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By J. J. Gilman, T. A. Read

S URFACE effects in the cleavage of brittle crystals have been known for some oftime,1, 2 but our knowledge of surface effects in the plastic deformation of crystals is of relatively recent origin. In 1936, Roscoe9 eported his observations comparing oxidized and clean cadmium crystals. He found that cadmium crystals 1/2 mm in diam when covered by an oxide film less than 1200 atoms thick had critical shear stresses about twice those for clean crystals. This effect is anomalous in that it cannot be caused by the inherent shear strength of a normal oxide film. Either an interaction between the film and the crystal causes the large increase in strength, or the oxide film has an abnormal mechanical strength. Several authors since Roscoe have studied surface effects in crystal plasticity. A complete review of the literature will not be presented, but most of the results may be summarized as follows: 1—The critical shear stress for slip is increased markedly by very thin oxide films on zinc4 and cadmium crystals;" ' also, the entire stress-strain curve is raised by an oxide coating;3,4 both effects increase with decreasing specimen radius. 2—Surface active substances such as oleic acid destroy the hardening effect of oxide films.4, 6-8 The time required for the reduction of the hardening effect to begin increases with the viscosity of the solvent4~ 3—There has been dispute in recent years about the effects of surface active substances themselves on plastic deformation. Rehbinder, Lichtmann, and Maslenikov9 state that surface active substances reduce the strength of metal monocrystals markedly and increase the number of slip lines per unit length at a given strain. The effect varies with orientation for tin crystals being smallest for x, = 0, largest for x, = 45", and intermediate as x, + 90°.10 Several workers claim to have disproved the results of Rehbinder')"." but Rehbinder and Lichtmann9 have defended themselves and Masing with his collaborators" has confirmed some of Rehbinder's results. 4—Immersion of metal specimens in electrolytes such as sodium chloride reduces their strength12,13' and subsequent cathodic polarization increases the strength reduction. For noble metals, the strength reduction occurs for both anodic and cathodic polarization," increasing with increasing polarizing voltage. 5—Electroplated copper coatings effect the creep rates of zinc monocrystals. Poly crystals are not affected." 6—Immersion in dilute acid destroys the hardening effect of an hydroxide film. When an acid solution is applied to a steadily creeping crystal, the creep rate jumps to a very high value and then drops gradually to a steady value which is higher than the initial steady rate.*' " If the hydroxide film to be removed is very thin (about 100A thick), the creep rate does not change measurably, but a small rapid strain-increment is observed when dilute acid is applied." 7—Crystal plasticity depends on specimen dimensions. This was observed by Lichtmann and Ven-stroml" for monocrystalline tin and by Andrade and Kennedy" for polycrystalline lead. 8—Immerson of copper crystals in mercury has no effect on their stress-strain curves.'" 9—Bombardment of creeping cadmium crystals with a particles which penetrate the surface to only 0.005 mm may increase their creep rates as much as five times.''' The experiments which will be described in this paper pertain to: (a) the effect of a crystal's shape on its plastic deformation, and (b) the effect of metallic surface films on plastic deformation. For the work pertaining to (a), crystals of zinc, tin, and lead were grown which had various shapes. These were tested in simple tension. Macroscopic rotations about the tension axis which are unpredicted by the classical theory of slip were observed, and serrated edges were observed in tin crystals. For the work pertaining to (b), the effects of evaporated and electrodeposited films of copper, nickel, gold, and zinc on the mechanical properties of zinc, tin, and lead crystals were determined. The films influenced both slip and twinning of the crystals in creep and tensile tests. Experimental Details Chemically pure zinc, tin, and lead were used in this investigation. The zinc was 99.999t pct pure;

Jan 1, 1953

By R. J. Charles

SEARCH for a consistent theory to explain the relationship between energy input and size reduction in a comminution process has accumulated, over the years, an enormous amount of plant and laboratory data. Although some correlation of these data has been possible for purposes of engineering design and for the advancement of research in fracture, there is still great need of a means of predicting behaviour of a solid when it is reduced in size by mechanical forces. The best known hypotheses proposed to describe the energy-size reduction relationships in crushing and grinding stem from a common origin. The present article analyzes problems of comminution in the light of the precepts of this origin. Its object is to reconcile points of difference between these well known hypotheses and to present relationships more widely applicable to comminution studies. Theoretical Considerations: Most existing relationships between energy and size reduction of a brittle solid stem from a single, simple, empirical proposition.&apos; Although this proposition can be demonstrated by observation and experiment, no theoretical derivation is yet possible. Mathematically, the proposition may be stated as follows: dE = -Cdx/xn [1] where dE = infinitesimal energy change, C = a constant, dx = infinitesimal size change, x = object size, and n = a constant. Eq. 1 states that the energy required to make a small change in the size of an object is proportional to the size change and inversely proportional to the object size to some power n. No stipulations are placed on the exponent n in either magnitude or sign. In 1867 Rittinger2 postulated that the energy required for size reduction of a solid would be proportional to the new surface area created during the size reduction. As far as can be determined there is as yet no physical basis for Rittinger&apos;s hypothesis. Rittinger&apos;s hypothesis can be stated mathematically as follows: E, = K(oa-a-0 . [2] Er = energy input per unit volume, K = a constant, <ti = initial specific surface, and o2 = final specific surface. In the size reduction of particles of size x, to particles of another smaller size, x2, Eq. 2 becomes the well known relation: ET = K&apos; {l/x2-l/xx) [3] where K&apos; is a constant. Eq. 3 may be arrived at from the proposition given in Eq. 1 by integrating and by assigning a value of 2 to the exponent n. J dE = J - C dx/x2 E = Kt (1x - 1x) where K&apos; = C. In 1885 Kick3 proposed the theory that equivalent amounts of energy should result in equivalent geometrical changes in the sizes of the pieces of a solid. For example, if one unit of energy reduced a number of equal-sized particles to particles of one half the size, then the same amount of energy applied to the particles resulting from the first test should result again in a size reduction of one half or a final size one quarter the original size. The Kick concept may be expressed as follows: Ek = K" log x1/x2 [41 K" = a constant and E, = energy per unit volume. The expression for Kick&apos;s law may be arrived at by again integrating Eq. 1 and in this case assigning a value of 1 to the exponent n. dE= J - C dx/x Eh = - C In {x/x2) = K" log (x,/x,) where K" = 2.3 C. Application of Kick&apos;s and Rittinger&apos;s laws to comminution has met with varied success. Gross and Zimmerley4 and Piret5 have shown that Rittinger&apos;s equation applies under certain conditions of experimentation. Walker and Shaw6 express the belief that in metal turning and shaping and in grinding of both metals and minerals the production of very fine particles (less than lP) follows Kick&apos;s hypothesis, whereas Rittinger&apos;s concept is valid for the size reduction of coarse particles. For the practical case of crushing and grinding, however, neither of the above hypotheses has received general acceptance. Bond&apos; has lately proposed that since neither Kick&apos;s nor Rittinger&apos;s hypotheses seem correct for plant design work, an energy-size reduction relationship somewhere between the two would be more applicable. The fundamental statement of Bond&apos;s work

