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By John H. Schemel

Large Zircaloy-2 hammer or press forged bars did not exhibit the uniform excellent corrosion resistance to steam normally expected of the alloy in wrought form. Weight gains of coupons cut from forged bars were 40 to 60 mg per sq dm compared to the 28 mg per sq dm obtained on hot rolled sheet and strip. The mechanism of this corrosion and its relation to microstructure is discussed. After these observations, a solution heat treatment followed by rapid cooling was tried on coupons from eight heats of forged bars. The basket-weave structure resulting from the quench did not show agglomeration of intermetallic compounds. These coupons showed uniformly good corrosion resistance with weight gains very close to the 28 mg per sq dm expected of Zircaloy-2 after the 14-day steam test. A large forging was solution heat-treated and tested for structure, mechanical properties, and corrosion resistance. Corrosion resistance was excellent and uniform throughout the section. The normally anisotropic mechanical properties were changed to completely iso-tropic. Strength levels were raised while there was a small loss in ductility at the service temperature. Tempering of the quenched structure below the ß transus did not improve the ductility at the test temperature of 600°F. ZIRCALOY-2 end caps for nuclear fuel elements Zircaloy-2 is an alloy of 1.5 pct Sn, 0.1 pct Fe, 0.1 pct Cr, and 0.05 pct Ni, balance hafnium-free zirconium patented by Westing-house Electric Co. used in pressurized water reactors are machined from large hammer-finished forged bars. The bars forged for this application range from 3 1/2 in. to 7 1/2 in. squares. One of the tests used to evaluate Zircaloy-2 for this service is a 14-day exposure to very high-purity steam at 75oF and 1500 psi pressure. Normally wrought products will exhibit a black lustrous film of zirconium oxide after the test and show a weight gain of approximately 28 mg per sq dm. Coupons representing the forged bars exhibited a wide variety of corrosion results ranging from acceptable black coupons to some covered with white crystals of zirconium oxide that had weight gains of nearly 100 mg per sq dm. One of the most common effects was a white corrosion product that looked like a stain to some observers and the outline of massive metal grains to others. Very careful specimen preparation prior to the corrosion test did not affect the result and metallographic examination did not reveal a structural feature of a size and shape that would correlate with the corrosion product. In addition to the relatively poor corrosion resistance, the forged product was not as ductile as desired. The problem of obtaining uniform and more acceptable properties in these heavy-forged sections seemed to be a function of the microstructure of the metal and, in particular, the distribution of the intermetallic compounds. None of the four alloying elements however are appreciably soluble in a zirconium and are present as compounds which usually appear scattered randomly throughout the structure. Moudryl showed that the distribution of these intermetallic compounds in Zircaloy could be related to a ostringero corrosion failure. Grozier et al. discussed another structural defect that causes a similar corrosion effect. In this case, an elongated gas-void was determined to be the cause. M. L. Picklesimer held in his discussion of the Grozier paper that at least a part of the observed =stringersn were caused by the distribution of the intermetallic compounds. He proposed a

Jan 1, 1962

By John D. Roach

DURING an investigation of the yttrium-hydrogen system aimed at producing solid yttrium hydride specimens containing various amounts of hydrogen, it was observed that yttrium containing approximately 2 wt pct H exhibited a tendency to crack and crumble to a powder on standing in air at room temperature. It was also observed that longer hydriding times, at a given temperature, increased this susceptibility to powdering without an increase in hydrogen content, also that moisture in the air is necessary for the observed effects to occur. Even if cracking did not occur, there was a continual formation of a light gray powder on the as-treated surface of the hydrided yttrium and this reaction continues until the entire hydrided piece has been reduced to a powder. Storing the hydrided specimens in the absence of air or removing the surface either by machining or grinding were effective means of preventing this disintegration of hydrided yttrium. In an attempt to determine the reason for this powdering phenomenon, the surfaces of a number of as-hydrided yttrium specimens were examined by X-ray techniques. In all cases the X-ray pattern obtained showed the major phase to be yttrium hydride (YH2) as would be expected since the specimens contained 2 to 2.2 wt pct H. In some cases a trace of yttrium oxide was observed. There was also a third phase present on the surface of these hydrided specimens which could not immediately be identified. This unknown phase was a face-centered cubic material, NaC1-type structure, with a lattice parameter of 4.855 and a calculated density of 5.914 g per cc. Very slight hand polishing of the surface of the hydrided yttrium specimens completely removed both the unknown phase and the traces of oxide so that only the yttrium hydride pattern remained. Based on the X-ray patterns the quantity of the unknown phase on the surface of the hydrided yttrium appeared to be directly related to the susceptibility of the material to powdering. Work at the Denver Research Institute on the yttrium-nitrogen binary system showed that yttrium nitride (YN) is a face-centered cubic material with a lattice parameter of 4.878A and a density of 5.890 g per cc. They also noted that this compound rapidly disintegrated to a powder on standing in air. The unknown pattern observed in the above specimens corresponds very closely to that of the nitride—fcc structure, 4.885 parameter, and density of 5.914 g per cc. The presence of this thin film of nitride on the surface of the hydrided specimens probably accounts for the observed powder formation and crumbling. The nitride reacts with the water vapor in the air (verified by private communication from Dr. C. Huffine, General Electric Co.) to yield yttrium oxide and ammonia. Ammonia is readily detected when hydrided yttrium specimens were allowed to stand in bottled moist air. The powder formed on the surface of the hydrided specimens was shown by X-ray analysis to be yttrium oxide. This reaction appears to occur primarily at the grain boundaries since discrete particles of yttrium hydride separate from the specimens during this powdering process. The reaction of yttrium nitride with water vapor is believed to be as follows: 2YN + 3H2O - Y203 + 2NH3. Despite the fact that this nitride is present only as an extremely thin surface film, if the above reaction is not prevented by removing this film from the surface either by machining or grinding, the reaction continues until the entire hydrided piece has been reduced to a powder. To account for this continuation of the reaction, it is believed that the following reactionalsooccurs: 2YH2 + 2NH3 -2YN + 5H2. The nitride produced by the latter reaction reacts in turn with water vapor. The reaction therefore becomes autocatalytic and continues until the hydride has been consumed and the entire piece reduced to oxide powder. The amount of nitride required to initiate this reaction is quite small and this nitrogen contamination can occur from a number of sources—hydrogen gas employed, minute leak in the hydriding apparatus or even from degassing of the reaction vessel itself. Longer hydriding times increase the possibility of nitrogen contamination and this is especially true when a dynamic gas system is employed in the hydriding process. The production of stable, solid hydrided yttrium is dependent on the complete absence of nitrogen contamination during processing. If such contamination does occur, powdering of the hydrided product can be prevented by removing the nitride from the surface e.g. grinding or by preventing access of air to the pieces e.g. sealing in wax or plastic. The author wishes to express his appreciation to General Electric Co. for sponsoring this research and for permission to publish the results of work under Subcontract AT-93.

