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By M. D. Banus, M. B. Bever, A. K. Jena

The heals of formation at 78", 195, and 273°K of the ternary compound h3SbTe2 based on the elements and based on the binary compounds In Sb and [inTe have been measured. The heats of formation at these temperatlcres of the binary compounds In Sb and In Te based on the elements have also been determined. Heal contents and free energies of the three compounds have been calculated from 0° lo 80I)°K. The free energies of joyrrzalion, heats of formations, and entropies of formation at 298°K have also been calculated. The results shown that the tertnary compound is metastable with vespecl to InSh and ln Te below 696 °K. bul is slable above that temperature. The weaker bonding of results in a positice entropy of formation which with incrensirzg temperature makes increasing negative conlvihtclions to the free energy and above 696°K renders the compound slable. THE ternary compound In3SbTez occurring in the quasi-binary system In Sb- In Te' forms on cooling at 829°K by a peritectic reaction.' Observations at 673" and 573 K have shown that this ternary compound decomposes slowly into the binary compounds InSb and1n~e.l'' It has not been possible to analyze the metastable behavior of the ternary compound because up to the present time data on its thermodynamic properties have been lacking. Some information on the binary compounds, however, is available. The heat of formation of InTe at 273°K and its free energy at 673°K are kn~wn.~'~ The heats of formation of InSb at 78", 273', 298", and 723°K have been measured5-' and its heat capacity between approximately 12" and 300"Kg9l0 is also known. In the investigation reported here the heats of formation at 78% 195% and 273°K of the ternary compound In3SbTez have been measured. The heats of formation of the binary compounds InSb and InTe at these temperatures have been obtained by combining new calorimetric results with previously published data. The heat contents and free energies of the three compounds at various temperatures from 0" to 800°K have been calculated. Against the background of this information, the metastability of the ternary compound will be discussed. 1) EXPERIMENTAL 1.l) Preparation of Specimens. The materials used consisted of the elements indium, antimony, and tellurium, the binary compounds InSb and InTe, and the ternary compound In3SbTez. The elements, obtained from American Smelting and Refining Co., had a nominal purity of 99.999+ pct. The compound InSb was Cominco semiconductor grade; the compound InTe was prepared from the elements by melting under a vacuum of 10-h m Hg followed by slow cooling. Three batches of specimens of the compound In3SbTez were used. One batch was prepared by melting appropriate amounts of the elements in an evacuated and sealed Vycor tube. The melt was held at approximately 100°K above the liquidus for about 8 hr, shaken repeatedly, and quenched into a mixture of ice and water. The specimen was annealed in vacuum at 760°K for 4 weeks. In preparing a second batch, a mixture of the component elements was melted and quenched in water. The resulting ingot was powdered. The powder was pressed into pellets, which were annealed in vacuum at 748" to 773°K for 4 weeks. A third batch was prepared in the same manner as the second, except that the starting materials were InSb and InTe rather than the elements. Metallographic examination of samples of the three batches and X-ray diffraction examination of a sample of the second batch did not reveal evidence of microsegregation or a second phase. The results obtained with the three batches showed no systematic differences. 1.2) Calorimetry. The calorimetric method has been described in detail." Samples of the compound In3SbTez, mechanical mixtures of InSb and InTe in the proportion of 1:2, and mechanical mixtures of indium, antimony, and tellurium in the proportion of 3:1:2 were added to a bismuth-rich bath at 623°K in a metal-solution calorimeter. These additions were made from 78°K (liquid nitrogen), 195°K (dry ice and acetone), and 273°K (ice and water). The heat effects of the additions were measured. The difference in the heat effects of the additions of a compound and the additions of the mixtures of its constituents, adjusted for differences in the concentration of the bath, is the heat of formation of the compound. In the concentration range not exceeding 1.5 at. pct solute, the heat effect of the additions was a linear function of concentration. The heat of formation refers to the temperature from which the additions were made, namely, 78", 195", or 273°K. Several calibrating additions were made in each calorimetric run. The calculated heat capacity of the calorimeter and hence the calculated heat effects of the additions of samples depend upon the values adopted for the heat contents of the calibrating substance. In this investigation bismuth at 273°K was used and a value of 4.96 kcal per g-atom was taken for (HGZ3"k . 2) RESULTS AND DISCUSSION 2.l) Heats of Formation. The heats of formation of the ternary compound In~SbTez from the component elements indium, antimony, and tellurium and from

Jan 1, 1968

By T. R. A. Davey

IN 1947 the author became interested in the fundamental aspects of the desilverizing of lead by zinc, conducted some experimental work, and searched the technical literature for all available fundamental data. Since then a revival of interest in the subject in Europe resulted in the appearance of quite a number of papers. It became evident that it would be more profitable to collect together and examine thoroughly the results of various workers, than to attempt to duplicate the experimental determinations. There are many inconsistencies in the various publications, and it is opportune to review at this time the present status of knowledge on the Ag-Pb-Zn system. There is also a need for a clear description, in fundamental terms, of the various desilverizing procedures. This paper is presented in four sections: 1—There is an historical review of the origins of the Parkes process, of the results of many attempts to find a satisfactory fundamental explanation for the phenomena, and of the modifications proposed to date. 2—A diagram of the Ag-Pb-Zn system is presented. This is believed to be free of obvious inconsistencies or theoretical impossibilities, although thermodynamic analysis subsequently may reveal errors. 3—The fundamental bases of the various desilverizing procedures, which have been used up to the present day, are described; and a new method is suggested for desilverizing a continuous flow of softened bullion in which the bullion is stirred at a low temperature in two stages producing desilverized lead at least as low in silver as that from the Williams continuous process and a crust which, on liquation, yields a very high-silver Ag-Zn alloy. 4—A suggestion is made for the revival of de-golding practice, following a recently published account which does not seem to have attracted the attention it deserves. The terms "eutectic trough" and "peritectic fold" as used in this paper are synonymous with "line of binary eutectic crystallization" and "line of binary peritectic crystallization" as used by Masing.' The German literature on ternary and higher systems is rather extensive and a fairly general system of nomenclature has arisen, whereas in English usage the corresponding terms are not as well established. For this reason the meanings of terms used in this paper, together with the equivalent German terms, are given as follows: 1—Eutectic trough—eutektische rinne: line at which a liquid precipitates two solids S1 and S2 simultaneously. If the composition of a liquid which is cooling reaches this line, it then follows the course of this line until a eutectic point is reached, or until all the liquid is exhausted. The tangent to the eutec-tic trough cuts the line joining S1S2. 2—Peritectic fold—peritektische rinne: line at which a solid S1 and a liquid L transform into another solid S2. If the composition of a liquid which is precipitating S1 reaches the line, on further cooling only S2 is precipitated. The liquid composition moves from one phase region (L + S1) into the other (L + S2), and does not follow the course of the boundary. The tangent to the peritectic fold cuts the line S1S2 produced nearer S,. 3—Liquid miscibility gap, or conjugate solution region—mischungslucke: the region within which two liquid phases coexist in equilibrium over a certain range of temperature. A system whose composition is represented by a point in this region comprises one liquid at high temperature; then as the temperature is progressively reduced, two liquids, one liquid and one solid, one liquid and two solids, and finally three solids. 4—Liquid miscibility gap boundary—begrenzung der flussigen mischungsliicke: the line along which the surface of the miscibility gap dome, considered as a solid model, intersects the surrounding liquidus surfaces. 5—Tie lines—konoden: lines joining points representing the compositions of two liquids, a liquid and a solid, or two solids, in equilibrium. In binary systems the only tie lines customarily drawn are those through invariant points, e.g., through the eutectics of the Pb-Zn and Ag-Pb systems, or the various peritectics of the Ag-Zn system, as in Figs. 1 to 3. In ternary systems it is desirable to draw sufficient tie lines to indicate the slopes of all possible tie lines. 6—Ternary eutectic point—ternares eutektikum: point at which liquid transforms isothermally to three solids, S1, S2, and S Such a point can lie only within the triangle 7—Invariant peritectic (transformation) point— nonvariante peritektische umsetzungspunkt: (a) — On the miscibility gap boundary, the point at which two liquids and two solids react isothermally so that L, + S, + L, + S2. (b)—On the eutectic trough, the point at which a liquid and three solids react iso-thermally so that L + S, + S2 + S3. Such a point must lie on that side of the line joining S,S which is further from S,. (c)—A further possibility, not found in this ternary system, is that the point is at the intersection of two peritectic folds when the reaction concerned is L + S, + S, + S Historical Introduction Karsten discovered in 1842 that silver and gold may be separated from lead by the addition of zinc.2 Ten years later Parkes used this fact to develop the well known desilverizing process which bears his