Jan 1, 1958

By A. W. Sommer, H. H. Kellogg

It is shown that SO3-O2 mixtures react with sphalerite at an appreciable rate ill the temperature range of 361° to 527°C to fornz ZnSO4. The rate of reaction follows a parabolle lax. Oxygen, or O2-SO2 mixtures, have a negligible effect on sphalcrite in the same temperatuee range. PRACTICAL roasting of sphalerite is usually performed at 800°C or higher. The calcine is composed of zinc oxide unless the roaster atmosphere contains relatively large amounts of SO2 and the temperature is held to 800oC or lower, in which case zinc sul-fate may also form. Ong, Wadsworth, and assell&apos; have made a careful kinetic study of sphalerite oxidation under these "normal conditions" and have concluded that the rate of the reaction is controlled by the decomposition of an activated complex adsorbed on the sphalerite surface. They found the rate of oxidation to be small at 700°C. Extrapolation of their data to 400°C would indicate an almost negligible rate at this temperature. In our work sphalerite was reacted with air, mixtures of SO2, O2, and N2, and mixtures of SO3, O2, and N2 in the temperature range 361o to 527OC. Negligible rates of oxidation were found, except for the gas mixtures containing SOs. With this latter gas, the oxidation of finely divided sphalerite was fairly rapid and zinc sulfate was the product. Based on the limited evidence available, the rate of sphalerite oxidation by SO3 is postulated to be controlled by gaseous diffusion through pores or cracks in the zinc-sulfate coating. This evidence for the direct reaction of sphalerite and SO, at low temperature may prove of importance to the understanding of zinc-sulfate formation in the dust-collecting equipment usually associated with zinc roasters. The roaster gas carries off fine dust, much of which may be unreacted sphalerite. The temperature in dust-collecting equipment drops from the roaster temperature (about 800°C) through the range of temperature we studied, to ambient temperature. Such dusts are known to contain far larger amounts of zinc sulfate than the primary calcine. It has been assumed in the past that this sulfate is formed by reaction of ZnO dust with SO3 (or SO, plus 0,) in the partly cooled gases. Our work shows that an alternative possibility exists—the direct reaction of SO3 with ZnS dust. EXPERIMENTAL Reaction rates for sphalerite at 350° to 600°C are relatively small so that it was necessary to use finely divided material with a relatively large surface area in order to obtain measureable amounts of reaction. In the preliminary experiments, pure mineral sphalerite, ground to pass a 325-mesh sieve, and chemically precipitated ZnS (in the form of an impalpable powder) were used. In the quantitative rate experiments the ground mineral sphalerite was processed in an Infrasizer to obtain a product with particle size between 9 and 18 µ. The analysis of this material was 66.7 pct Zn, 0.09 pct Fe, and 32.7 pct S (theoretical sphalerite is 67.1 pct Zn, 32.9 pct S). The sized powder was carefully mixed and divided into l-g samples. The apparatus used for the quantitative rate measurements is shown in Fig. 1. For the preliminary experiments the following change was made: The external catalyst furnace (B, C)* was not used. *Letters refer to Fig._______1 .___- Rather, when catalysis of the SO2 + O2 reaction was desired, the glass beads in basket M were replaced by vanadium-oxide pellets. Procedure—A l-g sample of ZnS was placed on a shallow stainless-steel tray, I, and spread evenly to a depth of about 1mm. The tray was placed in the reaction assembly and the assembly inserted in the cold furnace. The furnace tube was flushed with dry argon and then heated to the desired reaction temperature. The temperature was controlled to ±0.5oC. Gas mixtures (O2 + N2 or O2 + SO2) were prepared from tank gases by means of a mixing device identical to that employed by Darken and Gurry.2 The total flow rate of gas was 205 ml per min to point A of Fig. 1. The accuracy of the individual and

Jan 1, 1960

By Alan J. Strauss

The Group IV elements germanium, tin, and lead form nine 1:1 compounds with the Group VI elements sulfur, selenium, and tellurium. This paper reviews the properties of the pseudobinary solid solutions formed by these compounds, including the extent of mutual solid solubility, temperature-composition phase diagrams, transport properties, deviations from stoichiometry, optical properties, and energy band structure. Particular emphasis is placed on the Pbl-xSnxTe and Pb1-xSn,Se alloys with rocksalt structure, because of current interest in these malerials for generating and detecting infrared ,radiation. ThE Group IV elements germanium, tin, and lead form nine 1:1 compounds with the Group VI elements sulfur, selenium, and tellurium. Some of the physical and electronic properties of these compounds, including their melting points1-8 and energy gaps,4&apos;9-12 are listed in Table I. Four compounds (SnTe, PbS, PbSe, and PbTe) have the cubic rocksalt (Bl) structure. At room temperature GeTe has a rhombohedra1 structure closely related to the B1 structure, into which it is transformed at about 400°C. Four compounds (GeS, GeSe, SnS, and SnSe) have the orthorhombic B29 structure. In samples which have not been intentionally doped with impurities, the electrical conductivity is due primarily to electrons or holes produced by the ionization of donor or acceptor lattice defects associated with deviations from stoichiometry. Undoped samples of PbS, PbSe, and PbTe may be either n type or p type, depending on whether they contain excess lead or an excess of the Group VI element, respectively, but only p-type samples of the other compounds have been reported. This paper will review the properties of the pseudo-binary solid solutions formed by the nine 1:l compounds. The topics to be considered include the extent of mutual solid solubility, temperature-composition phase diagrams, transport properties, deviations from stoichiometry, optical properties, and band structure. Particular emphasis will be placed on the Pb]-xSnxTe and Pbl-xSnxSe alloys with B1 structure, which are promising materials for generating and detecting infrared radiation in the 8 to 14 µm atmospheric window and beyond. MUTUAL SOLID SOLUBILITY The extent of mutual solid solubility in the pseudo-binary systems has been investigated for fourteen of the eighteen ternary systems (in which the two terminal compounds have a common element) and for nine of the eighteen quaternary systems. In most cases, X-ray diffraction measurements made at room temperature were used to determine the structure and lattice parameter(s) of the phase(s) present in samples of various compositions prepared by freezing from the melt. In many investigations, including the extensive studies of Krebs and co-workers,13&apos;14 the samples were annealed at elevated temperatures before X-ray measurements were made. In some cases, metallographic examination and thermal analysis have also been employed. The results for the ternary and quaternary systems are summarized in Tables II and III, respectively. (The original references should be consulted for the annealing temperatures.) The solubility of one compound in the other is at least 5 mol pct in all cases, and is often much larger. Complete solid solubility has been observed in all systems so far investigated in which the terminal compounds have the same structure, although in the PbS-PbTe system complete solubility is limited to elevated temperatures. Thus complete solid solubility occurs in five systems where both compounds have the B1 structure (SnTe-PbTe, PbS-PbSe, PbS-PbTe at temperatures above 805°C, PbSe-PbTe, and SnTe-PbSe) and in three where both compounds have the B29 structure (GeS-SnS. GeSe-~n~e-, and SnS-SnSe), as well as in two involving GeTe and a compound with B1 structure (GeTe-SnTe and GeTe-PbTe). On the basis of thermal analysis data, complete solid solubility at sufficiently high temperatures has also been reported for the GeSe-GeTe2 and SnS- pbS22 systems. This seems unlikely, however,

Jan 1, 1969

By L. E. Murr, P. J. Smith

A study has been made by transmission electron microscopy of thin foils of 304 stainless steel fatigued external to the electron microscope in reversed bending, and of thin foils fatigued directly within the microscope in alternating tension. The build-up of stacking faults in the thin foils during fatigue zoas correlated with the dislocatirm structures found in thin films prepared fror fatigued bulk specimens. The performance of the special devices designed for fatigue of thin foils so outlined and the importance of alternative methods of preparation of more uniform fatigue specimens bY vapor deposition are emphasized. INVESTIGATIONS on fatigued bulk aluminum1,&apos; and stainless stee13j4 have revealed the existence of dislocation substructure on examination by transmission electron microscopy of electrolytically thinned foils representative of these bulk specimens. While this technique has proved extremely valuable, it has several shortcomings. First, the method of fatiguing bulk specimens and then thinning to foil for electron-transmission observation allows only one observation of internal structure at any one portion of the fatigue life. Second, thinning the bulk fatigued specimens to foil results in the loss of at least one original surface. Thus, what one sees in the remaining electron-transparent sections is an internal dislocation or fault structure which in many cases cannot be correlated with the original surface markings. This is an undesirable feature, since it is well-known that metal surfaces play an important part in the fatigue process.5 An obvious third undesirable feature of the thinning-from-bulk technique is the fact that static observations have difficulty (in the case of fatigue) explaining the mechanism of a dynamic process. What is required then is a method whereby a selected thin area can be continuously observed either while undergoing cyclic deformation or at various fixed stages of fatigue deformation. While Murr and wilkov6 have reported some success with an apparatus designed to fatigue thin metal foils directly within the electron microscope, the nature of the specimen-mounting procedure and the mechanical features involved in the adaptation of the fatigue device to the electron microscope make this method difficult to operate. It was not possible, for example, to make frequent observations of a selected area because of difficulty in maintaining a chosen area in a stable viewing position inside the electron microscope. Except for the build-up of a dislocation substructure and what are commonly referred to as "slip striations", little else has been reported from observations on thin-foil sections prepared from bulk fatigue specimens. segal17 has found "slip striations" in stainless-steel fatigued specimens which were electropolished from both sides, but gave no explanation as to their origin or identity in terms of lattice imperfections. The research to be reported in this paper was undertaken with the following objectives in mind. First, an attempt was made to devise a technique or techniques whereby thin metal foils could be fatigued and repeatedly observed by transmission electron microscopy. Second, it was hoped that some correlation could be made between deformation striations found in fatigued thin transmission specimens and thin foils prepared from bulk fatigued specimens. These investigations illustrate quite convincingly that a feasible method is available for the direct study of the fatigue mechanism and similar dynamic phenomena in thin transmission specimens inside the electron microscope. I) EXPERIMENTAL METHODS Three modes of specimen fatigue and observation of fatigue damage were used. These involved fatigue of thin-foil specimens in a special arrangement external to the electron microscope and observation of a selected area at various stages in the fatigue life, the fatigue of thin-foil transmission specimens inside the electron microscope, and the fatigue of bulk specimens external to the electron microscope followed by thin-foil preparation for direct observation at predetermined stages. Design of the External Fatigue Clip and Specimen Holder for the Hitachi H.U.11 Electron Micro-scope. The purpose of the fatigue clip was to provide a reversed bending fatigue stress to a thin-foil transmission specimen outside the electron microscope. In order to accomplish this, a flat-bottomed, U-shaped brass clip was made as shown