Jan 1, 1962

By D. I. Cameron

A graphical method has been developed and tested for separating the effects of grain boundary and lattice diffusion in polycrystalline materials. The method is based on the assumptions that for unidirectional diffusion from a plane source of radioactive material, the penetration of activity far into the specimen from the source is due solely to grain-boundary effects, and 2) pure grain-boundary penetration is described by a linear plot of log activity vs the perpendicular distance x from the source. The former is based on the fact that at any temperature the grain-boundary diffusion coefficient is always very large relative to the lattice diffusion coefficient; and the latter is based on the derivation of Fisher.1 Using these criteria along with appropriate penetration data (in this case, data for the diffusion of Cb95 in pressed and sintered UO2) one first plots the data as log activity vs x2 and as log activity vs x, as shown by curves 1 and 2, respectively, in Fig. 1. A tangent line to curve 2 for large x (curve 3) is then transferred to the x2 plot as curve 4. The subtraction of curve 4 from curve 1 yields curve 5 which represents only lattice diffusion and may therefore be related to the diffusion coefficient by using the appropriate solution to Fick's second law. It should be noted that the method has inherent inaccuracies for small and large values of x2 and only the subtraction at intermediate values can be used. For the illustrated specimen the calculated diffusion coefficient is 3.4 X 10-11 sq cm per sec at 1445°C while data using a single crystal of UO2 at the same temperature yielded a value of 2.9 x 10-11 sq cm per sec.2 The same method of subtracting grain-boundary diffusion effects to obtain lattice diffusion coefficients has been successfully used to determine self-diffusion coefficients of Th230 in polycrystal- line thoria.

Jan 1, 1962

By Norman Brown

It is suggested that the difference in ease of cross-slip among the fcc metals determines the relative amounts of [111] and [100] wire texture which occur in each metal. Since the ease of cross-slip is controlled by the stacking fault energy, it turns out that the amount of [111] texture should increase as the stacking fault energy increases. Arguments and existing data are presented to support the above suggestion. THE fcc metals generally have a dual texture, [11 and [loo], after wire drawing. As yet no fundament explanation exists concerning the variation of the amounts of each texture among the metals. Barrett&apos; has compiled data which show how the relative amounts of each texture vary from 100 pct [Ill] in the case of aluminum to 25 pct [l1] for silver. In this paper it is suggested that the value of stacking fault energy plays a major part in determining the amount of each type of texture. The double texture has its origin in the classical rotation of a single crystal under tension. An equilibrium position of the crystal is one in which three or more equivalent slip systems are operating simu taneously. Most crystals, initially, tend to rotate toward the [1ll] or the [l00] pole depending upon its initial orientation. This single-crystal behavior is essentially the same as the rotational behavior of the polycrystalline metal as worked out by Taylor.2 The next point to consider is whether the [Ill] or [100] orientation is more stable. There have been many discussions of this question3&apos;" which, in general, have lead to the conclusion that 11111 is most stable. For example, Pickus and Mathewson 4 suggested that a [Ill] texture produces more effective flow becake the [ 110] slip direction makes a smaller angle with the [111] than with the [loo]. A crude statistical argument will be presented which again favors the (1111 orientation. In order to maintain a pure [loo] wire texure, slip must occur in equal proportions in four of the six possible <110>slip directions. In order to maintain a pure [Ill] texture, slip must occur in equal proportions in only three of the six <110>directions. Since the <110> directions are the only slip directions in a fcc metal and if it is assumed that each of these six directions is equally probable, then the relative probability of a [1ll] texture vs a [l00] texture may be calculated. The statistical weight of a particular texture is the multiplicity of a texture times the probability of obtaining any one. The statistical weight for [Ill] is