Jan 1, 1955

By S. Usui, I. Iwasaki

The effect of pH on the adsorption of dodecylamine at the mercury-aqueous solution interface was investigated by differential capacity and electrocapillary measurements. With dodecylammonium acetate, the differential capacity curves showed two desorption peaks in the cathodic branch with their relative intensities varying with the solution pH. With dodecyltrimethylammonium chloride, only one cathodic de-sorption peak was observed in the same pH range. Through thermodynamic analysis of the electrocapillary curves, the adsorption density of undissociated amine was evaluated separately from that of aminium ion. The adsorption densities of the un-dissociated amine and of the total amine increased with increasing pH. The ratio at the interface of undissociated amine to aminium ion was several orders of magnitude greater than the ratio in the solution and increased with increasing pH. The potential at the closest distance of approach of counter ions to the mercury surface was compared with values of zeta potential on quartz previously reported. The most important variable in the flotation separation of minerals is probably the pH of the pulp, and a number of theories have been proposed to explain its effect on the condition of the mineral surfaces, on the dissociation of collectors and of inorganic and organic species (accidentally present or intentionally added) in the pulp, and on the mineral-collector interaction. In the development of a theoretical background for oxide flotation systems, an experimental approach based on electrokinetic measurements has been of much value, although the effect of pH becomes confounded since it governs both the electrochemical conditions of the oxide surface and the dissociation of the collector. For investigation of the adsorption behavior of long-chain collectors on oxide minerals, however, electrokinetic potential measurements are the most widely used technique. Hydrogen and hydroxyl ions are found to be the potential determining species, thereby governing the interfacial electrical conditions. The electrostatic interaction between the charged mineral surfaces and ionized collectors is regarded as the driving force for the adsorption of the collectors. An association of alkylamine collectors adsorbed on quartz surfaces has been postulated from streaming potential measurements, and a term "hemi-micelles" has been proposed.' The possibilities of coad-sorption of undissociated amine along with aminium ion has been inferred from contact angle measurements? and from adsorption studies.~ Electrochemical titration as applied to silver sulfide provides a more quantitative approach to the analysis of the electrical double layer at an ionic solid-solution interfaceqG and the electrochemical evidence for the adsorption of amine at pH 4.7 indicates a specific affinity of dodecylammonium ion towards silver sulfide surfaces, whereas at pH 9.2 the adsorbed species might be free arnine." A combination of differential capacity and electrocapillary measurements on a dropping mercury electrode was reported to be a sensitive method of provid- ing reliable information on the adsorption behavior of dodecylammonium acetate (DAA) at a natural (near neutral) pH.? It was also shown that there were striking similarities in the properties of the double layer and in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide. The effect of pH on the differential capacity curves at a mercury-sodium fluoride solution interface has been investigated by Austin and Parsonss who reported that between pH 7 and pH 11 there was very little effect. In the present paper, the adsorption behavior of DAA was investigated as a function of pH through differential capacity and electrocapillary measurements and the information gathered was correlated with that available in literature on quartz and silver sulfide. Experimental The apparatus and the method used for determining the differential capacity and the electrocapillary curves were identical to those described previously.' The ionic strength of the supporting electrolyte was fixed at 0.1 M with potassium fluoride, and the pH of the solution with potassium hydroxide. Only the neutral to alkaline range was covered in order to avoid the dissolution of the glass vessel with hydrofluoric acid. Results In Fig. 1 the differential capacity has been plotted against the applied potential at a DAA concentration of 10-' M at three different pH values. The curves are characterized by one capacity peak in the anodic branch, by two capacity peaks in the cathodic branch, and by a marked depression in capacity between the peaks. The depression indicates an adsorption of the arnine in this potential range. One of the cathodic peaks appears at pH 7.3 near -1.4 v and decreases with increasing pH. The other appears at pH 8.9 near —1.2 v and increases with increasing pH. At pH 9.6 only the latter peak is observed. Beyond the cathodic peaks, all the curves tend to converge with the curve in the absence of DAA, implying that two different species are being desorbed in this potential region. The anodic peak near 0.0 v increases markedly with increasing pH. The well-defined anodic peaks at pH 8.9 and 9.6 were accompanied by an appreciable increase in the current flow (in excess of O.luA), and, therefore, is a "pseudo-capacity"'" due to a

Jan 1, 1971

By A. R. Calawa, T. C. Harman, M. Finn, P. Youtz

A study has been made of the growing, annealing, and diffusion parameters in PbSe, Pb1-ySnySe, and Pb1-xSnxTe. Single crystals of these materials have been grown using the Bridgman technique. For all of the above materials the as-grown crystals are p type with high carrier densities. To reduce the carrier concentration and increase the carrier mobility, the samples are annealed either isothermally or by a two-zone method. From isothermal anneals, the liquidus-solidus boundary on the metal-rich side of the stoichiometric composition has been obtained for some alloys of Pb1-xSnxTe and on both the metal- and seleniunz-rich sides for PbSe and alloys of Pbl-ySnySe. In Pbo.935 Sno.065 Se carrier concentrations as low as 5 x1016 Cm-3 and mobilities as high as 44,000 sq cm v-1 sec-1 at 77°K have been obtained. Inter diffusion parameters mere also studied. The ddiffusion experiments mere identical to the isothermal or two-zone annealing experiments except that the samples were removed prior to complete equilibration. The resulting p-n junction depths were determined by sectioning and thermal probing. Inter diffusion coefficients for various temperatures were calculated for both PbSe and Pb0.93Sn0.0,Se. RECENTLY, there has been considerable interest in the PbTe-SnTe and PbSe-SnSe alloys with the rock salt crystal structure. The unusual feature of these systems is the variation of energy gap EG with composition. Several investigations1-3 have shown that EG for the lead chalcogenides decreases as the tin content increases, goes through zero, and then increases again with further increase in tin content. The possibility of obtaining an arbitrary energy gap by selecting the composition is an especially attractive feature of these alloys for applications involving long-wavelength infrared detectors and lasers. In addition, some unusual magneto-optical, galvanomagnetic, and thermomag-netic effects should occur for alloys with low band gaps. If uncompensated low carrier density crystals can be obtained, then a small carrier effective mass, a large dielectric constant, and the resultant high carrier mobility should yield enormous effects at low temperature in a magnetic field. The relative variation of the energy gap with pressure should also be very large for these low gap materials. The primary purpose of this paper is to provide some information concerning the preparation of low carrier concentra- tion, high carrier mobility, and homogeneous single crystals with a predetermined alloy composition. I) DETERMINATION OF ALLOY COMPOSITIONS In all of the work described in this paper, the composition of lead and tin chalcogenides in the alloys was determined by electron microprobe analysis. Separate X-ray spectrometers are used to make simultaneous intensity measurements of the Pb La1 and Sn La1 lines emitted by the sample under excitation by a beam of 25 kev electrons focused to a spot about 2 µm in diam. These intensities are compared to the intensities of the same lines emitted by standards under the same conditions. The standards used are the terminal compounds of each pseudobinary system, i.e., PbTe and SnTe for Pbl-xSnxTe alloys, PbSe and SnSe for Pbl-ySnySe alloys. The composition of the sample is then obtained from theoretical calibration curves which relate the weight fractions of lead and tin in the alloy to the measured ratios of X-ray intensities for the sample and the standards. The lead and tin calibration curves for each alloy system were calculated by using corrections for backscattered electrons,4 ionization,5 and absorption,6 and assuming that the atom fraction of tellurium or selenium in the sample and standards is exactly +. Results obtained by using the microprobe are in good agreement with those obtained by wet chemical analysis. II) CRYSTAL GROWTH FROM THE VAPOR Early work on the vapor growth of PbSe was carried out by Prior.7 He used small chips of Bridgman-grown single crystals as the source material and frequently converted the whole charge of a few grams into one crystal. In the present work, vapor growth occurred using a metal-rich or chalcogenide-rich two-phased alloy powder as the source material. Small, nearly stoichiometric crystals are formed on the walls of the quartz tube. The procedure will now be described in detail. Initially, a 100-g charge containing (metal)o.51(chalco-genide)o 49 proportions or (metal)o.49(chalcogenide)o. 51 proportions of the as-received elements in chunk form are placed in a fused silica ampoule. After the ampoule is loaded, it is evacuated with a diffusion pump and sealed. The sealed ampoule is placed in the center of a vertical resistance furnace. The region containing the ampoule is heated to about 50°C above the liquidus temper-ature for the particular composition used. After about one-half hour at temperature, the elements are reacted and the molten material homogenized. The ampoule is quenched in water. The quenched ingot is crushed to a coarse powder for vapor growth experiments and to a fine powder for the isothermal annealing experiments which are discussed in a later section. Vapor growth experiments were carried out using the powdered, metal-rich or chalcogenide-rich alloys