Jan 1, 1965

By I. B. Cadoff, J. C. Bilello, R. Rosenberg

Diffiusion of magnesium into the surface of LiF crystals to controlled depths and subsequent heat treatments provided a wide range of surface zone harahesses and structure, The bend strength of the LiF crystals was increased by as much as an or-dev of magnitude. Ductility was achieved when dislocation generation occurred in the diffusion zone or when dislocations penetrated to the surface from the intevior. A critical surface hardness of 130 to 140 kg per sq mm was found helozu which generation could take place in the diffusion zone and ahoue which the zone was impenetrable, This hardness was obtainable by several methods, among them the aging of quenched MgF2 -LiF solutions to produce MgF, precipitation. Maximum hardness was ohtained in quenched specimens with no visihle evidence of MgF,. Diffusion-zone formation followed a parabolic rate law and an activation energy of 20.9 kcal per mole was obtained for the process. RECENTLY, the properties of ionic crystals as related to surface condition have been receiving much attention, specifically the transitions between ductile and brittle behavior. Originally Joffe 1 showed that NaCl crystals could be made ductile by immersion in water and related this to the elimination of surface microcracks. Aerts and DeKeyser 2 and Gorur 3&apos; have subsequently shown that ionic crystals are inherently ductile and are embrittled through contact with air. Machlin and Murray4 hypothesized that a layer of NaCIO3 produced by contact of ozone with NaCl induced embrittlement by acting as a barrier to outward dislocation flow. westwood,&apos; Rosenberg and Cadoff,9 and Bilello and cadoff&apos; have reported surface strengthening of LiF crystals by coating with a magnesium compound and then heat treating for adherence. The major effect of the coat was to inhibit dislocation-slip lines from reaching the specimen surface. westwoods showed microcrack formation and fracture to be caused by slip-band interactions at the surface. The material presented in this paper is an extension of the work reported earlier by Bilello, Rosenberg, and cadoff&apos;6,7 and illustrates the wide range of surface properties and bulk behavior obtainable by use of heat-treated magnesium-diffused surface regions in LiF crystals. EXPERIMENTAL PROCEDURE The LiF single crystals were obtained from the Harshaw Chemical Co. Some batch to batch variation was observed; therefore all specimens for a given test series were cleaved from the same crystal. The typical dimension used was 1 by 0.1 by 0.40 in. Surface damage resulting from cleavage was removed by chemically polishing in a 2 pct NH4OH solution. Each group of specimens was given a vacuum anneal at 700°C for 4 hr to provide a base standard for measuring comparative effects of various surface treatments. To produce the reacted surface zone, the annealed specimens were immersed in a boiling suspension of MgF, in doubly distilled HzO, agitated slbwly for 30 sec, removed, and dried at room temperature. Uniform coatings of MgF, were deposited with a thickness of approximately 5 mils. It should be noted that this technique can be modified for use with crystals which are soluble in water by using boiling absolute alcohol as the dissolving medium. This was found effective for the coating of NaCl with MgF2. The diffused surface zone was obtained by annealing the coated samples at elevated temperatures in a vacuum of lob4 mm Hg. Penetration depth was controlled by varying the annealing time from 1/2 to 28 hr. After heat treatment, the samples were tested for bend strength and hardness. Load was applied by four-point bending in a hard-beam testing jig. Four-point rather than three-point bending was used to provide a wide area of constant stress and to minimize the effect of localized inhomogenities in the specimen. The deflection rate was 8 x min-&apos; and the distance between knife edges was 1/4 in. Load-time curves were obtained from a chart recorder coupled to the machine and converted to resolved shear stress on the shear plane vs deflection, as plotted in the figures. The unstressed portions of the sample outside of the two outer knife edges were used for the microhardness studies. Microhardness measurements were made with a Bergsman tester attached to a Reichert metallograph. All hardness impres-

Jan 1, 1964

By E. S. Machlin, Morris Cohen

The martensite reaction in single crystals and polycrystals of 70 pct Fe-30 pct Ni alloys is shown to be autocatalytic in nature, producing bursts of transformation during cooling. The temperature of the first burst of transformation, called Mb, occurs below M, in these alloys. Experiments were devised to test the athermal embryo and strain embryo theories of martensite nucleation. The results indicate that internal strains, either within the virgin austenite or around existing martensitic plates, control the nucleation process in these alloys. Furthermore, the growth of martensitic plates is not limited by the attainment of an elastic balance with the austenitic matrix, but by the occurrence of plastic deformation at the martensite boundaries which interferes with the propagation mechanism. IN an investigation of the martensitic habit in single crystals of a 69 pct Fe-31 pct Ni alloy,&apos; it was observed that about 25 pct of the austenite transformed during subatmospheric cooling within the time-interval of an audible click. This event proved quite spectacular: The shock wave sent out from the specimen freely suspended on a thread in the refrigerating liquid was occasionally sufficiently intense to shatter the Dewar container and to separate the toluene column in the immersed thermometer. The Present investigation was undertaken to determine- the kinetics and mechanism of this "burst" type of martensitic reaction. The analyses of the alloys studied are given in Table I. The composition of the single crystal specimens is designated by alloy A, while the polycrystal-line specimens were made of alloys B and C as noted in the text. The single crystals were prepared in a vacuum furnace, using a modified Bridgman technique. Most of these crystals were homogenized by holding for 24 hr at about 1300°C just after solidification. However, it may be emphasized here that the degree of homogenization was not a controlling factor in the subsequent experiments, inasmuch as specimens having different degrees of homogenization yielded the same results. All of the single crystals were fully austenitic as slowly cooled to room temperature. An illustration of the burst phenomenon is given in Fig. 1, which shows oscillograms of electrical resistivity and temperature vs. time during the continuous quenching of 1/16 in. wire specimens (alloy B) in a dry ice and acetone bath at —77°C. There are at least two observable bursts in this case, as indicated by the sharp decreases of resistance accompanying the sudden formation of substantial quantities of martensite. The thermal arrest during the quench probably corresponds to the larger burst. Usually the bursts are followed by more or less progressive transformation during continuous cooling. It will also be noted that the resistance continues to decrease after the specimen has reached the bath temperature. This isothermal change denotes the formation of martensite at constant temperature, and will be the subject of another paper. Examination of fiducial scratches on the surface of a transformed single crystal has shown2 that the scratches in adjoining nonparallel martensitic plates are usually bent in opposite directions, as though one plate forms in such a way as to relieve the matrix stresses set up by the adjacent plate. This, together with some of the results described in ref. 1, Table I. Compositions of Alloys Studied, in Percent Alloy Ni C N Mn Si P S Cr A 31±0.3 0.048 0.027 0.003 0.56 0.007 0.002 B 29.5±0.2 0.036 0.02 0.19 0.09 0.008 0.006 C 19.99 0.52 0.37 0.47 0.010 0.015 0.04 led to the tentative concept that a cooperative action exists which provides the impetus for much of the transformation that appears during the burst. The following series of experiments were performed in order to test this idea. Cooperative Nature of the Burst Two adjacent disks, Va in. thick x % in. diam, were cut from a single austenite crystal of alloy A using a jeweler&apos;s saw. One of the disks was then cut into 15 parts. Then 12 of the latter pieces and the second disk were austenitized (stress relieved) at 600°C for 30 min and water quenched to room temperature. The temperatures at which the first burst of transformation appeared were determined for