Jan 1, 1962

By A. Szirmae, Hsun Hu

The early stages of recrystallization in a 70 pct cold-rolled Si-Fe crystal of the (110) (0011) orientation were studied with a Siemens electron microscope. Orientation studies based on electron-diffractzotz. patterns confirm the results of previous texture analysis. The driving energy for recrystallizatior and the critical radius for growth were calculated from the dislocation energy and the energy of the subgrain bourzdaries, and it was found consistent with the observed size of the recrystallized grains. The recrystallization characteristics of crystals with different initial orientations are discussed. The recrystallization of cold-rolled (110)[001] crystals of Si-Fe has been widely studied by various investigators.1-4 Their results on both deformation and annealing textures are in good agreement. The rolling texture after 70 pct reduction consists mainly of two crystallographically equivalent (111) [112] type textures and a minor component of the (100) [011] type. The latter is derived from the deformation twins, or Neumann bands, which are formed during the early stages of deformation and later rotate to the (100) [011] orientation upon further rolling reduction. Between the two main (111) [112] type textures, there is some orientation spread, because of which very low intensity areas appear in the pole figure. If these very low intensity areas are considered to be a very weak component in the texture, then a (110) [ 001 ] orientation may be assigned to them. When this rolled crystal is annealed at a sufficiently high temperature for recrystallization, the texture returns to a simple (110) [001]. The purpose of the present investigation was primarily to seek a better understanding of the recrystallization process by using the electron transmission technique. The (110) [0011 type of crystal was selected because orientation data for it are well known from previous studies with conventional techniques. Direct observations on the recrystallization of such a crystal have also been made by using a hot-stage inside the electron microscope, and the results will be reported in another paper. MATERIAL AND METHOD A single-crystal strip of the (110) [001] orientation was prepared from a commercial grade 3 pct Si-Fe alloy by the strain-anneal technique.= The strip was approximately 0.014 in. thick, and was rolled 70 pct at room temperature to a thickness of 0.004 in. Specimens were cut from the rolled strip and were annealed in a purified hydrogen or argon atmosphere. They were then electrolytically polished in a chromic-acetic acid solution to very thin foils. Best results were found by polishing first between two narrowly spaced flat cathodes with the specimen edges coated with acid-resisting paint, followed by polishing between two pointed electrodes until a hole appeared in the center as described by Bollmann.6 It was found that a thin transparent film always formed along the thin edges of the polished specimen. This film was then removed by rinsing the specimen very briefly in a solution of alcohol with a few drops of HF or HCl. RESULTS AND DISCUSSION 1) The Deformed Crystal. From the electron-diffraction patterns taken at various areas of an as-rolled specimen, the texture components as deduced - from ordinary pole-figure analysis were confirmed. Over most of the areas where orientation was examined, a (111) pattern with a [112] direction parallel to the rolling direction was obtained. This corresponds to the main deformation texture of the (111) [112] type. In a few areas the diffraction pattern was (100) [Oil], corresponding to the minor-texture component derived from the Neumann bands. The (110) [001] orientation, which corresponds to the very weak intensity area in the pole figure, was found infrequently. A typical example of the deformed matrix having the (111) type main texture is shown in Fig. 1, where (a) is the microstructure and (b) is the diffraction pattern taken from that area. It was also frequently observed that in other areas more or less continuous rings of weaker intensity were superimposed on the simple (111) diffraction pattern, suggesting the presence of a wide range of additional orientations. Other evidence indicated that the recrystallization characteristics are different in these two different types of areas. The hot-stage observations which provide this evidence will be discussed in another paper. AS shown in Fig. l(a), numerous dislocation-free areas of very small size are embedded in the "clouds" of high-dislocation density. This indicates that the deformation of a single crystal, even after a rolling reduction of 70 pct, is far from uniform on a micro-

Jan 1, 1962

By John T. Norton, Matthew J. Donachie

Residual lattice strai?zs were produced in 2024 aluminum and ingot iron by uniaxial tensile deformation. These strains were rneasured on the original surface and ulith depth below the surface. The strains conformed approximately to those from a macroscopic stress distribution but they were not truly macroscopic in nature. The exact mechanism which apparently causes the coherently difi9,acting region of each grain to behave as if macroscopically stressed was not determined. MACROSCOPIC stresses in metals produce strains in the lattice which result in X-ray line broadening and line displacements. The latter effect can be utilized in a technique for determining stresses in metals as first shown by Lester and born.&apos; Subsequent advances in technique have enabled the X-ray method of stress measurement to be satisfactorily applied to many problems involving residual stresses of a macroscopic nature, such as those due to welding, grinding, shot-peening, and so forth. In the case of stresses such as those described above, the correlation of X-ray- and mechanically determined data has been generally good. However, plastically extended polycrystalline metals have sometimes been reported2 to show line displacements upon release of the applied tensile load, yet the nature or origin of the residual lattice strains, rls, producing these displacements has never been clear. As will be pointed out, this lack of clarity regarding the macroscopic or microscopic nature and origin of these stresses casts doubt on the validity of results achieved by the commonly accepted techniques of X-ray stress measurement. This anomalous behavior requires clarification to remove the doubts concerning X-ray stress measurement. The present paper is the result of an investigation of the interesting behavior of such plastically extended polycrystalline metal bodies. The studies were originated to carry out the following tasks: 1) Observe whether a residual lattice strain is produced as a result of plastic extension and show whether any residual lattice strains produced can be related to the usual concept of a macrostress. 2) Examine the origin of any residual lattice strains observed. 3) Consider the implications or consequences of the existence of such residual lattice strains on the problem of X-ray stress measurement. THEORY 1) Lattice Strains. The theoretical developments necessary for the treatment of lattice strains and their relation to stresses follow from the classical theory of elasticity and have been adequately covered by arrett. For an isotropic solid under homogeneous deformation, it can be shown that, for uniaxial stresses where Dl is the macrostress acting in the longitudinal direction; E$L is the lattice strain in the plane defined by the surface normal and the longitudinal direction at an angle, , from the surface normal; ET is the similar strain in the transverse plane; E is Young&apos;s modulus; and v is Poisson&apos;s ratio. Eq. [2] is independent of angle + and Eq. [I] is a linear function of sin2, see Fig. 1, and can be solved analytically for DL if E and u are known and EL is measured. Thus, a uniaxial macrostress will be indicated by a linear E,L vs sinZ plot and a