Jan 1, 1969

By C. S. Sivaramakrishnan, Manjit Singh, Rajendra Kumar

Regarding liquid nzetals structurally as a suspm-sion of clusters , having derivated solid-state coordination, in truly liquid atoms, the recently developed Kuvlar-Samarin technique of centrifuging- in liquid state enabled the determination of the cluster sizes inAl-Cu mid Pb-Sn systems. It is shown that the colutne fraction of the clusters does not exceed 9 pct and the energy of their formation in Al-Cu is about 5.5 kcal per g-atom and in Pb-Sn eutectic alloys about 25 kcal per y-atoni. STRUCTURAL investigations of liquid state have principally followed the following three courses: i) studies with X-ray, electron, or neutron diffraction; these investigations have shown that there is a certain amount of regularity in the structure of liquid metals which can be defined by a coordination number and that the structure is a derived function of that in the solid state; ii) thermodynamical investigations which are based on the concept of ideal behavior; these describe the liquid state in terms of free-energy values and other thermodynamic functions; although these investigations are of help in the study of the general effects of alloying, they do not provide any structural insight into the precise atomic distribution in liquid state; iii) measurements of surface tension and viscosity; although it is natural to expect that the viscosity is related to the structure in liquid state, these investigations have so far only provided information which can be used by the foundry technologists and has been little utilized in formulating models of the structure of liquid state. As it happens, investigators in the three groups have worked almost independently of each other and there is practically no structural correlation between the results of one group with those of another. The purpose of the present paper is to indicate that the experimentally measured parameters of these three groups of research are closely related to the structure in the liquid state. STRUCTURE OF LIQUID METALS Although atomic distribution in solid and gaseous states is rigorously known, that of the liquid state is only appreciated on the fringes. There is no universal model of atomic distribution in liquid state, but two diverse models are at present hotly contested. The first, largely expounded by ~ildebrand,' regards the liquids as condensed gas since many of their properties and much of their behavior can be adequately described by regarding them as fluids. The second mode12j3 considers that some form of near-solid as- sociation of large number of atoms exists in the liquid state. On the other hand, ~ernal' was able to predict rather precisely the radial distribution functions in liquids on the basis of statistical geometric approach which considered that liquids are "homogeneous, coherent, and essentially irregular assemblage of molecules containing no crystalline regions or holes large enough to admit another molecule". He introduced the concept of pseudonuclei in the otherwise random structure as aggregates of closely packed tetrahedra which gradually merge into irregularity and continually replace each other. To what extent the pseudonuclei can be regarded as regions of near-solid association is indefinite but Bernal suggested that the concept of pseudonuclei can be compromised with the latter model if the near-solid associations are regarded as extremely dense and not necessarily crystalline. The difficulty in projecting the structure of liquid metals arises because they exhibit duplicity of character as some of their properties are closer to those of crystalline solids and others to fluids. There is an increasing tendency to discuss the structure of liquid metals in terms of the second concept according to which the structure of liquid metals may be conceived as consisting of i) clusters of atoms where the aggregation is a close derivative of that in the crystalline state, ii) individual atoms which behave like true liquids in respect to degrees of freedom and iii) excess number of vacancies. It is noteworthy that the introduction of only 5 pct vacancies is sufficient to transform crystalline matter into the liquid state. At any instant of time thermodynamic equilibrium exists between i, ii, and iii, but the relative proportion of the clusters and random atoms is not known. That this is so can be appreciated by the fact that, when liquid metal is rapidly cooled, liquid state vacancies may condense in the form of dislocation loops and vacancies in excess of their equilibrium number in solid state. These dislocation loops have been observed in thin foils of aluminum prepared from rapid cooled aluminum. As temperature increases above melting point the number and volume fraction of clusters decrease but those of vacancies and random atoms increase. Clusters are transient in nature. In pure metals the cluster is an aggregation of the metal itself. In alloys, however, the nature of the cluster largely depends on the interaction between solvent and solute atoms. If the interaction between unlike atoms is greater than between like atoms: the clusters are then aggregates of unlike atoms. Examples of this kind of system are A1-Cu, Mg-Pb, and so forth, i.e., systems which exhibit negative departures from the Raoult's law. In systems where the interaction between unlike atoms is smaller than be-

Jan 1, 1968

By S. Jana, C. M. Wayman

The reverse transformation of bcc martensite to the fcc phase was studied in an Fe-33.95 wl pct Ni alloy by nzeans oj dilatometry, melallography, and electron microscopy. Upon "slozc" heating (-1°C per min) length cJmnge us temperature plots showed u gradual contracLion over the temperature range 200" to 280"C ,followed by a more abrupt contraction beginning a1 -280°C. Howet,ev, zchen the heating rate was increased -4°C per tnin, no gradual contraction was observed and only the abrupt contraction starting at -2BO"C was found. Thus on slower heating- the AS "temperature" for the subject alloy, unlike the MS temperature, is better defined as a range of temperatures. Both optical and transmissiorl electron microscope observations showed that some of the martensite plates exizibited a partial loss of transformation twins during reversal. The midvib region of the martensite plates disappeaved relatively early duirng the reversal. Metallographic observations slowed that the earliest detectable stage of the rezlerse tvansforrvration begins (axd Moues inulardly) at The Martensens i te - parent interface. At higher temperatirres, the. formation of martensitically reversed jcc plates within the bcc martensite plales was observed. It is concluded that the reverse transformation consists of a diffusion less process (martensitic); but this is ps-obably aided by a prior or simultaneous dijjusiorz-comltvolled process, at leasl in the case of slower heat-ing' experiments. ALTHOUGH numerous investigations have dealt with the parent-to-martensite ("forward") transformation (fcc — bcc) in Fe-Ni alloys, comparatively little is reported on the ("reverse7') martensite-to-parent transformation.'-4 Even though such reverse transformations have been studied in detail in some nonferrous systems, one of the difficulties of studying the reverse transformation in most ferrous mar-tensites is that the martensite decomposes by tempering during heating. However, carbonless Fe-Ni alloys do not exhibit this difficulty since the transformation in these alloys is completely reversible. The present investigation represents an attempt to shed more light on the nature and mechanism of the martensite-to-parent transformation. 1) EXPERIMENTAL PROCEDURE 1.1) Alloy Prepatation. Fe-Ni alloys of compositions near 34 wt pct Ni were prepared from zone-refined iron (99.994 wt pct Fe) and high-purity nickel (99.999 wt pct Ni) by induction melting in recrystallized alumina crucibles in an argon atmosphere, with prior vacuum evacuation to 10"3 mm Hg. The alloys were homogenized by induction stirring in the molten state for 5 min. After solidification, the alloys were further homogenized in evacuated quartz capsules for 96 hr at 1230°C. 1.2) Dilatometry. Slices of the ingot were hot-forged (750°C in air) into approximate rod form and these specimens were then hot-swaged (750°C in air) into long cylindrical rods 0.55 mm diam. From the rods, specimens about 1 in. long were cut. These were then vacuum-annealed for 24 hr at 1200°C, cooled to room temperature, and subsequently transformed to martensite in liquid nitrogen (whereby about 40 pct transformation was obtained). Dilatation measurements were made by observing length changes in a vacuum dilatometer with an externally mounted LVDT sensing element. 1. 3) Preparation of Electron Microscope Specimens. Slices of the ingots were cold-rolled (with intermediate vacuum anneals) to -0.020 in. Out of these rolled sheets, specimens (about 1 by 1 in.) were cut. These were then vacuum-annealed, transformed to martensite by cooling in liquid nitrogen, and subsequently heated from room temperature to various temperatures to effect either partial or complete reverse transformation. These specimens were then chemically polished to 0.002 in. in l:l HsOz (30 pct) and &PO4 (85 pct) solution, and thinned to electron transparency in an electrolyte consisting of 150 g CraOs, 750 ml glacial acetic acid, and 30 ml ~~0.~ Observations were made with a 100-kv Hitachi HU-11 electron microscope equipped with an HK-2A tilting device. 1.4) Optical Microscopy. Metallographic observations were made with a Leitz MM5 metallograph on the same 0.020-in. sheet specimens as were used for electron microscopy and on bulk specimens which were 0.2 in. or more on a side. The chemical thinning solution when cooled below 20°C also served as an etchant for this alloy. Observations of surface relief were made with a Zeiss interference microscope employing a Thallium light source of wavelength 0.54 p. Specimens for interference studies were prepared by two-stage polishing on Buehler vibromet polishers using 0.3 and 0.05 p alumina abrasives. 2) EXPERIMENTAL RESULTS 2.1) Comparison of the MS,AS, and Af Tempera-tures wTth Previous Re sults. The AS aLd Af tempera -tures of several Fe-Ni alloys were determined dila-tometrically. The MS temperatures of the same alloys were determined by continuously lowering the temperature using a mixture of isopentane and liquid nitrogen and observing the highest temperature at which a prepolished specimen showed surface upheavals. For the present the As temperature is defined as the temperature at which an abrupt decrease in length occurs in the dilatation plot. The Ms,As7 and A determinations in the present investigation and those of Kaufman