Jan 1, 1952

By C. G. Dunn, P. K. Koh

Microstructure, magnetic torque, and texture data before and after grain growth were obtained on two 3.25 pet Si-Fe specimens having initially the same cold-rolled textures and the same primary recrystallization textures. The latter textures consisted of four components, two only of which were strong; the strong components were near (120) [001] and (320) [001]. The textures of the two specimens obtained by grain growth were different. In one specimen the two weak components were converted into strong components by a secondary recrystallization process; in the other specimen the primary recrystallization texture was retained by a normal grain-growth process. The difference in behavior of the two specimens was interpreted in terms of a difference in the relative grain sizes between weak and strong components; i.e., in terms of a geometrical factor that would alter the early growth rates of grains belonging to the two weak components of the texture. Specifically the growth rate was considered as the product of two terms: a driving force and a boundary mobility. The texture changes observed are considered to favor the oriented-nucleation growth-selectivity theory more than the oriented-growth theory. WHEN primary recrystallization and grain-growth textures form as a result of annealing deformed metals or alloys, the fundamental processes involved are nucleation and growth. Knowledge, therefore, about nuclei and the factors influencing their growth is required not only for the understanding of texture development but also for its control. In the oriented-growth theory of texture formation1, 2, 3 the problem of nuclei is generally disposed of by the assumption that nuclei are available in all orientations; the theory then has to explain the final texture from the initial texture and the way boundary mobility depends on orientation. In the oriented nucleation theory of texture formation"&apos; nuclei are considered to be present only in certain orientations but the importance of growth selectivity is still recognized. For example, the mobility of boundaries of approximately the same orientation and of the coherent type in twins is believed to be low while that of high-angle boundaries, in general, is high. Because of this the theory may be described as an oriented-nucleation growth-selectivity theory. The main feature of the oriented-nucleation theory, however, is the importance given to nuclei; i.e., how they form in specific orientations and how they grow. In the present investigation two cold-rolled single crystals were used to study the effects of growth after primary recrystallization. The cold-rolled textures and the primary recrystallization textures were determined from portions of these specimens and reported earlier.",&apos; The two cold-rolled crystals were in the (111) [112] stable end orientation, the recrystallization textures were nearly identical and consisted of two strong components, designated M and M&apos;, which were near (120) [00l] and (320) [00l], respectively, and also some specific weak components near (111) [110] and (111) [110]. It is well recognized that a single strong component in the primary recrystallization texture may be needed for secondary recrystallization3, 5, 8 but unfortunately when this is the case the amount of material left in deviating orientation may be too small either for growth or for positive identification. The present samples proved to be almost ideal for the study of minor components and their influence on texture changes produced by growth after primary recrystallization. The results obtained are interpreted in terms of present knowledge of grain-growth processes. Experimental Procedure Two lots of silicon-iron alloy of essentially the same composition, namely, 3.25 pet Si, 0.004 C, 0.009 P, 0.010 S, 0.035 Mn, 0.070 Ni, 0.090 Cu, 0.009 Sn, with traces of A1 and Cr and the balance Fe, were converted into single crystals 0.025 in. thick and 1.25 in. wide. The orientations were predetermined by the method of reorienting a seed crystal as described elsewhere.3 pecimen 1 from one lot had the (335) [556] orientation while specimen 2 from the second lot had the (111) [112] orientation.* Both crystals were cold rolled to a reduction in thickness of 70 pet while widening approximately 20 pet. Samples of each were selected for determining 1) the cold-rolled texture, 2) the time required at

Jan 1, 1959

By Y. Shimomura, M. Serizawa, Y. Takahashi, K. Miyagawa

The "semi-pellet" sintering method developed and currently being used at the Fuji Iron & Steel&apos;s Hirohata Works is discusssd. It is shown that the method makes fine-sized material easily sinterable and increases sinter production. The operation can be incorporated readily into conventional sintering plants. Sintering plant raw materials currently being used in the Hirohata Works consist of 40 pct pyrite cinder, 40 pct fines resulting from crushing and screening of imported ores, and 20 pct others, such as mill scale and iron sands. Pyrite cinder, a major component in the sinter feed, has been getting finer since 1952, due to the increased grinding required for the improvement of the results in the iron sulfide flotation and to the adoption of FluoSolid roasters in sul-furic acid plants; some fines pass 100-mesh sieve almost completely. Increased use of the fine-sized pyrite cinders in the sinter raw mix resulted in such difficulties as decreased bed permeability, uneven firing conditions, and low yield. In an attempt to study the cause and to find a remedy for this problem, a series of experiments were made, using an 80-kg experimental sintering pan. As a result it was established that, by rolling the fine-sized pyrite cinders into small balls of 10 to 3 mm diam (hereafter called semi-pellets) and mixing them into the sinter raw mix, the bed permeability was improved, the sintering time shortened, and the yield and production rate increased. It is proposed that this new method be called the semi-pellet sintem&apos;ng. In recent years the pelletizing process has taken the spotlight in the agglomeration field for treating fine-sized ores here in Japan as well as in the U.S. and Europe. This process produces pellets suitable for the blast furnace charge as such, and consists of three major operations: fine grinding, balling, and firing. With regard to the firing technique, some problems still appear unsolved. In the semi-pellet sintering, however, several ad- vantages can be claimed: the balling operation is relatively simple because only small-sized balls are shown to be acceptable and the operation can be readily incorporated into the conventional sintering plant, since only balling, not grinding or firing, equipment is needed. Basic test work on the process was initiated in 1954 and favorable results were obtained. Accordingly a pilot plant was built in 1955 and the test work was continued. The semi-pellets thus prepared in the pilot plant were tested further by USing them in the actual sintering pan and their beneficial effects ascertained. In late 1956 a drum-type balling machine (2.4X4 m) was installed and it went into operation in April 1957 in conjunction with the Greenawalt sintering plant (8 pans having dimensions of 7.2 m in length, 3 m in width, and 0.3 m in depth). In October 1958 a cone-type pelletizer, with a 2.2 m diam, and later a disk-type pelletizer were further added in the plant. In the DL sintering plant (2000 tpd), newly built in July, 1960, four disk-type pelletizers (3.2 m diam, 10 tph capacity) were installed. By mixing the semi-pellets thus prepared with the feed, the sintering operation was found to be greatly improved. The results of the basic test work, and the equipment and operation of the semi-pellet sintering operation at the Hirohata Works will be described. ON THE SINTERING CHARACTERISTICS OF FINE SIZED PYRITE CINDERS To ascertain the effect of addition of fine-sized pyrite cinders on the sintering characteristics, a series of measurements on bed permeability was carried out by varying the size distribution of pyrite cinders. The composition of the raw mix used in the tests was fixed at 50 pct pyrite cinder, 20 pct Larap magnetite fines, 30 pct sinter return, and 5 pct coke; only the size distribution of the pyrite cinder was varied. Also the moisture content was changed at each size distribution. The results are given in Fig. 1. For all pyrite cinders tested the bed

Jan 1, 1961

By Donald B. Evans, Robert D. Pehlke

The solubility of nitrogen in liquid Fe-B alloys has been measured up to the solubility limit for the formation of boron nitride. The activity coefficient of nitrogen increases with increasing boron content in the range 0 to 7 wt pct B. From experimen -tal data, values have been calculated for the B-N interaction parameter e3 at temperatures in the range 1550" to 1750°C. A value of 0.038 has been estimated for the boron self-interaction parameter eg at 1550°C. The standard free energy of decomposition of boron nitride into the elements dissolved in liquid iron has been determined to be: ?F° = 45,900 -21.25T in the range from 1550° to 1750°C. The nitride is assumed to be of composition BN. BORON nitride has an unusual combination of properties which make it appear attractive in a wide range of engineering applications. Some of its more important and most recent applications are in the nuclear area, particularly in connection with the liquid-metal cooled reactor concept now receiving considerable emphasis. Boron nitride has a high degree of stability at elevated temperatures. It also has excellent ma-chinability and the ease with which its crystals deform suggests applications as a lubricant. These properties stem from a hexagonal layer-type structure similar to the structure of graphite. One of its primary uses to date has been for seals in liquid-metal pumping systems. It is also used in nuclear reactors as an insulating layer to separate two solid metals which are not themselves compatible under the conditions of temperature and atmosphere in which they are used. Its inertness to liquid metals has also suggested use as a mold-release agent in casting processes. In addition to its excellent machinability and reported inertness to liquid metals such as iron, silicon, aluminum, copper, and zinc, boron nitride has high thermal conductivity and excellent thermal shock resistance. This combination of properties would make it appear ideal as a refractory crucible material for refining of high-purity liquid metals, for example high-quality steels. However, since it is known that concentrations of boron as low as 50 ppm can have a marked effect on the physical properties of certain steels,&apos; in particular on the creep and stress-rupture properties, an investigation was undertaken to define accurately the chemical equilibrium among boron, nitrogen, and liquid iron in the range of steelmaking temperatures. EXPERIMENTAL PROCEDURE Two experimental approaches to this problem were employed: a Sieverts&apos; method and a quenching method. In the first method, the Sieverts&apos; technique was used to measure the equilibrium nitrogen solubility in liquid Fe-B alloys of 0 to 7 pct B as a function of nitrogen gas pressure over the melt. The solubility limit of the boron nitride phase formed was determined by the point of departure of the nitrogen absorption from Sieverts&apos; Law. This technique has been applied to liquid Fe-Ti alloys by Rao and parlee,&apos; to liquid Fe-A1 alloys by Evans and Pehlke,3 and to solid Fe-V alloys by Fountain and Chipman.4 In the second method a melt of liquid iron was held in a crucible of boron nitride under a known partial pressure of nitrogen gas. After thermodynamic equilibrium was attained, the melt was quenched in a stream of helium and then analyzed by wet-chemical methods for boron and nitrogen. The Sieverts&apos; apparatus used in the first method was essentially of the same design as the one described by Pehlke and Elliott.5 The charge materials were vacuum-melted high-purity iron (Ferro-vac E) supplied by the Crucible Steel Co. and -325 mesh boron powder supplied by Cooper Metallurgical Associates of Cleveland, Ohio. The boron contained less than 0.02 wt pct O, according to supplier&apos;s analysis. Recrystallized alumina crucibles were used to contain the melt. Examination of solidified melts showed these crucibles to be satisfactory with no evidence of any reaction or physical penetration of the crucible wall by the melt. The melt temperature was measured by a disappearing filament-type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diam sight hole in the crucible lid. The pyrometer was calibrated against the melting point of pure iron in the same apparatus, taking the emissivity of