Jan 1, 1962

By O. J. Malacarne, D. G. Millenbruch

The use of a series of thickeners for washing of the slime fraction of a leached ore is not uncommon in the uranium industry; however, few ore processing mills have used a thickener circuit for washing leached total ore. The common practice is to wash the sand fraction in classifiers and the slime fraction only in thickeners. At the Uravan mill of Union Carbide Nuclear Co., a total ore acid leach is employed to extract uranium values from sandstone ores. These leached ores are then washed at a nominal rate of from 1000 to 1300 tpd in a series of washing thickeners. A typical screen analysis of the ore being washed in these thickeners is: 25 pct, -200 mesh; 3 pct, +35 mesh; and about 1 pct, +14 mesh. The amount of slimes (-200 mesh) will vary from 20 to 30 pct as the mill receives ore from 150 different mines. The washing liquor is acidic, from a pH of about 2 in the first thickener to 0.6 pH in the last thickener and, of course, all acid duty equipment must be used. The Uravan mill of Union Carbide Nuclear Co. is located in Montrose County, Colo. and is physically located on a canyon wall along the San Miguel River. The thickeners referred to in this paper are located on top of the mesa above the canyon. For purposes of identification, these thickeners are numbered 1 through 8 from south to north. GENERAL DESCRIPTION OF CIRCUIT The circuit utilized consists of eight wooden fir tanks, 60-ft diam by 12-ft deep, set in a line and staggered in elevation by approximately 3 ft. The washing water flows through the thickeners by gravity, while the ore pulp is pumped uphill from thickener to thickener. Adequate piping and pumping capacity are available so that any of the thickeners can be bypassed in the circuit. All the controls for the

Jan 1, 1962

By R. M. Rose, D. P. Ferriss, J. Wulff

The effect of orientation on the stresses, nctivation energies, and activation volumes for yielding and plastic flow of tungsten single crystals was investigated. Tensile tests showed the proportional limit to be a function of orientation: crystals whose tensile axes were near the [I10} direction were roughly three times as strong as [loo] crystals. The [ 1101 crystals showed low strain hardening and displayed yield phenomena, whereas the other orientations yielded smoothly and showed considerable strain hardening. The fracture mode was cleavage, except for crystals near the [1101 , many of which gave "chisel" fractures at 300°and 373°K. The activation energy for yielding was approximately one- half an electron; volt at all orientations, and the volume of activation was (12 to 14)b3, except near the [1101, where it was 7b3. Activation volumes generally increased after yielding. The most common theoretical models for yielding and strain hardening of bcc metals were. found to be insufficient to the intepretation of the observations here in. An explanation is proposed, based on the dislocation reaction dislocation networks and jogs, md jogs formed during plus tic flow. PRECLSE knowledge of the Drocesses involved in the yielding and plastic flow of the refractory metals is essential to the formulation of models for their flow and fracture. Despite this need, the single -crystal investigations, especially of tungsten, have been sparse. Slip occurs at low temperature, according to schadler,i in <111> directions on {110) planes; as the temperature rises to room tempera-

Jan 1, 1962

By R. A. Vandermeer, Paul Gordon

On the basis of a unified concept, theoretical erPressions for grain boundary migration in recrys-tallization are derzved for impurity-controlled and impurity-independent migration. The expression in the former case is analogous to that Previously derived by Lucke and Detert, and in the latter is shown to be equivalent to that usually obtained on the basis of absolute reaction rate theory. The equations are tested with quantitative experimental data for boundary migration obtained for the recrystallization of poly crystalline zone-refined alumimnz and for binary "alloys" of this aluminum with 0.00021, 0.00043, 0.0017, 0.0034, 0.0068, 0.0124, and 0.0256 at. pct Cu, respectively. All the essential characteristics of the e@erimentally determined boundary migration rates check both qualitatively ard quantitatively with the predictions of the theoretical equations. THE rates of transformations are customarily analyzed phenomenologically in terms of the two component rates—N, the rate of nucleation and, G, the rate of growth of the nuclei. The scientific aim of both theory and experiment is to describe the fundamental atomic phemmena involved in these two component processes with the hope that parameters calculated from theoretical equations will check those found experimentally. In solid state transformations, the theoretical and experimental problems are both generally of almost prohibitive complexity, for in addition to changes in composition and in such properties as density which may accompany transformations in amorphous, nonrigid materials, transformations in crystalline substances also involve structural changes, crystal reorientations, and the development of stresses. In studying such transformations it thus becomes; highly desirable, if not essential, to focus on a transformation and a set of conditions which minimize the number of active variables. This principle has been applied with considerable success by Cohen and his associates&apos; in their evaluation of nucleation theories using the martensite transformation as the basis of study. A similar possibility exists for the evaluation of growth theories by the use of recrystallization after cold-deforming. If an unalloyed metal is employed as the subject of investigation, the recrystallization transformation involves basically only a change in strain-conditions and orientations. In spite of this possible simplilfication, however, until recently little quantitative success has attended attempts to correlate recrystal1ization parameters measured experimentally with those calculated theoretically. It seems highly probable that this lack of success may be attributed, both in the experimental and theoretical treatments, to one or more of the following factors: a) conditions have usually been studied under which apparently* both nucleation and growth are active;

Jan 1, 1962

By S. J. Matas, R. F. Hehemann

The existence of two distinct forms of bainite—upper and lower bainite—in hypoeutectoid steels is confirmed by a systematic study of the structure of the product resulting from this mode of austenite decomposition. The transition between these two forms occurs at about 650° F regardless of the alloy content of the steel and their structural differences can be interpreted in terms of the kinetics of carbide precipitation from supersaturated ferrite. In the past few years, a renewed interest has been displayed in the kinetics and mechanism of the bainite reaction in steels. Several rather divergent models for the transformation mechanism have evolved from these studies,&apos;-&apos; however, it is difficult to evaluate these models critically on the basis of the existing experimental data. In particular, a more detailed knowledge of the structure of bainite should be helpful in providing a framework for the construction of an appropriate model. Metallographic studies7-l4 have led to a recognition of at least two distinct forms of bainite—frequently termed upper and lower bainite. Although the morphology of bainite changes with reaction tem- perature, there appears to be a relatively sharp transition between the two forms. This occurs in a narrow temperature range near 650° F. Transformation at temperatures below about 650° F results in the presence within the bainite of small plates of carbides oriented at an angle of 60 deg with respect to the direction of growth of the plate, while at higher temperatures carbides are oriented parallel to the growth direction. There is no generally accepted view regarding the significance of this structural transition. Some authors feel that carbides precipitate from austenite at all reaction temperatures1&apos; while others claim, at least for low-temperature bainite, that carbides precipitate from supersaturated ferrite.14.15 It was recognized many years ago that the nature of the carbide in bainite depends on the reaction temperature. The carbide hase in upper bainite is unmistakenly cementite.16-19 The exact nature of the carbide in low-temperature bainite is less certain. Magnetic measurements of lower bainite reveal no cementite Curie point21&apos;22 and dilatometric studiesz0 produce total expansions which are larger than those predicted on the basis of a ferrite-plus cementite structure. These effects have been attributed to the