Jan 1, 1968

By William D. Klopp, Joseph R. Stephens

A substantial reduction in the 300°F ductile-to-brittle transition temperature for unalloyed chromium was achieved in alloys from systems which resemble the Cr-Re system. These alloy systems include Cr-Ru, Cr-Co, and Cr-Fe. Transition temperatures ranged from -300° F for Cr-35 at. pct Re to -75°F for 0-50 at. pct Fe. The ductile alloys have high grain gvowth rates at elevated temperatures. Also, Cr-24 at. pct Ru exhibited enhanced tensile ductility at elevated temperatures, characteristic of superplas-ticity. It is concluded that phase relations play an importarlt role in the rhenium ductilizing effect. The ductile alloys have compositions near the solubility limit in systems with a high terminal solubility and which contain an intermediate o phase. The importance of enhanced high-temperature ductility to the rhenium ductilizing effect is not well understood although both may have common basic features. CHROMIUM alloys are currently being investigated for advanced air-breathing engine applications, primarily as turbine buckets and/or stator vanes. The inherent advantages of chromium as a high-temperature structural material are well-known1 and include its high melting point relative to superalloys, moderately high modulus of elasticity, low density, good thermal shock resistance, and superior oxidation resistance as compared to the other refractory metals. Additionally, it is capable of being strengthened by conventional alloying techniques. The major disadvantage of chromium is its poor ductility at ambient temperatures, a problem which it shares with the other two Group VI-A metals, molybdenum and tungsten. For chromium, the problem is further amplified by its susceptibility to nitrogen em-brittlement during high-temperature air exposure. In cases of severe nitrogen embrittlement, the ductile-to-brittle transition temperature might exceed the steady-state operating temperature of the component. The low ductility of chromium would make stator vanes and turbine buckets prone to foreign object damage. The present work was directed towards improvement of the ductility of chromium through alloying, with the anticipation that any improvements so obtained might be additive to strengthening improvements achieved through different types of alloying. The alloying additions for ductility were selected on the basis of the similarity of their phase relations with chromium to that of Cr-Re. The reduction in the ductile-to-brittle transition temperatures of the Group VI-A metals as a result of alloying with 25 to 35 pct Re is well established.a4 the temperature range -300" to 750° F. This phenomenon is commonly referred to as the &apos;<rhenium ductilizing effect"; this term is also used to describe systems in which the ductilizing element is not rhenium. Other alloy systems which have recently been shown to exhibit the rhenium ductilizing effect include Cr-Co and c-Ru.= In order to explore the generality of this effect, alloys were selected from systems having phase relations similar to that of Cr-Re, primarily a high solubility in chromium and an intermediate o phase. The following compositions were prepared: Cr-35 and -40Re; Cr-10, -15, -18, -21, -24, and -27 pct Ru; Cr-25 and -30 pct Co; Cr-30, -40, and -50 pct Fe; Cr-45, -55, and -65 pct Mn. Seven other systems were also studied which partially resemble Cr-Re. These systems have extensive chromium solid solutions or a complex intermediate phase, not necessarily o. The compositions evaluated include the following: Cr-20 pct Ti; Cr-15, -30, and -45 pct V; Cr-2.5 pct Cb; Cr-2.5 pct Ta; Cr-20 pct Ni; Cr-6, -9, -12, and -15 pct 0s; Cr-10 pct Ir. The compositions of alloys in these systems were chosen near the solubility limit for the chromium-base solid solutions, since in the Group VI-A Re systems, the saturated alloys are the most ductile. These alloys were evaluated on the basis of hardness, fabricability, and ductile-to-brittle transition temperatures. In addition to the studies of alloying effects on ductility, an exploratory investigation was conducted on mechanical properties at high temperatures in Cr-Ru alloys EXPERIMENTAL PROCEDURE High-purity chromium prepared by the iodide deposition process was employed for all studies. An analysis of this chromium is given in Table I. Alloying elements were obtained in the following forms: Commercially pure powder — iridium, osmium, rhenium, and ruthenium. Arc-melted ingot — titanium and vanadium. Electrolytic flake — iron, manganese, and nickel. Sheet rolled from electron-bearn-melted ingot — columbium and tantalum. Electron-beam-melted ingot — cobalt. Sheet rolled from arc-melted ingot — rhenium. All alloys were initially consolidated by triple arc melting into 60-g button ingots on a water-cooled hearth using a nonconsumable tungsten electrode. The melting atmosphere was Ti-gettered Ar at a pressure of 20 torr. The ingots were drop cast into rectangular slabs and fabricated by heating at 1470" to 2800° F in argon followed by rolling in air. Bend specimens measuring 0.3 by 0.9 in. were cut from the 0.035-in. sheet parallel to the rolling direction. The specimens were annealed for 1 hr in argon, furnace cooled or water quenched, and electropolished prior to testing. Three-point loading bend tests were conducted at a crosshead speed of l-in. per min over

Jan 1, 1969

By R. J. Fruehan, F. D. Richardson

Electrochemical measurements have been made of the activity of oxygen in copper and its alloys with silver and tin at 1100" and 1200°C. The galvanic cell used was Pt, Ni + NiO/solid ellectrolyte/[O] in metal, cermet, Pt The results do not support any of the equations so far designed for predicting the activities of dilute solutes in ternary solutions from activities in the corresponding binaries. If, however, a quasichemical equation is used with the coordination number set to unity, agreement between observed and calculated activities shows that this empirical relationship can be useful over a fair range of conditions. SEVERAL solution models have been proposed for predicting the activity coefficients of dilute solutes in ternary alloys from a knowledge of the three binary systems involved. Alcock and Richardson1 have shown that a regular model, and a quasichemical model,&apos; in which the dissolved oxygen is coordinated with eight or so metal atoms, can reasonably predict the behavior of both metal and nonmetal solutes when the heats of solution of the solute in the separate solvent metals are similar. But when this is not so, neither model gives useful predictions unless coordination numbers of one or two are assumed. Wada and Saito3 subsequently adopted a similar model to derive the interaction energies for two dilute solutes in a solvent metal. Belton and Tankins4 Rave proposed both regular and quasichemical type models in which the oxygen is bound into molecular species, such as NiO and CuO in mixtures of Cu + Ni + 0. However, their models have only been tested on systems in which the excess free energies of solution of the solute in the two separate metals differ by a few kilocalories. Ope of the reasons why more advanced models have not been proposed is because few complete sets of data exist for ternary systems in which the solute behaves very differently in the two separate metals. For this reason measurements have been made of the activities of oxygen dissolved in Cu + Ag and Cu + Sn. Measurements on both systems were made by means of the electrochemical cell, Pt, Ni + NiO/solid electrolyte/O(in alloy), cermet,Pt [1] The activity of oxygen was calculated from the electromotive force and the standard free energy of formation of NiO, which is accurately known.5 Before investigating the alloys, studies were made of oxygen in copper to test the reliability of the cell and to check the thermodynamics of the system. Of the previous studies those by Sano and Sakao,6 Tom-linson and Young,7 and Tankins et al.8,7 have been made with gas-metal equilibrium techniques; those by Diaz and Richardson,9 Osterwald,10 wilder," Plusch-kell and Engell,12 Rickert and wagner,13 and Fischer and Ackermann14 have been made by electrochemical methods. EXPERIMENTAL The apparatus employed was the same as described previously,9 apart from slight modification. The molten sample of approximately 40 g was held in a high grade alumina crucible 1.2 in. OD and 1.6 in. long. The solid electrolytes were ZrO2 + 7½ wt pct CaO and ZrO2 + 15 wt pct CaO; the tubes 4 in. OD and 6 in. long were supplied by the Zirconia Corp. of America. They were closed (flat) at one end. In one experiment with Cu + O, both electrolytes were used in the cell at the same time. The reference electrodes inside the electrolyte tubes consisted of a mixture of Ni + NiO. They were made by mixing the powdered materials and pressing them manually into the ends of the tubes, with a platinum lead embedded in them. The tubes were then sintered overnight in the electromotive force apparatus at 1100°C. By sintering the powders inside the tubes (instead of using a presintered pellet9) better contacts were obtained between the electrolyte, the powder, and the platinum lead. Troubles arising from polarization9 were thus much reduced. The electromotive force was measured by a Vibron Electrometer with an input impedence of 1017 ohm; the temperature was measured with a Pt:13 pct Rh + Pt thermocouple protected by an alumina sheath. The couple was calibrated against the melting point of copper. The cermet conducting lead of Cr + 28 pct Al2O3, previously found to be satisfactory9 for use with Cu + 0 was also found satisfactory with Cu + Ag + 0 and Cu + Sn + 0. Superficial oxidation was observed, but it did not interfere with the working of the cell. The reaction tube containing the cell was closed at each end with cooled brass heads and suspended in a platinum resistance furnace. The tube was electrically shielded by a Kanthal A-1 ribbon which was wound round it, and the ribbon was protected by a N2 atmosphere between the furnace and the reaction tube. The cell was protected by a stream of high purity argon which was dried and passed through copper gauze at 450°C and titanium chips at 900°C. All the metals used were of spectrographic standard. Procedure. In studies of the system Cu + 0, be-