Jan 1, 1964

By J. W. Downey, S. T. Zegler

A study has been made of the occurrence of Phases having the Cr30-type structure in ternary alloys having the general composition where B cept for iron and copper all the B components are known to form binary compounds having the type structure. The occurrence of the struc-ture type in the ternary alloys was investigated using optical and X-ray metallography. The results indicate that iron can replace virtually none of the cobalt in at 900°C, but substitutes for nickel in up to the approximate composition tually insoluble in V3Ni and 2) and exhibit complete solubility. At 100 nickel can be substituted for cobalt in VSCo up to the composition solubility; and 3) in the system , two solid solutions having the type structure occur. At the same temperature, 1000°C, V3Si exhibits limited solubility for V3Co but is completely mis-cible with V3Ga. Lattice parameters have been determined for all the binary and ternary phases. The solid solutions are discussed in terms of the atomic size and electronic factors which are thought to influence the occurrence of Cr30-type phases. The binary compounds V3Co and V3Ni were found to form peritectoidally from o phases and a vanadium, the former compound at a temperature between 1000" and 1050°C, the latter between 800°and 900°C. The substitutions of nickel and rhodium for cobalt in V3Co were determined not to raise the superconducting transition of VSCo to a temperature as high as 2°K. The occurrence and stability of binary intermediate phases having the Cr30- or A15-type structure (space group o;, Pm3n) have been discussed in several recent papers . Vanadium forms the struc -ture at or near V3B stoichiometry with all the mem -bers of the cobalt and nickel groups in the periodic table and also with Au, Ga, Si, Ge, Sn, P, As, and Sb. This paper describes a survey of the occurrence of the CrsO-type structure in ternary alloys having the general composition V3(B, B&apos;) where B and B&apos; are Fe, Co, Ni, Cu, Rh, Ir, Si, and Ga. The purpose of the survey was to clarify the connection between the position of the B partner in the periodic table and its CrsO-type phase-forming tenden~y.~,~ The survey is part of a broader program concerned with the influence of B-partner substitutions on the superconducting transition temperatures of CrsO-type compounds. The transition temperatures, Tc, of some of the ternary Cr,O-type phases found in the survey are also discussed in this paper. EXPERIMENTAL PROCEDURE The alloys were prepared by arc-melting in an A-He atmosphere and were in the form of buttons, weighing approximately 3 g. The metals used in their preparation were received from commercial sources and were in all cases 99.9+ pct pure. The vanadium was spectrochemically pure except for 800 ppm of Si, 200 ppm of Fe, and 200 ppm of Al. For study of each pseudobinary system at least seven alloys were prepared having the general compositions case of alloys containing gallium, melting losses were small, usually less than 0.3 pct of the total weight of the metals charged for melting. Melting losses were somewhat greater for gallium alloys, ranging in general from 0.9 to 5.0 pct. Ternary V-Si-Ga alloys were chemically analyzed and the results are given in Table I. The analyses show most alloys to be within 2 at. pct of the intended composition. Throughout the balance of the paper the intended compositions are used in discussing the alloys. The cast buttons were annealed within evacuated quartz capsules for times ranging from 3 to 6 weeks at temperatures between 800" and 1000°C and water-quenched. The phases present in the annealed and quenched alloys were identified by optical and X-ray metallography. X-ray diffraction photograms were made with powders prepared from the bulk specimens, by the use of a 114.6-mm-diam powder camera with copper irradiation. The lattice parameter of CrsO-type phases and their standard errors

Jan 1, 1963

By R. D. Stover, F. O. Shuck

The variation of binary-diffusion coefficients with composition in the liquid Bi-Sn system at 300°C was measured using the capillary-reservoir technique. The experimental coefficients did not exhibit a simple composition dependence. A number of tests were also made to determine the effect of variation of density with composition on convection within the capillaries. These tests indicate that the density changes arising from composition duferences may give rise to high diffusion coefficients unless care is taken to maintain a stable configuration. In recent years there has been considerable interest in diffusion in liquid metals. However, the bulk of the work done to date has involved measurements of self-diffusion or diffusion of dilute concentrations of "solute" metals. Because there are possible applications to liquid phase processing of metal alloys and since additional data may help to clarify the nature of diffusion in liquid metals, investigations of the concentration variation of diffusion coefficients in binary alloys have been undertaken. Of past studies only two have covered large ranges of binary composition. Niwa et al.&apos; investigated the Pb-Sn, Bi-Pb, and Bi-Sn systems and Grace and Derge2 investigated the Bi-Pb system. Because of the discrepancy between the data of these investigators, it was deemed desirable to check the possibility of convection arising from the variation of density with composition. The capillary-reservoir technique of Anderson and saddington3 was chosen for the present investigation since it has been widely used for measurements involving dilute solute concentrations and it was the technique used by Grace and Derge.2 It was necessary, however, to modify the normal procedure of using a pure metal bath to avoid measurement of integral diffusion coefficients over large concentration ranges. The alloy system chosen for study was the Bi-Sn system for which there are some data available.&apos; EXPERIMENTAL PROCEDURE In order to utilize the capillary-reservoir technique for measurements of diffusion coefficients as a function of composition, it was necessary to modify the normal procedure slightly. This modification consisted of using a reservoir composition which was only slightly different from that in the set of capillaries, in order that the integral coefficients measured might be taken over a small composition range and might thereby be assumed to approximate the differential coefficient at some average composition between that of the capillary and that of the bath. It was found that a composition difference of approximately 0.10 mass fraction provided a satisfactory compromise between a small increment in composition and reasonable accuracy in measuring changes of composition. The alloys were prepared from tin and bismuth of 99.999 pct purity. The materials were first cleaned of surface oxides, then weighed and melted to form a homogeneous alloy in a Pyrex filling apparatus. The capillaries used were of precision bore Pyrex tubing 1.000 *0.005 mm bore. Capillaries of various lengths (from 2.85 to 5.85 cm) were cut and sealed at one end by fusing a 3-mm Pyrex rod to the end. The capillaries were filled by inserting them into the filling chamber, evacuating the chamber, submerging the capillaries, and pressurizing the chamber with argon. Two sets of capillaries were prepared for each run. One set contained an alloy more dense than the bath alloy and one set a less dense alloy. This procedure was followed so that the effect of density difference on the measurement could be determined. After filling one set of capillaries, these were placed open end up in a capillary holder and transferred to the diffusion chamber which consisted of a Pyrex tube inserted into a graphite block. The second set of capillaries was then filled and placed into the diffusion chamber. The reservoir alloy, which had been melted in a separate crucible, then was poured carefully into the diffusion chamber. Sufficient reservoir alloy was used to cover all capillaries to a depth of several centimeters. All of these operations: capillary filling, melting of alloys, and diffusion anneal, were carried out in a fused-salt bath which maintained a temperature of 300"*1°C. All capillaries were permitted to diffuse for approximately 48 hr. At the end of the diffusion period the capillary holder was removed from the bath and