Jan 1, 1962

By E. T. Turkdogan

The activities of SiO2, FeO, and Fe2O3 are calculated from previous experimental data on the activity of oxygen in Fe-Si-O melts at 1550°C. Using the oxide-activity data, the free energy of formation of fayalite from its oxides is evaluated for 1550°C. A number of investigators1-4 contributed to the study of the state of oxidation of iron in SiO,-FeO-Fe,O3 melts and the phase equilibria in the system Fe-Si-O. In a more detailed study, Schuhmann and Ensio5 and Michal and Schuhmann% easured the state of equilibrium in the SiO,-FeO-Fe,O3 melts saturated with y-iron or silica or both under low-oxygen potentials and within the temperature range 1250" to 1350°C. Similar measurements were also made by Turkdogan and Bills7,&apos; over wide ranges of composition and oxygen potentials at 1550"C. Using the experimental data on the oxygen activities in the ternary system, Schuhmann&apos; calculated the activities of silica and ferrous oxide in Si0,-FeO-Fe2O3 melts for 1350°C. Adequate knowledge on the activities of the constituent oxides of melts is essential in the study of reaction-equilibria and reaction-kinetics in oxide-melts. With this in view, the activities of oxides in SiO2-FeO-Fe2O3 melts at 1550°C are computed using the experimental data of Turkdogan and Bills7&apos;8 on the oxygen activities in these melts.

Jan 1, 1962

By J. W. Downey, M. V. Nevitt

MUELLER and Knott&apos; have reported that Ti2Cu has the Si2Mo-type (Cllb) structure. The lattice parameters of Ti2Cu and the positions of the titanium and copper atoms are given by them as follows: ao = 2.944A; co = 10.786A 6 atoms per unit cell: 2 Cu (a) 000; 1/2: 1/2, 1/2 4 Ti (e) 002; 1/2, 1/2, 1/2 + z 00 -2 ; 1/2. 1/2. 1/2- z where z = 0.341 We have found eight other binary compounds which appear to be isostructural with Ti2Cu. All of them involve the combination of a titanium group element with a copper group element or a titanium group element with palladium. The compounds and their lattice parameters are given in Table I. The alloy samples were prepared by arc melting metals having a purity of 99.9 pct or better. They were homogenized for 72 hr at 900°C in evacuated capsules and quenched in tap water. Filings were prepared, and these were reannealed for 4 hr at 700°C, also in evacuated tubes. The lattice parameters were determined by a least squares Bnalysis of the back reflection lines of patterns made with cobalt radiation. It was not possible to make a precise determination of the lattice parameters of Zr2Au because the filings underwent rapid oxidation at room temperature. The evidence supporting the large tetragonal cell containing 6 atoms involves the presence of the reflections 002, 101, 004, 112, 114, 202, and other reflections with higher indices for which I = 3n. Three or more reflections corresponding to these indices, which cannot be indexed on the basis of a small body-centered tetragonal cell containing 2 atoms, are observed in the patterns of all of the compounds listed in Table I. They are strongest and most numerous when the components have large differences in their atomic scattering factors, as is the case in Ti2Pd, Zr2Cu, and Hf2Cu. The values of the z parameter should be regarded as approximate They were selected on the basis of the best agreement between the observed intensities of two pairs of closely spaced powder pattern lines (004): (112) and (114): (202) and the corresponding intensities calculated for several values of z. An ordering scheme was assumed in which titanium, zirconium, or hafnium atoms occupy the titanium positions of Ti2Cu, and copper, silver, palladium, or gold atoms occupy the copper positions. Calculated and observed intensities of the aforementioned lines and the other lines of the patterns are in satisfactory agreement, but a refinement of the z parameters and a final confirmation of the ordering arrangement must await a more detailed study. It is interesting to note that in transition metal systems at A2B stoichiometry the Si2Mo-type structure competes for stability with two other fre-

Jan 1, 1962

By W. A. Griffith

The fundamental principles and modern techniques of experimental planning and data analysis, applicable to any type of research, are particularly important in flotation experimentation. Since they constitute the modern science of experimentation, they should be among the working tools of any scientist, research engineer, or plant operator engaged in flotation investigates. This chapter is a review of these principles and techniques. Equipment and procedures for the actual conduct of experiments will not be discussed here since these subjects are well covered elsewhere in this volume. Neither will any attempt be made to impart a working knowledge of statistical methods of data analysis since this would be impossible in the space allotted, and many excellent texts are available to the diligent inestigator.1-4 The objective here is simply to interest the reader in the application of statistical techniques to flotation experimentation by illustrating their utility in situations frequently encountered, and to point out the principles of experimental planning necessary for their proper use. Any conscientious metallurgist engaged in flotation experimentation or operations is well aware of the inherent complexity of the flotation process, and of the often frustrating difficulties this introduces into experimentation. The raw materials normally treated by the process are complex both physi- cally and chemically, and often highly variable even when from the same source. The flotation process itself is characterized by a very large number of potentially important process variables. Many of these are beyond the con- trol of the metallurgist, and some cannot even be measured quantitatively with available instruments. Those which can be measured and controlled with reasonable precision often produce effects which are intricately interrelated. Not only are the variables many, but the physical and chemical mechanisms by which they function are imperfectly under stood. To compound the difficulty, experimental techniques are relatively crude. Controls are not very precise, and the human factor looms large in most flotation experiments. These situations lead inevitably to experimental data of a relatively low degree of precision or reproducibility. Some are inclined to think that these conditions are unique to flotation experimentation. They are not. The experimental problems met by the agronomist, the biologist, the social scientist, and others are equally complex. Investigators in these fields pioneered in the development of methods for handling just such situations by proper experimental planning and the application of statistical methods in the analysis of data. Their pioneering work has grown into a well established modern science of experimentation which has spread into every field of science. This science is based upon statistical

Jan 1, 1962

By Leonard P. Colvin

Like all successful American enterprises, the mining industry is constantly trying to increase production, lower costs and improve working conditions. Companies are, of course, intensely interested in new equipment to help them gain these important ends, and one recent development-the mechanical raise climber--contributes to all three goals. Properly used, it increases production, cuts costs and has a number of important safety aspects all of which are the subject of this article.