Jan 1, 1970

By J. B. Hess, C. S. Barrett

TO reach equilibrium between different phases in cobalt-rich alloys requires prohibitively long annealing cobalt-richalloystimes when temperatures are below about 700°C. The fact that a transformation from face-centered cubic to close-packed hexagonal readily tered takes place at temperatures below this in the cobalt-rich solid solutions is not an indication that thermally activated processes occur at an appreciable rate, for the transformation is well established as martensitic in nature. Wide divergence between heating and cooling experiments and high sensitivity to prior heat treatment make it difficult to judge temperatures of equilibrium between the phases.&apos; One object of the present work was to see if the information object of on the relative stability of phases could be gained by substituting plastic deformation for thermal agitation. Procedures were worked out that led to the determination of a diffusionless type of phase diagram, which represents the temperature of of phase equal stability for phases of the same composition, and the technique was applied to the Co-Ni system. Another object of the work was to see whether or not deformation would generate frequent stacking faults when these were thin lamellae of quentstackingfaultsa phase having higher free energy than the parent phase. The alloys were prepared in 80 to 100 g melts from cobalt (with metallic impurities estimated spectrochemically as follows: Ni, 0.05 pct; Fe, 0.001 pct.; Mg, Si, Cu, Cr, Al, < 0.001 pct) and Mond Car-bony1 nickel (with Fe, 0.05 pct; Si, 0.003 pct; C, 0.61 pct.; Cu, 0.001 pct; Co, Cr not detected, < 0.01 pct). The metals were melted in pure Al2O3 crucibles. An atmosphere of argon, that had been purified by passing over hot magnesium chips, was used for the alloys that, by analysis of the portions of the ingots actually used, were found to contain 15.3, 25.7, and 35.0 pct Ni, and vacuum melting (after degassing) was used for those containing 29.4 and 31.5 pct Ni. After induction melting the alloys were allowed to solidify in the crucible, and slices % in. thick x ½ in. in diam were annealed 12 hr at 1350°C for homogenization. These same specimens were used throughout the series of experiments, with annealing treatments of 4 hr at 900°C in purified hydrogen followed by furnace cooling, alternating with the deformation and X-ray tests discussed below. Results Spontaneous transformation was observed on cooling to room temperature in all alloys containing 29.4 pct Ni or less and by cooling the 31.5 pct alloy to — 195°C but was not observed in the 35 pct alloys after cooling to —195°C. These results are in satisfactory agreement with the cooling experiments of Masimoto.4 From these data it is clear that the temperature of beginning transformation M,,, drops to 20°C with the addition of about 30 pct Ni. The test for spontaneous transformation was metallographic. Specimens were thermally polished by annealing 10 hr in hydrogen at 1350°C, then furnace cooled; if trans- formation had occurred there were relief effects visible on the thermally polished surfaces. These markings were narrow straight lines, usually resolvable at high magnification as clusters of fine lines that resembled slip lines. It was concluded that they resulted from displacements on (111) planes, for the number of directions in individual grains often reached but never exceeded four, and lines could always be found parallel to the thermally etched (111) boundaries of annealing twins. The markings were thus consistent with the idea that the transformation occurs by (111) plane displacements (Shockley partial dislocations moving on (111) planes). This was further confirmed by X-ray tests for stacking disorders. Using an oscillating crystal technique previously employed to detect strain-induced faulting in Cu-Si alloys," streaks indicative of the stacking faults were looked for and found on X-ray films of the spontaneously transformed 25.7 pct Ni alloys, as expected by analogy with Edwards and Lipson&apos;s results on pure cobalt." The streaks were much intensified after rolling at room temperature. Transformation induced by plastic strain was investigated as a function of alloy composition and temperature of deformation. A series of tests was made to determine suitable straining and X-raying techniques. Filing was found inferior to abrasion in converting cubic samples to hexagonal, and abrasion was less effective than peening in producing smooth unspotty Debye rings in the X-ray patterns. Because the diffraction lines were broad, Geiger-counter spectrometer records of filings were less sensitive in revealing small amounts of transformed material than X-ray patterns recorded on films in a small diameter camera. After these exploratory tests the following methods were adopted. Specimens that had been annealed at least 4 hr at 900°C and furnace cooled were mounted in a block of aluminum, brought to temperature, and peened thoroughly with a mullite pestle preheated to the same temperature. The specimens were then quenched to room temperature. In peening, a circular area of % in. diam was given 500 blows. A few control tests showed that an additional 1000 blows did not detectably change the proportions of the phases present. The amount of transformation was judged by X-ray reflection patterns from the peened surface, using the innermost four lines of the cubic and the hexagonal patterns with filtered CoKa radiation,

Jan 1, 1953

By N. J. Grant, Per Knudsen, J. T. Blucher

The fatigue behavior of three SAP alloys was studied in ternzs of strain rate and temperature, at high strains. The k values in the modified Manson-Coffin equation, Nk4 = C, were less than 0.5 under all test conditions, and change with strain amplitude for the lower-oxide alloys at about 2 pct strain. Lowest k values were near 0.25. Strain rate had no effect on life at 80 F, but had an increasingly greater effect with increasing temperature above 500". Life decreased with decreasing strain rate, above 500"F, and with increasing temperature. Ductility at fracture in a tension test was indicated to be an important factor in determining 1ife in these big+-strain tests with the SAP alloys. INEVITABLY, in the course of mechanical tests at elevated temperatures, particularly if significant time at temperature is involved, there are large changes in structure; these changes make it difficult to relate behavior patterns over ranges of temperature or strain rates at high temperatures. Such changes are to be expetted in low cycle fatigue at low strain rates and high temperatures. Accordingly, it was of great interest to examine the low cycle fatigue behavior of SAP / an aluminum oxide dispersion-strengthened aluminum, a type of alloy which had shown unusual structure stability to temperatures as high as 1000" to 1150°F and resisted recrys-tallization essentially to the melting temperature.&apos;j3 Since the matrix is pure aluminum, there are no complications of averaging, agglomeration, or phase solution. It was also desirable to check the Manson-Coffin equation4?&apos; for the SAP alloys, namely N~E~ = , where ep is the total plastic strain amplitude, k and C are constants, and N is the number of cycles to failure. Here, too, was an opportunity to check the roles of temperature and strain rate with a very stable material. Tavernelli and coffin6 had concluded that k had a value of about 0.5 for many alloys and C was equal to ~/2, where E is the fracture ductility determined from a static tension test. The results were obtained from low-temperature tests where creep and diffusion processes are unimportant. Manson7 found k = 0.6 fitted his data reasonably well; however, in later analyses of a large amount of low cycle fatigue data generated at room temperat~re@"~ he found k to vary from 0.6 for short lives to 0.21 for long-life fatigue tests. In the latter studies,89g Manson separated the total strain range into elastic and plastic components when he found that k was influenced by the nature of the strain. The use of EL (total strain) instead of EP (total plastic strain)4&apos;5 makes a difference in the resultant k value. The ratio of changes with temperature, strain rate, and strain; further, there are the problems in the determination of the elastic strain. Based on these considerations, and the improved fit of points in a plot of by Wells and Sullivan,&apos; is also utilized in these studies. Anderson and wahl,14 using commercial 1100 aluminum, and Blucher and Grant,15 using 99.99 pct pure aluminum, found an increase in life with increasing test temperature. Anderson and Wahl were the first to report low cycle fatigue results from SAP materials. With increasing temperature, the role of strain rate becomes more important. In this regard, care must be exercised to differentiate between frequency (wherein strain rate may vary from zero to a maximum in each cycle, sinusoidally, for example), and constant strain rate, as used in the present study, in a saw-tooth type cycle; in the latter case, the frequency is not specified but can easily be calculated from the strain and strain rate data. It has generally been found that life in low cycle fatigue tests decreases with decreasing frequency16 or with decreasing strain rate at elevated temperatures.15 Coffin,17 reviewing Eckel&apos;s work,16 also reported that k increased with decreasing frequency for acid lead, yielding values from 4.0 at a frequency fo 6.6 cycles Per day to 1-46 at a frequency of 7440 cycles per day; the value of k decreased to 0.58 at a frequency of 2.38 x lo6 cycles per day. EXPERIMENTAL PROCEDURE Three SAP alloys, of two nominal compositions, were tested. Alcoa supplied XAP 005 as 2-in.-diam extruded bar, of nominal composition A1-7 wt pct A1203. The Danish Atomic Energy Commission supplied SAP 930 (A1-7 wt ~ct Ala3) and SAP 865 (A1-13 wt pct Al&) manufactured by Swiss Aluminium Ltd., in the form Of $-in.-diam extruded rod. Metallographic comparison of the structures of XAP 005 and SAP 930 showed the former to have a more uniform oxide distribution. Button-head specimens were machined in the longitudinal direction of the bar with 0.4 in. gage length by 0.2 in. diameter, with a fillet radius of j-B in. After machining, the specimens were electropolished in a 1 to 4 mixture of perchloric acid to methanol to remove all machining marks. All test bars were in the as-extruded condition. The fatigue tests were performed on a hydraulically activated, axial strain machine, with complete reversal of strain.15 Test conditions were:

Jan 1, 1969

By C. L. Sollenbeger, R. B. Greenwalt

PERHAPS the most widely used dispersants or gangue depressants in nonmetallic flotation are sodium silicates, which vary in silica-to-soda ratio from 1 to 3.75. Typical manufactured silicates in order of decreasing solubility and increasing amounts of silica are Metso, silica-to-soda ratio of 1.00; D, 2.00; RU, 2.40; K, 2.90; N, 3.22; and S-35, 3.75.* References in flotation literature1,2 to the use of sodium silicates are often weak because they fail to mention the type of silicate used. Metso and silicate N have occasionally been mentioned, but when the type of silicate is not mentioned, it is usually assumed to be N, the cheapest of the soluble silicates and the one recommended by sodium silicate manufacturers as a flotation agent. In the All is-Chalmers Research Laboratories a systematic study was made of the effect of different alkali-silica ratios on the concentration by flotation of two scheelite ores. One of these was a high grade ore from the Sang Dong mine in Korea. The effect of such factors as pH; addition agents; and conditioning time, temperature, and pulp density on the flotation efficiency of this ore have been described previously. The other ore was a low grade ore from Getchell Mines Inc., Nevada. The mineralogy and techniques of concentrating this ore have been described by Kunze. Hereafter these ores will be referred to as the Korean and Nevada ores. Experiments were made with both to determine the effect of three factors—-type of silicate, concentration of silicate, and pH of the pulp—on recovery and grade of tungsten in a rougher concentrate. Average WO, content of the Korean ore was 1.50 pct and of the Nevada ore 0.27 pct. The predominant tungsten mineral in both ores was scheelite, which was accompanied by a small amount of powellite. The powellite and scheelite were finely disseminated through both ores and required a —200 mesh grind for liberation. Major gangue minerals in the Korean ore, in decreasing order of abundance, were amphi-boles, quartz, biotite, garnet, fluorite, and calcite. Bulk sulfides composed about 3 pct of the total weight. Gangue in the Nevada ore, in descending order of abundance, was garnet, alpha quartz, calcite, phlogopite, wollastonite, and amphiboles. Sulfide minerals were 3 to 4 pct of total weight. Batch flotation experiments were made with 500-g samples of ore, each sample wet-ground to 90 pct passing 200 mesh. The finely ground ore was floated in a Fagergren batch cell at 25 pct solids. The natural pH of the Nevada ore was 8.9 and of the Korean ore, 8.5. The D, RU, K, N, and S-35 sodium silicates were obtained in colloidal dispersions with varying amounts of water. The most alkaline, Metso, was in dry powdered form. For convenience in addition, 5 pct solutions by weight were prepared from each of the silicates, on the basis of dry sodium silicate dissolved in the correct amount of distilled water. Chemical analyses of the various silicates are given in Table I, together with the pH of the 5 pct solutions. A preliminary bulk sulfide float was made with secondary butyl xanthate as the collector and pine oil as the frother. The WO] analysis of the sulfide concentrate was nearly 1 pct for the Korean ore and about 0.1 pct for the Nevada ore. The tungsten contained in the sulfide concentrate constituted about 3 pct of the total tungsten in each ore. No effort was made to recover these tungsten values. The scheelite was floated with oleic acid. Adjustments in pH were made with sulfuric acid or sodium carbonate. A 1 pct solution of 85 pct Aerosol OT was sprayed on the froth and sides of the cell during the scheelite float to aid in dispersing the minerals and to decrease the entrapment of gangue particles. Six tests were planned for each of the six types of silicate in which concentrations of 1, 2, and 4 1b of silicate per ton of dry ore were investigated at both 6.5 and 10 pH. All tests were made at room temperature. The performance of each silicate was judged from the grade and recovery of WO, in the scheelite rougher concentrate. Tungsten recovery was calculated on the basis of the scheelite remaining in the ore after the preliminary sulfide float. Testing of each silicate at three levels of concentration and two levels of pH required 36 tests with each scheelite ore. Variance analyses were performed on the concentrate grades and recoveries to determine whether or not the type of sodium silicate, the concentration of sodium silicate, or the pH significantly affected recovery or grade. Results Concentrate Grade: A variance analysis of the concentrate grades for the Korean ore showed that concentration of the silicate and pH of the ore pulp were major factors in producing a high grade concentrate. Also, the silica- to-so da ratio was important as an interaction with pH. The concentrate grade vs silica-to-soda ratio is plotted in Fig. 1. The curves show that the concentrate grade improved with an increase in concentration of sodium silicate and also

Jan 1, 1959

By R. G. Wayland

SINCE the installation at Kropfmuehl, Bavaria, of a modern flotation concentrator in 1938, the flake and fine graphite from the Passau area can now be delivered in about any normal specified carbon content of any size range up to a flake averaging about 0.7 mm. The graphite finds a wide German and export market for crucible manufacture, pencil leads, dry cells and other uses. A controversy over the origin of the graphite deposits is being resolved in favor of syngenesis rather than epigenesis. The syngenetic theory is newly supported by the yet unpublished work of Hartmann of the Bavarian Geological Survey. Development work and exploration for graphite in the area may be changed in direction as the syngenetic theory is accepted. Crystalline graphite is produced in the area east of Passau near the junction of Germany, Austria and Czechoslovakia, as shown in Fig. 1. This is the only graphite area of importance in Germany, and Gra-phitwerk Kropfmuehl AG is the only operating firm in the area. The plant and mine are located at Kropfmuehl near Hauzenberg, Kreis Wegscheid, about 10 miles east of Passau. A narrow gage railway from the mine connects with the German Railway at Schaibing Bahnhof. The Pfaffenreuth mines date from about 1730. Until the early 20th century mining operations were carried out in a haphazard fashion. During World War I graphite mining and milling was increased, since it had to cover almost all of the crucible needs of the Central Powers. Between the wars some 11 mines were operated by two large and several small companies, but under the Nazis these were consolidated by 1938 into the Kropfmuehl enterprise. Kropfmuehl built a modern flotation mill to treat its own ores and small amounts of custom ores and tailings from the area. Since Graphitwerk Kropfmuehl AG was an I.G. Farbenindustry subsidiary, it has been under Military Government Property Control and probably will be sold to private German capital. Geology The country rock of the graphite area is part of the "kristallines Grundgebirge," the series of old gneissic and schistose rocks that constitutes the bed rock of most of the Bohemian basin and rims the Sudeten-land. The gneissic rocks of the graphite area are considered to have been metamorphosed during the Carboniferous period. They are bordered on the north by granite stocks and penetrated by numerous smaller granite and pegmatitic intrusive rocks, as shown in Fig. 1. The gneiss is classed as a micaceous, coarse-grained cordierite gneiss by most investigators. It is much metamorphosed by the granite, particularly in the north near the larger granite bodies. Interbedded in the gneiss are the graphite seams and lenses, and also beds and lenses of crystalline limestone containing disseminated graphite in noncommercial quantities. The gneiss, together with the included graphite and limestone seams and lenses, is cut and displaced by a number of granite sills of medium to fine grain and by a large number of diorite lamprophyre dikes and a few syenite-pegmatite dikes. The lamprophyre dikes are of various mineral compositions and textures, but many are banded and richly impregnated with pyrite; while the syenite-pegmatite dikes are coarse-grained with good crystals of titanite, pyroxene, uralite and other green amphiboles. Most investigators and the miners speak only of diorite and granite dikes cutting the graphite seams. The diorite dikes are later than the granite and some of the faulting, as is evident from Figs. 1 and 2. Individual graphite seams and lenses may be mined for thicknesses of several feet up to several scores of feet, and for distances of several hundred feet. The aggregate thickness of a series of some 20 seams of graphite, limestone and interbedded gneiss at Kropfmuehl is stratigraphically about 450 ft. Laterally, the graphite in a seam may pinch out or grade into crystalline limestone. Graphite crystals also are found disseminated in the gneiss itself, although in unmineable concentrations. The faults that cut the graphite seams carry graphite for some feet or tens of feet away from the seams, apparently mechanically. Similarily, the graphite lenses themselves often contain mechanically introduced inclusions of wall rock, probably from flowage during folding. Graphite crystals make up 10 to 30 pct of the fresh, mineable graphite lenses at Kropfmuehl, averaging about 20 to 25 pct after hand-sorting by the miners. In weathered lenses, the graphite concentration is said to be as high as 50 pct. The associated primary and hydrothermal minerals are dom-inantly feldspar and calcite, plus quartz, pyrrhotite, pyrite, biotite and occasional garnet, hornblende, sphalerite and galena. Associated secondary minerals include kaolin, nontronite, mangano-oxide-silicates (mog), adularia and chlorite. The superimposed suite of siliceous cementation minerals present consist largely of opal, chloropal, chalcedony, jasper, and hyalite. The kaolin is of special interest since it too was mined as early as 1730 and was used in the well-known Nymphenburg porcelain from 1756 on. The kaolin is derived from the gneiss and the syenite pegmatites. The crystals of graphite vary in size within a given seam, but in seams more than a mile away from the granite on the north the average crystal-linity is less coarse, lowering the commercial value. The lenses in the Kropfmuehl-Pfaffenreuth area are the most developed, and are the only ones with deep workings now accessible. Other similar crystalline graphite lenses are known from older workings at Habersdorf, Oberoetzdorf, Ficht, Diendorf, and