Jan 1, 1969

By W. C. Leslie, R. M. Fisher, K. G. Carroll

A nitride, believed to be Si3N, has been separated from three nitrided silicon steels. Germanium nitride, Ge3N4, has been prepared from pure germanium. Comparison of the diffraction patterns indicates that the two nitrides are isomorphous; on orthorhombic structure is suggested in place of the rhombohedral structure previously reported for Ge3N4. THE possibility that a nitride of silicon may, under appropriate conditions, precipitate in silicon steels or in steels killed with silicon makes it desirable to have some positive means of identifying such a compound. One such means is the X-ray or electron diffraction pattern of the nitride. A review of the meager data in the literature indicates that the nitride most likely to form is Si3N4, a conclusion supported by the results of a study of nitrided silicon steels to be published shortly by L. S. Darken and R. P. Smith, of this Laboratory. Unfortunately, there is available no diffraction pattern for this nitride. Data have been reported, however, for Ge3N4 which, judging from the similarity between germanium and silicon, might be expected to be isomorphous with Si3N4. An effort was made, therefore, to form such a silicon nitride, to determine its composition and diffraction pattern and, if possible, its structure. To this end a series of three silicon steels was nitrided under controlled conditions with the resultant formation of nitride particles which yielded an electron diffraction pattern in situ. The particles were then extracted from the steel and an attempt was made to determine their chemical composition. X-ray and electron diffraction patterns were also obtained from the extracted particles, which indicate that the nitride is isomorphous with Ge3N4, although a complete determination of the structure has not been possible. These results show that a silicon nitride with a well-defined diffraction pattern can form in silicon steels, and they suggest that this nitride is Si3N4. Materials and Procedures The sillicon steels investigated were In the form of thin sheet or strip and had the composition shown in Table I. The 0.58 and 1.21 pct Si steels were nitrided by holding them at 1110°F in an H2-NH3 atmosphere containing 3 pct ammonia for 48 hr. The nitride particle size was increased by subsequent heating at 1500°F for 13 1/2 hr in helium. The resulting microstructure is shown in Fig. 1. The steel containing 3.20 pct Si was nitrided at 1200°F for 16 1/2 hr after which it was held in helium at 1500°F for 4 hr. Its structure as seen under the electron microscope is illustrated by Fig. 2. As would be expected from the higher silicon content and the shorter holding time at 1500 °F, the nitride particles are smaller and more numerous than those in the 1.21 pct Si steel. The ammonia-hydrogen treatment reduced the carbon content of the steels to a very low level, so no interference was encountered from carbon or carbides. In the case of the 3.2 pct Si steel, the carbon was reduced to 0.003 pct before nitriding by heating in dry hydrogen. Attempts to obtain an X-ray diffraction pattern from polished and etched surfaces of the 1.21 and the 3.20 pct Si steels were unsuccessful. However, an electron diffraction pattern was obtained from the surface of the steels. The interplanar spacings obtained from these patterns arc shown in Table 11, col. 5. The nitride particles were then extracted from all three steels by dissolving the ferrite matrix in bromine-methyl acetate, the solution used in the Beeghly method for the extraction of aluminum nitride from steel. X-ray diffraction patterns of these residues, obtained by means of a spectrometer and by a 57 mm Debye-Scherrer powder camera using filtered cobalt or chromium radiation, are given in Table II along with the pattern obtained by

Jan 1, 1953

By G. M. Schwartz, G. A. Thiel

THE first record of the quarrying of dimension stone in Minnesota dates back to 1820 when limestone was quarried locally for part of old Fort Snelling. Limestone quarries were operated at Stillwater, Mankato, and Winona as early as 1854. Granite was quarried first at St. Cloud in 1868, and within a few years thousands of tons were shipped to widespread points. Rough dimension stone for large buildings furnished the first important market, but beginning in 1886 paving blocks were in demand. The largest shipment was in 1888, when 1925 cars were shipped from the St. Cloud area. Quartzite was quarried first at New Ulm in 1859 and somewhat later at Pipestone and elsewhere in southwestern Minnesota: The productive dolomite quarries at Kasota were opened first in 1868 and have continued as large producers of a variety of stone to the present time. At present, the industry is controlled by relatively few operators, and for that reason detailed figures on dimension stone are not released for publication. A general idea may be obtained from the data in the Minerals Yearbook for 1948. The figures for total stone produced in Minnesota are 1,804,000 tons valued at $5,090,652. Probably the largest item in the latter figure is received from dimension stone. A better idea of the situation, in relation to the country as a whole may be gained by using the data for 1930 when more companies were operating in Minnesota, and complete figures were published. In that year Minnesota produced granite valued at $2,668,119 and ranked third among the states in value. Minnesota&apos;s production of granite was almost exclusively for dimension stone. In the same year Minnesota produced 300,000 tons of limestone (dolomite) valued at $840,860, and this likewise was mainly dimension stone. In finished limestone Minnesota ranked second among the states in 1930. Sandstone and minor amounts of quartzite are the only other dimension stones that have been produced in Minnesota, but the quarries are now inactive. The commercial stones of Minnesota have been described in two reports by Bowled and by Thiel and Dutton.2 The early history of quarrying in Minnesota and extensive notes on the various rocks are given by N. H. Winchell.3 Small limestone and dolomite quarries were numerous throughout the area of Paleozoic rocks in southeastern Minnesota. Early production was largely dimension stone. With the increased use of Portland cement, most of these ceased production, and today only those at Kasota and Winona remain in operation. In recent years many quarries have reopened and new ones started, but these are devoted to the production of crushed rock and agricultural lime. As the application of modern quarrying and finishing methods increased, small companies in the granite business have dropped out, and the remaining companies have modernized their plants, purchased old quarries, and opened up new ones, thus furnishing a wide variety of granites suitable for most of the customary uses. It is the purpose of this review to present notes on&apos; the geology and operations of each of the quarries now operating within the state. Granites and Related Igneous Rocks The term granite as used in this report includes granites, gneisses, diorites, gabbros, and other igneous rocks. The granites of greatest economic importance are found in three widely separated regions, see Fig. 1. 1-Central Minnesota in the region of the city of St. Cloud, 2-the upper Minnesota River valley region, 3-the northeastern portion of the state, commonly referred to as the Arrowhead region. The St. Cloud Region: The rocks of the St. Cloud region are mainly granites and related rock types such as monzonites and quartz diorites. The stones may be grouped into three major types, namely, pink granite, red granite and gray granite. Most of the pink granite occurs in the area to the southwest of St. Cloud. The rock is best described as stone with large pink crystals set in a finer grained black and white background. The minerals of the matrix occur in remarkably uniform sizes, and the pink crystals are sufficiently uniform in. their dis-

Jan 1, 1952

By M. Garfinkle

LITERATURE data1&apos;3 have suggested that the resolved shear stress necessary to initiate slip in a particular slip system in tungsten single crystals is strongly dependent on the tensile orientation of the crystals. This orientation dependence is contrary to the critical resolved shear stress criterion. Because the Schmid factors for slip on particular {110}( I l l), {112}(Ill), or {123}(111) slip systems in a (100) oriented tungsten crystal are virtually identical to the respective Schmid factors for a (110) oriented crystal, slip should initiate on the same system in both orientations, independent of the values of the critical resolved shear stresses. Thus, it would be expected that, for a critical resolved shear stress model to hold, the proportional-limit stress for these two orientations must be similar. The expectation of similar proportional -limit stresses has not been borne out by reported experimental observations. Rose et nl.&apos; reported that the proportional-limit stress for crystals near the (110) orientation was 92,000 psi, approximately three times that of (100) oriented crystals (31,000 psi). Garlick and probst2 reported greater than a fourfold difference. Most recently, Beardmore and ~ull~ examined tungsten crystals with orientations along the edge of the standard stereographic triangle and showed a gradual increase in proportional-limit stress from 28,000 psi for the (100) orientation to 93,000 psi for the (110) orientation. Again, the difference was more than threefold. As has been emphasized by these investigators, the apparent gross variation of proportional-limit stress with orientation precludes any meaningful analysis of slip mechanics using a simple critical resolved shear stress relation. The purpose of the present communication is to report that, by use of refined strain-measuring techniques, the proportional-limit stresses for the (100) and (110) orientations are quite similar. Obviously, to determine accurately the value of the proportional-limit stress, which is by definition the stress at which nonlinear stress-strain behavior first occurs, the method of measuring strain must be capable of high accuracy. The investigators cited used as the measured elongation the crosshead displacement of the tensile machine. This method, however, introduces extraneous strain contributions from the load train. Because these extraneous contributions are considerable in the initial portions of loading (as has been well-documented in the literature) the proportional-limit stress measurement, dependent on the deviation of a line from linearity, can be significantly affected. During the course of a recent study, room-temperature strain was measured directly on several (100)-and (110)-oriented tensile specimens axially oriented within 5 deg of the desired direction. Each specimen was fitted with two foil strain gages mounted on opposite sides of the 0.08-in.-diam reduced section. The tensile specimens were loaded at a crosshead speed of 0.01 in. per min on an Instron Universal Testing Machine. Strain was monitored through an external bridge circuit in which the specimen strain gages comprised two arms. The bridge output was recorded against the applied load. A strain of 2 x 10"" could be readily detected by this method. Some specimens were subjected to conventional loading while the load for others was cycled between zero and continually increasing values until the first deviation from linearity was observed. The results of these methods were similar, and the stress at which nonlinear behavior occurred was considered the proportional-limit stress. The proportional-limit stresses measured in this study are approximately 5000 and 6500 psi for the ( 100) - and ( 110) -oriented crystals, respectively, a range of values almost a magnitude less than those reported previously. Representative curves are presented in Fig. 1. Because of the nature of the measurements made, the point of departure of a line from linearity is often debatable. While the load-strain curve for the (100) -oriented crystals made a relatively abrupt deviation from linearity, the curve for the (110) -oriented crystal was more gradual, so that the actual point of tangency may be at a lower load than reported. Thus, the difference in values for the proportional-