Jan 1, 1962

By S. R. B. Cooke, Y. S. Kim, I. Iwasaki

lron oxides or the gangue minerals of iron ores can be made to float, depending upon the choice of collector. The selectivity of the separation is controlled by the accompanying chemical and operating conditions. In this report the findings on the general flotation characteristics of magnetite are summarized and the results are compared with those obtained for other iron oxides. Depending upon the choice of collector, either the iron oxides or the gangue minerals of iron ores can be made to float, the selectivity of the separation being controlled by the accompanying chemical and operating conditions. The mechanism by which a collector exerts preferential affinity for either group of minerals has been a subject of extended discussion. Previous investigations on the electrokinetic properties and flotation characteristics of hematite,&apos; goethite,2 and quartz3 have demonstrated the electrical nature of the interaction of the collector with these oxide surfaces; anionic collectors are effective on positively charged surfaces and cationic collectors on negatively charged surfaces. Thus, from the differences in the electrokinetic properties of the above-named oxides, a theoretical basis has been provided for their separation by some typical collectors. Examination of the results reported for hematite and goethite shows that their electrokinetic properties and flotation characteristics are remarkably similar. It is of considerable interest, therefore, to examine similar information for magnetite, another common iron oxide, in order to consolidate the flotation characteristics of the three principal minerals of oxide iron ores. Such information is practically significant in the up-grading of both natural and artificial mag- netite produced from taconite, and in the treatment of partially oxidized magnetite ores. Information on maghemite and lepidocrocite, polymorphs of hematite, and goethite, respectively, is also of some theoretical interest in ascertaining the effects of crystal structure and of hydration in the iron oxide group. This article reports the findings on the general flotation characttxistics of magnetite, and compares the results with those obtained for other iron oxides. Experimentally, tlhe surface properties of magnetite were investigated by electrophoresis, and by measurement of the aclsorption of some typical flotation collectors. Its flotation behavior was tested by contact angle measurements and by simple flotation tests using a modified Hallimond tube. The basic information thus gathered was shown to be directly applicable to the interpretation of the results of batch flotation tests made on an artificial mixture of magnetite and quartz. EXPERIMENTAL MATERIALS Magnetite: Magnetite concentrate from Port Henry, N. Y., was further purified by fine crushing and magnetic separaiion, and was used throughout this investigation. For flotation tests the 150/200 mesh fraction was iso1ated and was cleaned by leaching briefly with warn 0.1 N HC1 followed by repeated washing with demineralized water. The final sample analyzed 71.71 pct Fe, 22.37 pct Fe" and 0.47 pct insoluble, and was stored in demineralized water. For e1ectrophoresis and adsorption measurements, the —400 mesh fraction of the magnetite concentrate was ground dry in a pebble mill. The surface area of the ground sample, as determined by the gas permeability method, was 70,000 sq cm per g. Since artificial magnetite has been reported to possess somewhat different physical properties than those of natural magnetite, it also was briefly examined. Preliminary flotation tests on a sample of artificial magnelite, prepared by reducing Brazilian hematite in a C0/CO2 mixture and analyzing 71.94 pct Fe and 23.78 pct Fe&apos;&apos;, gave, however, nearly identical results with those using natural magnetite. It was concluded that artificial magnetite behaves similarly to natural magnetite. Samples which had been magnetically separated showed a tendency to cluster together due to residual

Jan 1, 1962

By J. M. Morkowitr

A. Sawatzky (Atomic Energy of Canada, Ltd.)—The detailed criticism by Markowitz of my simple treatment of the thermal diffusion of hydrogen in Zircaloy-2 indicates that my paper was not as lucidly written as it could have been. I would therefore like to reiterate several of the main points of my proposed mechanism and describe in more detail some of the features only implied in the original paper. The distribution equation derived in my paper was stated to hold only for the case where the volume taken up by the hydride was small compared to the volume taken up by the solid solution phase, subsequent work, mentioned below, having shown it to be out by only a few percent up to a hydrogen concentration of about 3000 ppm. Of course, hydrogen in the two-phase region alone is not conserved in my treatment as pointed out by Markowitz. On the contrary, one of the important features of my proposed mechanism is that in the presence of a temperature gradient a two-phase region cannot exist over the whole specimen. For example, if the specimen is entirely a + 6 initially, then on application of a temperature gradient, a single phase (a) region at the hot surface develops from time t = 0 onwards. As mentioned in my original paper, the interface between the a and a+d regions moves toward the colder surface of the specimen with a discontinuity in hydrogen concen- tration developing at the interface and increasing with time. This interface moves at such a rate that hydrogen in the specimen as a whole is conserved. It must be pointed out that my distribution equation (Eq. [5] in Markowitz&apos;s paper) holds only for linear geometry. It is easy to show that for the cylindrical geometry of Markowitz the assumptions used in my treatment lead to

