and minimum deoxidation values, i.e., values of the product [% All&apos; . [% O] differed by factors of 10 to 15; mean values of 9x10-11 and 7.5x10-9 ere reported at 1600" and 1700°C, respectively. Hilty and Craftsv determined the solubility of oxygen in liquid iron containing aluminum, using a rotating induction furnace. Pure alumina crucibles used in their experiments contained the liquid iron which in turn acted as a container for slags of varying compositions consisting mainly of Al2O3, Fe2O3, and FeO. The furnace was continuously flushed with argon, and additions of aluminum and Fe2O3 were made in the course of each experimental heat. The inner surfaces of their alumina crucibles were covered with a substance other than pure Al2O3, containing both iron oxide and alumina. Although frequent slag additions can change the composition of slag in the liquid iron cup formed by rotation, the inner surface of the crucible must depend upon the transfer of oxygen or aluminum through the liquid iron for any adjustment in composition. It is not clear that their metal was in equilibrium with the crucible wall, but it is clear that it was not in equilibrium with Al2O3. Their deoxidation product, [% A].]" • [% O]3, varied by a factor of more than 50; the average values of 2.8x10- and 1.0x10-7 were selected for temperatures of 1600" and 1700°C, respectively. Aside from the experimental determinations, attempts have been made to calculate the deoxidation constant for aluminum indirectly from thermody-namic data. Schenck4 combined the thermodynamic data for Al2O3 and dissolved oxygen in liquid iron by assuming an ideal solution. His calculated values are 2.0x10-15 and 3.2x10-13 at 1600" and 1700°C, respectively. Later, Chipman5 attempted to correct for the deviation from ideality and derived an expression which led to deoxidation values of 2.0x10-14 and 1.1x10-12 at 1600" and 1700°C, respectively. The errors in these treatments originate mainly from inaccuracies of thermal data and uncertainties regarding the activity coefficients of dissolved oxygen and aluminum. The purpose of this investigation was to study the equilibria represented in the following reactions in the presence of pure alumina: Al2O3(s) = 2Al + 3O K = aAl2.ao3 [1] Al2O3(s) + 3H2(g) = 2Al + 3H2O(g) H2O K2 = aAl2(H2O/H2 ) [2] H2(g) +O = H2O(g) K3 = 1/ao (H2) [3] The experimental method consisted of melting pure electrolytic iron, usually with an initial charge of aluminum, in pure dense alumina crucibles under a controlled atmosphere of H,O and H2 and holding

Jan 1, 1954

By Rollyn P. Jacobson

THE town of Pacific, in Jefferson County, Mo., is 127 miles west of St. Louis. Since the area lies entirely on the flood plain of a cutoff meander of the Meramac River, it was considered a likely environment for accumulation of commercial quantities of sand and gravel. Excellent transportation facilities are afforded by two major railways to St. Louis, and ample water supply for washing and separation is assured by the proximity of the river. As a large washing and separation plant was planned, the property was evaluated in detail to justify the high initial expenditure. An intensive testing program using both geophysical and drilling methods was designed and carried out. The prospect was surveyed topographically and a 200-ft grid staked on which electrical resistivity depth profiles were observed at 130 points. The Wenner 4-electrode configuration and earth resistivity apparatus" were used. In all but a few cases, the electrode spacing, A, was increased in increments of 11/2 ft to a spread of 30 ft and in increments of 3 ft thereafter. Initial drilling was done with a rig designated as the California Earth Boring Machine, which uses a bucket-shaped bit and produces a hole 3 ft in diam. Because of excessive water conditions and lack of consolidation in the gravel there was considerable loss of hole with this type of equipment. A standard churn drill was employed, therefore, to penetrate to bedrock. Eighteen bucket-drill holes and eight churn-drill holes were drilled at widely scattered locations on the grill. The depth to bedrock and the configuration will not be discussed, as this parameter is not the primary concern. Thickness of overburden overlying the gravel beds or lenses became the important economic criterion of the prospect.** The wide variety and gradational character of the geologic conditions prevailing in this area are illustrated by sample sections on Fig. 2. Depth profiles at stations E-3 and J-7 are very similar in shape and numerical range, but as shown by drilling, they are measures of very different geologic sequences. At 5-7 the gravel is overlain by 15 ft of overburden, but at E-3 bedrock is overlain by about 5 ft of soil and mantle. Stations L-8 and H-18 are representative of areas where gravel lies within 10 ft of surface. In most profiles of this type it was very difficult to locate the resistivity breaks denoting the overburden-gravel interface. In a number of cases, as shown by stations M-4 and H-18, the anomaly produced by the water table or the moisture line often obscured the anomaly due to gravel or was mistaken for it. In any case, the precise determination of depth to gravel was prevented by the gradual transition from sand to sandy gravel to gravel. In spite of these difficulties, errors involved in the interpretation were not greatly out of order. However, results indicated that the prospect was very nearly marginal from an economic point of view, and to justify expenditures for plant facilities a more precise evaluation was undertaken. The most favorable sections of the property were tested with hand augers. The original grid was followed. In all, 46 hand auger holes were drilled to gravel or refusal and the results made available to the writer for further analysis and interpretation. When data for this survey was studied, it immediately became apparent that a very definite correlation existed between the numerical value of the apparent resistivity at some constant depth and the thickness of the overburden. Such a correlation is seldom regarded in interpretation in more than a very qualitative way, except in the various theoretical methods developed by Hummel, Tagg (Ref. 1, pp. 136-139), Roman (Ref. 2, pp. 6-12), Rosenzweig (Ref. 3, pp. 408-417), and Wilcox (Ref. 4, pp. 36-46). Various statistical procedures were used to place this relationship on a quantitative basis. The large amount of drilling information available made such an approach feasible. The thickness of overburden was plotted against the apparent resistivity at a constant depth less than the depth of bedrock for the 65 stations where drilling information was available. A curve of best fit was drawn through these points and the equation of the curve determined. For this relationship the curve was found to be of the form p = b D where p is the apparent resistivity, D the thickness of overburden, and b a constant. The equation is of the power type and plots as a straight line on log-log paper. The statistical validity of this equation was analyzed by computation of a parameter called Pearson&apos;s correlation coefficient for several different depths of measurements, see Ref. 5, pp. 196-241. In all but those measurements taken at relatively shallow depths, the correlation as given by this general equation was found to have a high order of validity on the basis of statistical theory.

Jan 1, 1956