Jan 1, 1967

By Joseph Lindmayer, Karl M. Busen

If silicon is in contact with silicon oxide, a heterojunction is formed which induces an inversion layer ("channel"). Influences of impurities and structural parameters on the channel are discussed. There seems to be no relation between surface damage in silicon and the channel. Phosphorz~s doping of the silicon oxide has no pronounced effect on the channel. Channels which were well above the range predicted by the heterojunction model were related to the action of H* at the silicon/silicon oxide interface. Channels which were well below tlze range predicted by the heterojunc-tion model were related to a transition region in the oxide adjacent to the interface. In support of the assumed transition region and the H+ are the ex-periments described on the paper. Furthermore, the concept of metastable OH groups in silzca, known from other publications, has been used to explain certain channel characteristics by the formation and the accommodation of hydrogen in the silicon oxide. THE electrical characteristics of a semiconductor device in many cases are influenced by the conditions of its surface. Because these conditions often are changing with temperature, time, ambient, or other parameters, numerous attempts have been undertaken to stabilize them by suitable processes. Several years ago Atallal studied the silicon/silicon dioxide interface and since then increasing attention has been given to the silicon dioxide as a means to stabilize silicon surfaces. This led to the evolution of the planar silicon devices where oxide layers are used to protect places at which the junctions are intersecting the surface. The formation of the oxide layers on silicon can be carried out by a variety of processes: high-temperature thermal oxidation (exposing the silicon surface to oxidizing agents such as 02, HzO, COz), evaporation of SiOz, or anodic oxidation of silicon. Originally the oxides were considered able to "passivate" the silicon surface and it was understood that they 1) protected the surface against any influence from the ambient and 2) stabilized surface conditions which were necessary for proper device performance. It soon was realized that the second quality was not always obtainable: Atalla and Tannenbaum showed that, in the process of forming a layer on doped silicon by thermal oxida- tion, electrically active impurities in the silicon near the interface are redistributed, thus giving rise eventually to the formation of unwanted charge distributions. The degradation of planar junctions during reoxidation of silicon was observed by Barson et a. Surface studies with silicon planar junction structures indicated that the breakdown voltage depended on the kind of procedure which was applied during or after oxidation.*" Yamin and worthinge report on charge storage and dielectric properties of SiOz films at elevated temperatures. Another influential parameter on the silicon surface is discussed by Lindmayer and usen,&apos; namely the appearance of a surface potential on silicon as a consequence of the heterojunction formed by the silicon/silicon oxide interface. In the present paper the influence of impurities and structural parameters in silicon oxide in connection with the heterojunction is a particular object of our investigations. I) EXPERIMENTAL The material used was 10 ohm-cm p-type silicon slices with either damaged surfaces (mechanically lapped or polished) or damage-free surfaces (chemically polished). The majority of the slices were oxidized for 1 hr and 20 min at 1250°C in a steam + oxygen atmosphere generated by passing O2 through HzO at 90°C (wet oxygen). This led to oxide layers of about 9000 A. On some slices oxide layers were grown in pure oxygen (dry oxygen). By a photoresist process a set of 20 by 200 mil windows was then etched out from the oxide layer. The pattern of the windows is shown in Fig. 1. In a subsequent process n-type pockets with surface concentrations between 2 x 10" and 5 x 10" cm"3 were formed by phosphorus diffusion. This allowed ohmic contacts between the silicon surface and tungsten probes which for electrical measurements were placed into two adjoining windows and

Jan 1, 1965

By Strathmore R. B. Cooke, Eugene L. Talbot

THE perfluoro acids and derivatives show unusual surface-active properties that qualify them as possible flotation reagents. They lower the surface tension of water from 15 to 20 dynes below that obtainable with the corresponding hydrocarbon compounds.1, 2 Fluorochemicals adsorb very strongly on solid surfaces to give films that exhibit larger contact angles than films of the corresponding hydrocarbons."&apos; * The large contact angles probably result from the terminal —CF3 group. The perfluoro acids are made by electrolysis of the corresponding carboxylic acid in anhydrous hydrogen fluoride.5 From the perfluoro acids many derivatives may be obtained, such as amides, amines, alcohols, xanthates, ethers and esters and others. Since the fluorinated analogues of the conventional hydrocarbon flotation collectors possess enhanced surface properties, a few were selected for testing. Because a survey of all possible minerals and reagent combinations would be out of the question, hematite was chosen to represent a nonsulphide system and pyrite to represent a sulphide system. The fluorinated reagents used in these experiments were prepared in the research laboratories of Minnesota Mining & Mfg. Co. Some were synthesized especially for this research. They are not available cokmercially. Separation of Nonsulphide Ores: The separation of oxides from silica has always been a challenge to the flotation industry because differences in surface properties of the minerals are normally insufficient to produce clean concentrates. Oleic acid," rosin acids,&apos; and amine salts% ave been used to considerable extent to effect separation of metal oxides and silica. The system hematite-silica was chosen to represent the nonsulphides both because of its difficulty of separation and because large tonnages of easily obtainable material are available, such as gravity concentration tailings and nonmagnetic taconites on the Mesabi Range. The wash-ore tailings used here contained approximately 35 pct iron after desliming. Samples of the material used in this work were part of the same lot used by Chang, Cooke, and Huch9 and were prepared in an identical manner. Reagents for Nonsulphide Ores: Since one of the purposes of this investigation was to compare hydrocarbons with fluorocarbons, reagents of known behavior such as oleic acid, and the alkali metal salts of certain resin acids (Dresinates), were established as standards. Hydrocarbons and fluorocarbons of comparable chain length and other experimental fluorocarbons were tried as collectors for hematite. A list of the materials used and the concentrations of their stock solutions are given in Table I. Since silica can be selectively floated from hematite by conventional reagents," a few fluorocarbon reagents were also tried for this purpose. Their composition and concentrations are given in Table 11. Most of these reagents served the dual function of collector and frother. In the case of F-11 flotation did not occur but it served as a frother when F-6 was employed as a collector. Reagent grade sulphuric acid and sodium hydroxide were used to regulate the pH. Deionized water containing less than 0.1 ppm of salts expressed as NaCl was used for all solutions and flotation tests. The pneumatic flotation cell consisted of a 350-ml fritted glass Buechner funnel with a source of filtered air which could be controlled by a needle valve." A 50-g sample of ore and 250 ml of deionized water were added to the flotation cell and stirred slowly. The reagents were added and the pulp was conditioned before air was admitted to the cell. Approximately 15 ml of the pulp were removed for pH determination before flotation was started and were then returned to the system. The pH was again measured after flotation. Air was admitted to the cell until no further flotation occurred or until the character of the float changed markedly. Both the float and the nonfloat products were filtered, dried, weighed. and assayed for iron. The cell was washed in hot water and rinsed with deionized water after each test. Occasionally the cell was cleaned with concentrated hydrochloric acid to remove iron oxide particles from the glass frit. Experimental Results: Above a pH of 8, sodium oleate was an effective collector for hematite. The emulsification of equal parts of heavy fuel oil (20"