Jan 1, 1962

By R. G. Ward, John Henderson. R. G. Hudson, G. Derge

Densities of melts of the iron oxide-silica system in contact with solid iron have been measured by the maximum hubble pressure method in the composition range O to 37 wt pct SiOz and the temperature range 1255 to 1410C. The constitution of the melts is discussed and it is postulated that the structure changes from a dislribution of iron ions in an oxygen ion network at pure "FeO" to a distribution. of iron ions in a network of silicate tetrahedra at the orthosilicate composition. JOHN HENDERSON, Junior Member AIME, was formerly with the Metals Research Loborotory, Carnegie Institute of Technology, Pittsburgh, Pa., on leave from Broken Hill Proprietary Co., Ltd., Research Division, Shortland, Australia. R. G. HUDSON, formerly with Metals Research Laboratory, is now with the John Jay Hopkins Loborotory for Pure and Applied Science, General Atomic Division, General Dynamics Corp., LaJolla, Calif. R. G. WARD, was formerly with the Department of Metal lurgical Engineering, Carnegie lnstitute of Technology, while on leave from the Department of Metallurgy, University of Sheffield, England. G. DERGE, Member AIME, is Jones and Laughlin Professor of Metallurgical Engineering, Carnegie lnstitute of Technology. Manuscript submitted January 19, 1961. ISD The system iron oxide-silica is an important one metallurgically because it forms the basis of several complex slag systems in use for industrial smelting and refining processes. In recent years considerable work has been done on liquids of this system but there are still many points of difference among workers using different experimental techniques and theoretical approaches. Phase equilibria/"3 activity,4-6 electrical conductivity,&apos; current efficiency,&apos; transference number,8 viscosity,9 surface tension,&apos;&apos; and density" measurements have all contributed to an understanding of the problem. Measurement of density is one procedure which is directly indicative of liquid structure since any deviation from ideality must be a result of structural interactions. Liquids of the iron oxide-silica system are of special interest because this is one of the few metal oxide-silica systems on which measurements can be carried out conveniently over the entire composition range from pure oxide to silica saturation. This includes the range of high basicity which has received relatively little attention in other systems. Although one investigation of density in this system has previously been undertaken," the results seem of sufficient importance to warrant the independent redeter-mination reported here.

Jan 1, 1962

By C. N. Garman

Homestake-New Mexico Partners operate a 750-tpd carbonate leach uranium concentrate mill near Grants, N.M. The highly mineralized water available as process water leaves much to be desired. The 628 ppm as CaCO 3 makes the use of raw water very troublesome in pipes and on filter cloths. However, the residual sodium carbonate in the final filter cake going to tails makes an ideal softening agent. To take advantage of this fact, all makeup water used in the mill is first used as tailing slurry dilution water and comes to the mill from the tailings pond. The 5-acre tailings pond serves as a thickener and 100 to 150 gpm of nearly clear solution is decanted to a pump to be returned to the mill. Since this tailings water has small quantities of uranium in the solution an ion exchange scavenger unit was installed to remove as much uranium as possible. The ion exchange raffinate is then used as final filter wash ahead of the tailings slurrying step. In spite of the large settling area this return water is not clean enough for ion exchange feed. The solids present are very fine and composed of approximately 15 pct (by weight) burnable carbonaceous material common to the sandstone uranium ores in the area, 40 pct SiOz plus 45 pct CaC03. Laboratory work showed that this material responds very well to flotation. Before deciding to use flotation, various clarifying systems such as pressure leaf filters, sand filters, and continuous vacuum pre-coat filters, were considered. Each of these could have solved the problem but with much more operating labor, more reagents and greater installation costs than the flotation step. About 100 to 150 gpm of fouled water is fed to two 66-in. Fagergren cells, in series. Reagents used at the beginning were Arquad 2HT75 and Arquad C50, at the rate of about 1% lb per 8-hr shift, or about 0.0053 lb each per ton of ore. This did not completely remove the solids but does an acceptable job. Approximately 75 pct of the slimes are a size that can be caught on a 41-Whatman Paper are removed. Removal of these slimes also allows much better settling of the coarse nonfloatable material. Advantage is also taken of this fact in a small settling tank ahead of precipitation. Removal of this amount of the slimes makes the ion t:xchange feasible. PREGNANT SOLUTION CIRCUIT The carbonate? leach-caustic precipitation method of uranium concertration does not provide for any process purification step ahead of precipitation. Therefore, any fine solids getting into the pregnant solution through the filter cloth show up in the final concentrate. This, of course, lowers the grade, and, at times, the slimy nature of these very fine solids rendered final filtration of the concentrate difficult if not impossible At Homestake-New Mexico Partners a 75-ft thickener was available for gravity clarification of 100 to 120 gpm of this pregnant solution. However this did not sufficiently remove the slimes. Laboratory investigation of the whole range of flocculants that were suggested by literature, salesmen, and friends failed to turn up anything of consequence. A continuous vacuum pre-coat filter would do the job and was investigated. The capital cost and the operating labor and materials made this a last chance choice. Following work done in the metallurgical laboratory on the tailings return water, it was found that some changes in the reagent strengths and combinations made a very definite decrease in the solids in the pregnant solution. Concentrate grade improved about 5 pct anti the final product after drying had an appreciably greater bulk density. Compared to a cost of about 2.2e per ton for pre-coat filter opelation for cleaning just one circuit, flotation costs less than 1.0 per ton of ore for cleaning two circuits. While a pre-coat filter would do a more thorough job, the flotation does all that is required for either circuit. Gravity causes the froth produced to run back into the leach circuit. This does not appear to result in a build-up of objectionable slime. No extra manpower is required; the operators in the separate areas can observe the operation of the cells and mix the small quantities of reagents as needed. Normally the 66-in. Fagergren cell requires 15 hp per cell, but this very dilute slurry needs only 10 hp for both cells. Originally, a combination of the two Arquads mentioned previously served as frothers and promoters. As further testing