Jan 1, 1952

By J. R. Bell, W. J. Childs, J. H. Bucher, G. A. Wilber

A technique for determining recrystallization times as short as 0.10 sec was developed utilizing the "Gleeble", a commercially available testing system designed for the study of short-time, high-temperaLure themal and mechanical processes. The procedure consisted of heating a small tensile specimen to a given temperature of hot deformation, loading to a given reduction in area, unloading, delaying various intervals at temperature, and then reloading- to failure. The magnitude of the ultimate load obtained upon reloading decreased with delay lime as recrys-lallization proceeded. The technique was applied to austenite recrystallization in AISI 1010 and AISI 1010 uith 0.02 pct Cb steels. For each steel the reduction in area given the specimen on the first pull was mainlairred at 30 ± 5 pct and recrystallization times deterntined at various temperatures. The results indicaled a significantly slower rate of recrystallization for the columbium-modified composition, suggested the presence of- a recovery stage in the softening process , and indicated a greatly increased softening rate at a temperatuve where significant allotropic transformation to a partially ferritic Structure could occur. In recent years increasing attention has been paid to the fact that the process of recrystallization of austenite deformed at elevated temperatures is far from instantaneous at many practical hot-working temperatures.1-3 This realization has given rise to such terms as hot cold-working1 or warm-working,2 These terms generally describe processes where the recrystallization rate at the temperature of deformation is slow enough to have an appreciable effect on mechanical properties despite a relatively high deformation ternperature. The mechanical properties of interest can be either the properties at the deformation temperature as in hot-workability studies4 or the room-temperature properties after cooling as in the many recent studies of various thermomechanical processes172 where heat treatment and deformation are intentionally combined to give a unique set of room-temperature properties. Because of this interest in processes where the austenite recrystallization kinetics can be an important variable, the development of quantitative methods of following the course of short-time, high-temperature recrystallization has received increasing attention.l,3,5 The experimental methods to date have, in general, relied upon rapidly deforming the austenite, holding at temperature for various brief intervals, quenching as G.A.WILBER and W. J. CHILDS, Members AIME,are Research-Fellow and Professor, respectively, Rensselaer Polytechnic Institute, Troy, N. Y. J. R. BELL and J. H. BUCHER, Member AIME, are Research Engineer and Research Supervisor, respectively, Graham Research Laboratory, Jones & Laughlin Steel Co., Pittsburgh, Pa. Manuscript submitted March 13, 1968. IMD. rapidly as possible, and then using room-temperature measurements to follow the recrystallization process. Although such methods can be successfully applied to certain alloy steels, the existence of the allotropic transformation during cooling of plain-carbon or low-alloy steels tends to obscure the results. Thus, such room-temperature measurements as hardness and X-ray line widths do not correlate well with the extent of austenite recrystallization before quenching,5 and results based on room-temperature microstruc-tural observations are dependent upon the success in correlating the observed structure with the prior aus-tenitic grain structure.1,3,5 The purpose of the present work was to develop a quantitative method for the determination of short-time, high-temperature recrystallization rates, based on measurements made at the temperature of deformation. EXPERIMENTAL TECHNIQUE The basic technique consisted of heating a small tensile specimen to a given temperature of hot deformation, loading to a given reduction in area, unloading, delaying various intervals at temperature, and then reloading to failure. The data were obtained in the form of traces of load and elongation as a function of time. Due to the high deformation temperature, the strain hardening introduced during initial loading was progressively annealed out with holding time after unloading and the loads obtained upon reloading decreased as this softening proceeded. Although the value of the second load at any Consistent point On the load-elongation curve could have been used as a measure of the degree of softening, the most convenient to use was the ultimate load. The softening indicated by the decrease in the second ultimate load with time is essentially a process of annealing of cold-worked material at a high deformation temperature. Although some recovery grain growth may contribute to such a softening process, it is generally considered that the major softening which must take place to achieve complete removal of substantial Strain hardening will occur by the formation of new, stress-free grains. As the results of this work indicate that essentially complete removal of strain hardening did in fact occur. the primary softening process will be attributed to recrystallization, and specific reference made where it appears that other mechanisms may be contributing to the total observed softening. It would, of course, be of interest to attempt to correlate the results of this work with the actual austenite fraction recrystallized as determined by other techniques. This was not attempted in the present work because it would have required running a large number of additional specimens and, as discussed previously, there is limited assurance that the results would accurately reflect the prior austenite fraction recrys-

Jan 1, 1969

By Lo-Ching Chang, J. Chipman

The perennial and increasing interest in the chemical behavior of steelmaking slags has led to numerous attempts to formulate the thermodynamic properties of these solutions. The classical view is that of a solution of the component oxides in which certain acidic oxides are more or less completely held in combination with basic or metallic oxides, the nature of the interoxide compounds being derivable from the chemical behavior of the slag or from the mineralogy of a solidified specimen. The known electrical conductivity of slags has pointed to the existence of ions in the solution and a number of attempts have been made to account for the observed facts of slag behavior on the basis of a theory of complete ionization of the solution. It is the purpose of this paper to examine, in the light of ionic theory, a number of recently published series of data on slag-metal and slag-gas equilibria, with the purpose of obtaining a more complete or more satisfactory generalization than has been possible on either of the single bases of simple compound formation or complete ionization. The attempt to formulate the ionic constitution of a complex solution is fraught with many uncertainties. An ion is not something that can be plucked from the solution and examined in detail, nor can its true formula be determined with certainty by any single experimental method. In attempting to express the composition of a slag by various ionic formulas it can be expected that alternative hypotheses of essentially equal merit will present themselves. In the present state of early development of the ionic theory of slags, it may be necessary to make some rather arbitrary choices of ionic formulas in the absence of su- cient information to yield complete certainty. Acids and Bases The classification of slag-forming oxides as acidic or basic apparently dates back into the days of Berzelius. It is difficult to see how the concept could have originated in the early twentieth century when it was fashionable to define an acid or a base as an aqueous solution containing hydrogen or hy-droxyl ions. It is, however, entirely consistent with the modern and more general theory of acids and bases. In this theory, as originally formulated by G. N. Lewis,&apos; a basic molecule is one that has an electron pair which may enter the valence shell of another atom thus binding the two together by the electron-pair bond. An acid molecule is one which is capable of receiving such an electron pair into the shell of one of its atoms. The acid, the base, and the product of neutralization may be either ions or neutral molecules. The product of such a reaction may itself be a base or an acid if it is further capable of giving or accepting an electron pair. Thus a base is a donor of electrons, an acid, an acceptor. In oxide slags the typical and ever-present base is oxide ion, 0-—. In behavior and in importance it is analogous to hydroxyl ion, OH-, which is the typical base of aqueous solutions. There is nothing in the chemistry of slags which is quite analogous to the acid H30+ in aqueous solutions. This is not surprising for in slag systems there is nothing which can be designated as a solvent and no ubiquitous positive ion. The chemistry of slags is in fact more complex than the chemistry of aqueous solutions and the concepts which must be evoked in its study are correspondingly broader. In seeking a basis for a classification of slag-forming oxides as basic or acidic it must be remembered that these terms are not absolute but relative. A substance which acts as a base toward a second substance may act as an acid toward a third. This is less likely to happen among strong bases or acids than among the weak ones; there are numerous examples of weak acids which under the influence of a stronger acid behave as weak bases. Such substances are called amphoteric. A classification of the glass-forming oxides has been proposed by Sun and Silverman² and further developed by Sun3 in which the oxides are arranged in order of decreasing acidity or increasing basicity, each substance being potentially capable of acting as an acid toward substances below it in the list and as a base toward those above it. It is based upon the relative strengths of the metal-to-oxygen bond as determined by the energy required to dissociate the oxide into its component atoms.&apos; Data are available for computation of this energy, at least approximately, for the oxides of slags and glasses. In general those oxides from which it is most difficult to remove the positive atom are the strong acids while those in which it is most loosely held are the strong bases. It is in the latter, of course, that formation of oxide ion occurs most readily as, for example, in CaO which in solution ionizes to form the weak acid Ca++ and the strong base O—. The order of arrangement found by Sun is shown in the first column of Table 1, to which have been added the data for