Jan 1, 1956

By Margaret V. Doyle, R. W. Powers

INTERNAL friction measurements, carried out as functions of temperature, have been used extensively to obtain data on the mobility of interstitial impurities in the Group V metals, vanadium, colum-bium, and tantalum. For a given frequency of vibration, the internal friction peaks at a temperature which depends principally on the particular metal and interstitial impurity. Relaxation times and corresponding activation energies are determined from a knowledge of such peak temperatures for various vibration frequencies. These experimentally determined relaxation times are related to the average jump frequencies of the interstitial impurity atoms using the model of Snoek1 and can be related to macroscopic diffusion coefficients as shown by Polder.2 In these Group V elements, the impurity whose diffusion rate has been the hardest to pin down by the internal friction technique has been carbon. The experimental difficulties associated with carbon in these metals were not evident in the earliest investigation carried out by Ke on tantalum.3 The carbon peak was thought to occur near 140°C at 1 cps on the basis of the enhancement of the height of this peak measured on specimens which had been coated with colloidal carbon and heated in vacuo at 1200°C. Presumably on the basis of similar evidence, Wert identified a peak also near 140°C at 1 cps in columbium with the diffusion of carbon in that element." Later, the difficulties of admitting carbon into these metals without simultaneously introducing oxygen were pointed out by Ang and Wert- nd by Marx, Baker, and Sivertsen.6 The latter suggested that the peaks attributed to carbon in tantalum and columbium might arise from the presence of traces of oxygen, adventitiously absorbed during the carburization. Such suspicion was confirmed, at least in tantalum, when it was found possible to prepare C-Ta specimens without contamination by oxygen. Specimens sci prepared, aitnough high in carbon content, gave no evidence of a damping peak near 140°C.7 Recently, the authors were able to Show that carbon diffuses in tantalum at a rate only slightly slower than that for nitrogen.8 At 1 cps, the carbon peak lies at 34g °C, only a few degrees above the nitrogen peak at 341 °C. However, the two could be distinguished by a different stability with respect to aging at 400 °C and by a different dependence of peak height on solute concentration. On the basis of this experience with tantalum, it appeared worthwhile to search also for a carbon peak in columbium in the vicinity of the nitrogen peak." In this report, the location of the carbon peak in columbium is made known and its position relative to the nitrogen peak is compared with the authors&apos; previous findings in tantalum. In addition, a second source of internal friction seen only in specimens of very high purity is discussed. Columbium was obtained from the Fansteel Metallurgical Corp. as either 30 or 40 mil diam stock. The manufacturer gives the following analysis as typical of this material: 99.4 pct minimum Cb, 0.10 pct maximum C, 0.5 pct Ta, 0.04 pct Ti, 0.02 pct maximum Si, and 0.01 pct maximum Fe. Wires 13 in. long were degassed near 2200°C for 4 to 16 hr in an ultimate vacuum better than 2.10" mm Hg in an apparatus described previously.8 This treatment reduced the oxygen and nitrogen damping peaks observed in the as-received material to less than 0.0001 in Q-1 above background. The latter value varied somewhat from specimen to specimen in the range 0.0004 to 0.0008, depending chiefly on the wire diameter and the frequency of vibration. The high temperature evacuation left the specimen in a rather soft condition, the Vhn being reduced to 40 from a value near 121 in the as-received conGi~iur~. The gram size was about the diameter of the specimen. After outgassing, specimens were loaded with carbon by absorption of such hydracarbons as methane or ethylene. Carbon was also added to a few speclrnens by heating them at

Jan 1, 1958

By D. C. Hilty, W. Crafts

J. Chipman—It has been my privilege to discuss this work with the authors on several occasions and to observe at first hand the experimental methods employed. I wish, therefore, to emphasize certain points which they have mentioned only briefly with regard to the experimental techniques. The rotating induction furnace as here employed interposes liquid metal between slag and refractory thus preventing the two nonmetallic parts of the system from reaching equilibrium with one another. It is therefore impossible for the metallic phase to be completely in equilibrium with both the slag and the crucible. The metal also acts as a partially permeable membrane allowing certain components, including oxygen, to diffuse from slag to crucible. This transfer results in building up on the face of the crucible a layer of material whose composition is in part dependent on that of the bath. Reactions between the layer and the solid refractory are slow, as evidenced by the rather good life of the crucible. Hence it seems probable that the layer is more nearly in equilibrium with the metal than with the underlying crucible material and that, once it is established under a bath of a given composition, its further reactions with that bath are slow. Additions to slag or bath may be followed by changes in the layer; and time must be allowed for virtual completion of such changes, before it can be assumed that slag and metal are in equilibrium. We may judge from the results reported that, in general, this was the case and that the data represent at least quite close approximations to slag-metal equilibrium. Data on deoxidation and on oxygen solubility are no better than the analytical methods employed. The vacuum fusion method as used by the authors seems entirely adequate for the samples analyzed. I have had frequent occasion to compare results with their laboratory, always with very satisfactory agreement. The determination of aluminum at very low concentrations is perhaps an even more difficult procedure. Here also the colorimetric method used has been worked out with great care and is undoubtedly the most dependable method available. The discrepancy between observed and calculated deoxidation or solubility lines is not to be explained as the result of experimental errors, either in the sampling or analysis of the metal. Nor is it to be blamed upon inaccuracies in the several kinds of indirect data upon which the calculated results were based. It is true that both the observed and the calculated lines admit of some uncertainty as to their exact locations, but the uncertainties are small compared to the wide gap which separates the two lines. The authors have pointed out the real cause of the discrepancy. In all of their experiments the solid phase was not Al2O3 but a mixed oxide containing iron and aluminum. This suggests an extension of the calculated values to include equilibrium with the spinel FeO . A12O3. The free energies of FeO and A12O3 are known, that of the spinel is not. However, it cannot differ greatly from that of its component oxides for even in the more stable spinel, chromite, the free energy of formation from the oxides is less than 10,000 cal. For purposes of calculation we shall call this free energy X and solve for values of X lying between zero and 10,000 cal. The other data required are taken from the forthcoming revision of "Basic Open Hearth Steelmaking" and are given in the following equations in which underlined symbols indicate elements dissolved in liquid steel and the standard concentrations are 1 pct. ?F° at 1600°C, cal ?LA = 2 Al + 3 O; + 107,200 FeO = Fe + 0; + 5,460 FeO + A12O3 = Fe + 2A1 + 4 0; + 112,660 — X The corresponding equilibrium concentrations are shown in fig. 21. The line marked A12O3 corresponds to the first equation, those marked FeO . AL2O3 correspond to the last, with X = 0, 5000 and 10,000 cal, respectively. The two upper lines represent the data of Hilty and Crafts and of Wentrup and Hieber. The points are the observations of Hilty and Crafts in the presence of 0.50 pct Mn.

Jan 1, 1951

By V. G. Leak, R. A. Swalin

The dilhsion of silver and trace concentrations of tin in liquid silver has been rrzeasured in the temperature range from about 975° to 1350°C. The difBsion dala. fil lhe following equations: fov self-diffusion of silver The ratio of DSn to DAg is found to be about 1.34. The higher diffusivity of tin is interpreted in terms of the coullombic repulsion which results from the fact that tin dissolved in silver has a valence of +3 relative to silver. THE phenomenon of diffusion has been well-described theoretically for hard-sphere gases and solids and found to be in good agreement with experimental data for certain gases and solids. Liquid-diffusion phenomena have not been well described theoretically and there is generally a lack of good experimental data. In this investigation self-diffusion and solute diffusion in liquid silver were studied. Silver was chosen as a solvent for two main reasons. First, silver is a noble metal and the atoms are considered to have a spherically symmetric charge field; hence the liquid may be considered to be a random array of approximate hard spheres. Mercury, gallium, and other lower-melting metals were eliminated from consideration since it appears possible that in their liquid states there is some residual long-range order and directional bonding. Second, silver behaves as a monovalent solvent and, while cadmium, indium, tin, and antimony all have nearly the same atomic size, they have chemical valences relative to that of silver of +1, +2, + 3, and +4, respectively. Slifkin, Lazarus, and coworkers1-5 investigated the diffusion of these solutes in solid silver and found that their diffusion rates increased with an increase of the excess valence of the solute. In the solid state the diffusion-rate increase was calculated to be due to a change in local modulus of the solvent caused by the excess valence of the solute.1"3 For the present investigation it was planned to determine the effect of valence upon solute diffusion in liquid silver. It was deduced that a coulombic repulsion between solute and solvent might be responsible for larger volume fluctuations in the vicinity of the solute thereby enhancing the diffusion of the solute atoms. Tin was the first solute investigated and was chosen for experimental convenience. If an excess-valence diffusion effect exists in the liquid state, the solute tin with its excess valence of + 3 might show a large enough effect to distinguish it from the self-diffusion of silver in silver. The silver self-diffusion data were obviously required as a base line for comparison. In addition silver self-diffusion was investigated with a view toward examining the data in connection with the Sutherland- Einstein: Coheen-Turnbull,7 and swalin8 theories of diffusion in liquids. I) EXPERIMENTAL TECHNIQUES The diffusion coefficients for tin and silver in liquid silver were determined in separate experiments using the capillary-reservoir method of Anderson and saddingtono but following closely the experimental techniques outlined by Ma and Swa1in. The radioactive alloy bath was prepared by plating either tin-113 or silver-110 m isotope* onto 99.999 *Isotopes obtained from Oak Ridge National Laboratory. pct Ag rods.* The silver and isotope were melted *Silver obtained from Cominco Co. and mixed in a graphite crucible under a purified argon atmosphere, then outgassed for capillary filling. Some of the fused-silica capillaries were filled individually as reported by Ma and Swalin, but most were filled in a different manner. A long piece of capillary tubing was sealed off on one end and held in the system so that the open end was just above the surface of the molten alloy. The system was evacuated, the open end submerged into the alloy, and argon was admitted into the system up to atmospheric pressure. The molten alloy was forced up the capillary several inches where it solidified and was subsequently cut into segments of the proper length for diffusion annealing. The apparatus for diffusion annealing was the same as that used for capillary filling except that a Pt—Pt, 10 pct Rh therinocouple was placed in the solvent bath in order to accurately measure the temperature during the run. A diagram of the dif-

Jan 1, 1964