Jan 1, 1962

By E. H. Rennhack

Phase equilibria of the zinc-rich portion of the Zn-Fe-A1 system containing up to 20.0 wt pct Fe and Al have been investigated at 600°C (1112°F), 450°C (842°F), and room temperature by metallographic and X-ray diffraction techniques. The phase relationships were found to involve only those phases present in the three binary systems. THE presence of small quantities of aluminum (approx. 0.2 wt pct*) in zinc galvanizing baths is known to suppress the formation of Zn-Fe alloy layers within the coating.&apos; As part of an extended investigation of this suppression effect and the alloy reactions involved, the zinc-rich corner of the Zn-Fe-A1 equilibrium system containing up to 20.0 pct Fe and Al was determined at 600°C (1112°F), 450° F (842° F), and room temperature. The present paper reports the findings of this study. The constitution of the Zn-Fe system has been reported by Raynor2 based mainly on the work of Schramm3-3 and Truesdale et a1.6 The solid solubility of iron in zinc is extremely small and lies between 0.0009 and 0.0028 pct in the range 150° to 400°C (302°to752°F). Within the temperature and composition range of interest, a eutectic reaction involving nearly pure zinc, liquid = Zn+FeZn13, is observed at about 419°C (786° F) and 0.018 pct Fe along with a peritectic reaction, FeZn7+ liquid e FeZn13, at 530°C (986° F) and 6.2 pct Fe. The latter reaction is sluggish due to the large proportipn of solid phase involved in the transformation. Halla et al.,7 identified the compound FeZn13 as monoclinic with a = 13.68, b = 7.63, c = 5.07, and B = 128°44&apos;. The structure of FeZn7 was reported by Bablik, et al.,8 to be of hexagonal symmetry, belonging to either the C6v = C6/m mc or D46h = C6/mc space group. Divensions of the unit cell are a = 12.81A and c = 57.6a. The Zn-A1 diagram as composed by Raynor9 and later Gebhardt10 is characterized by a eutectic decomposition, liquid 382°C (720°F) and 95.0 pct Zn and a eutectoid decomposition, at 275° (527°F) and 78.0 pct Zn. The eutectoid reaction cannot be suppressed permanently by quenching. Above 275° (527° F), a and a&apos; co-exist in a closed miscibility gap between 31.6 and 78.0 pct Zn. Both phases are fcc and have nearly the same lattice parameter. The maximum solubility of aluminum in zinc (B) is approximately 1.0 pct at the eutectic temperature. PROCEDURE Materials. The experimental alloys were prepared from both massive and powdered material. Cast alloys were composed from three zinc-base master alloys containing 8.0 pct Fe, 16.0 pct Fe, and 50.0 pct Al which were made from C.P. zinc, Armco iron, and

Jan 1, 1962

By H. I. Aaronson, S. Toney

When the component grains of .ferritic hicrystals of an Fe-1.55 pct Si alloy are disoriented through an angle "6 " about a conzmon [ll0] axis, the tendency for preferential growth of austenite crystals along the grain boundary during transformation at elevated temperatures is small when 11 deg, but increases rapidly at larger angles. This type of orientation-dependence indicates that grain boundary diffdsion promotes preferential growth along large-angle boundaries. Morphological differences between austenite crystals formed at small-angle [1101 and [loo] boundaries suggest that precipitate morphology can be dependent on the dislocation structure of the boundary. ThE morphology of precipitate crystals nucleated at a grain boundary can be significantly affected by the structure of the boundary.&apos; The limited amount of experimental evidence available in the literature indicates that the morphological effects of boundaries made up of arrays of dislocations, such as subbound-aries and small-angle grain boundaries, are different from those of boundaries having essentially disordered structures, i.e., large-angle grain boundaries. On the basis of indirect evidence, it has been concluded that large-angle grain boundaries give rise to the formation of grain boundary allotriomorphs (crystals which nucleate at grain boundaries, and grow preferentially and more or less smoothly along them)2 in the proeutectoid ferrite and the proeutec-toid cementite reactions in plain-carbon steels, and apparently also in many non-ferrous alloys.&apos; At small-angle grain boundaries in a plain carbon steel, on the other hand, ferrite crystals were found to take the form of primary side plates. Similarly, Guinie, loys. Primary sideplates formed at a subboundary with a constant orientation tend to be parallel to only one, or occasionally two matrix habit planes, and a marked change in the orientation of the boundary is accompanied by a change in the habit plane. Previous studies on the morphological effects of grain boundary structure were performed on poly-crystalline aggregates. Information on the disorien-tation of the pairs of grains forming the boundaries at which the various morphologies appeared in these specimens was largely either qualitative or semi-quantitative. Precipitate morphologies accordingly could not be accurately and systematically correlated with grain boundary structure, and thus theories which have been proposed for the various morphological effects could not be satisfactorily tested. This investigation was undertaken in an attempt to remedy these deficiencies by studying the morphological effects of grain boundary structure with a method in which the boundaries are formed by matrix grains whose disorientations are known and controlled with reasonable accuracy. EXPERIMENTAL PROCEDURE The crystallographic requirements of this study were fulfilled by means of oriented bicrystals of silicon-iron. Disorientation of the component ferrite crystals was carried out about common, major crystallographic axes through angles ranging from 1/2 to 44 deg. The silicon content was low enough SO that the bicrystals could be partially transformed to austenite by heating to elevated temperatures. The silicon-iron used had the following initial composition: 1.55 pct Si, 0.04 pct C, 0.0031 pct N, 0.17 pct Mn, 0.020 pct S, and 0.002 pct P. The alloy was obtained in the form of 0.036-in. sheet. The procedures employed to prepare seed crystals in strips of this sheet, to reorient the seeds, and to grow them into bicrystals are essentially those described by Dunn and Nonken and aynes." The characteristics of the bicrystals are given in Table I. The "bicrystal type" indicates the crystallographic plane parallel to the broad faces of the strip in both grains and the crystallographic direction which was parallel to the long edges of the strip in both grains prior to disorientation. The angular disorientation of the grains, 8, which was performed about the direction normal to the plane of the broad faces of the strip, was measured between the [ 00l] directions. Orientation of the grain boundary, , was taken as the angle between the plane of the grain boundary and a plane containing the axis of disorienta-

Jan 1, 1962