Jan 1, 1950

By K. P. Mukherjee, K. P. Gupta, J. Bandyopadhyaya

Even though a lot of work has been done in the past to establish phase equilibrium in the Cu-Si system a re cent investigation casts some doubt about the existence and crystal structure of some of the phases that form in the composition range of 15 to 25 at. pct Si in Cu. The present investigation was carried out using high temperature X-ray diffraction technique along with other standard techniques to study the phases in this composition range. The high temperature 6 phase appears to be tetragonal with parameters a,, = 8.815A, c, = 7.903A, and co/ao = 0.896. The reported bcc E phase exists at room temperature and at least up to 780°C and appears to undergo a transformation near 600°C. The phase appears to be cubic but not of the bcc type. The ? phase appears to undergo a transformation, as has been indicated by earlier investigators, and the low temperature form of .? phase is tetragonal with parameters a, = 7.267A, co = 7.8924, and co/ao = 1.086. THE Cu-Si binary system has been investigated by several investigators1" and several intermediate phases,?,e,?&apos; at lower temperatures and ?,ß,0,e, and ? at higher temperatures, were observed between terminal solid solutions of copper and silicon. Even though the existence of the e phase and the transformation in the ? phase were reported in many early works, in a recent study of this system Nowotny and Bittner6 doubted the existence of the e phase and phase at 550°C. Among the high temperature phases, the 6 phase was reported to have a complex cubic structure with parameter a, = 8.805A.7 Nowotny and Bittner, however, suggested that the structure of the 6 phase might be of CsCl type. In order to check these contradictory reports the present study was taken up to investigate the Cu-Si binary system in the composition range of 17 to 25 at. pct Si. EXPERIMENTAL PROCEDURE Weighed amounts of copper (99.99 pct) and silicon (99.9 pct) were induction melted in recrystallized alumina crucibles under argon gas atmosphere. The alloys containing 17, 18, 20, 21, 21.2, 22, and 24 at. pct Si were annealed in evacuated and sealed quartz capsules at 700°C for 3 days and subsequently water quenched. Other than this annealing, the 21.2 at. pct Si and 24 at. pct Si alloys were annealed at 550°C for 10 days, the 17 at. pct Si alloy was annealed at 750°C for 3 days, and the 22 and 24 at. pct Si alloys were annealed at 780°C for 2 days. All annealing temperatures were controlled to within *l°C. Alloys after quenching were subjected to metallographic and X-ray diffraction investigation. A solution containing 5 g FeC13 + 10 cc HCl + 120 cc H2O diluted with six times its volume with water was used as etching reagent. A 114.6 mm diam Debye Scherrer camera was used for obtaining diffraction patterns. The 17, 21.2, and 24 at. pct Si alloys were subjected to high temperature diffractometry using a Tempress Research High temperature attachment and a GEXRD VI diffractometer. For the 6 phase (17 at. pct Si alloy) powder specimen from a 750°C annealed alloy was reheated to 750°C in the high temperature attachment for 1½ hr before taking a diffraction trace. A 550°C annealed and slowly cooled phase (24 at. pct Si) alloy was first reheated to 550°C. a diffraction trace was made after annealing it for 2 hr, and subsequently it was heated to 716OC and kept at this temperature for 2 hr before taking a diffraction trace. For the e phase (21.2 at. pct Si alloy) a 550°C annealed and slowly cooled specimen was heated first to 425°C and annealed at this temperature for 2 hr before taking a diffraction trace. Subsequently, the specimen temperature was raised to 495", 540°, 603", 635", 682", 720°, and 748°C and homogenized at each temperature for 1 hr before taking diffraction traces. The powder specimen temperature was controlled to within +2oC at each temperature and argon gas, purified by passing it at slow rate through a fused CaC12 column, hot (800°C) copper and titanium chips and finally through a P2O5 column, was used to prevent oxidation of the powder. For all X-ray work copper-radiations at 25 kv, 15 ma (for Debye Scherrer technique), and 40 kv, 20 ma (for diffractometer tech-nique) were used. RESULTS AND DISCUSSION At 700°C the alloys containing 17 to 21 at. pct Si showed two phases while the 21.2 at. pct Si alloy was found to be single phase. The X-ray diffraction patterns of the two-phase alloys were consistent with the phase (ßP-Mn type structure) and the phase (21.2 at. pct Si) patterns. The diffraction patterns of the 17 at. pct Si alloy quenched from 750" and 700°C were identical. According to the accepted Cu-Si phase dia-gram4,5,10 the 17 at. pct Si alloy at 750°C should be in the (k + 6) two-phase region and very close to the -phase boundary. The identical patterns possibly resulted from the decomposition of the 6 phase on

Jan 1, 1970

By C. T. Wei, A. Kelly

USING a recently developed X-ray method, reported by Schulz,2 it is possible to make a rapid survey of the perfection of a single crystal at a particular surface. This technique has the advantage of allowing a large surface of a specimen to be examined by taking a single photograph and it compares well with other X-ray methods in regard to sensitivity of detection of small angle boundaries. During the course of a survey of the perfection of large crystals of aluminum produced by a number of methods, an examination has been made of a number of single crystals produced from the melt using a soft mold (levigated alumina)." Crystals grown by this method are known, from an X-ray study carried out by Noggle and Koehler,3 to contain regions where they are highly perfect. In the present work, it has been possible to obtain photographs showing directly the distribution of low angle boundaries at a particular surface of these crystals. single crystals were grown from the melt using the modified Bridgman method with a speed of furnace travel of -1 mm per min. These were about 1/10 in. thick, 1 in. wide, and several inches long. The metal was 99.99 pct pure aluminum supplied by the Aluminum co. of America. The crystals were examined by placing them at an angle of about 25° to the X-ray beam issuing from a fine focus X-ray tube of the type described by Ehrenberg and Spear4 and constructed by A. Kelly at the University of Illinois. A photographic film was placed SO as to record the X-ray reflection from the lattice planes most nearly parallel to the crystal surface. The size of the focal spot on the X-ray tube was between 25 and 40 u, and the distance from the X-ray tube focus to the specimen (approximately equal to the specimen to film distance) was -15 cm. White X-radiation was used from a tungsten target with not more than 35 kv in order to reduce the penetration of the X-rays into the specimen. Exposure times were approximately 1 hr with tube currents between 150 and 250 microamp. The type of photograph obtained from these crystals is illustrated in Fig. 1, which shows a number of overlapping reflections from the same crystal. The large uniform central reflection is traversed by sets of horizontal white and dark lines. These two sets run mainly parallel to one another. Lines of one color are wavy in nature and often branch and run together. Large areas of the crystal surface show no evidence of these lines whatsoever. The lines are interpreted as being due to low angle boundaries in the crystal, separating regions which are tilted with respect to one another. A white line is formed when the relative tilt forms a ridge at the interface and a black line is found when a valley is formed. In a number of cases, the lines stop and start within the area of the reflection and often run into the reflection from the edge, corresponding to a low angle boundary starting from the edge of the crystal. The prominent lines run roughly parallel to the direction of growth of the crystal although narrow bands can run in a direction perpendicular to this; see Fig. 2. Although they may change their appearance slightly, the lines tend to occur in the slightly,Same place in the X-ray image and to maintain their rough parallelism when the crystals are reduced in thickness by etching. Thus the low angle boundaries can occur at any depth within the crystal. The appearance of the lines is unaffected by subjecting the crystal to rapid temperature changes, such as plunging into liquid nitrogen or rapid quenching from 620°C. From the width of the lines on the x-ray reflection, values can be found for the angular misorienta-tion of the two parts of the crystal on either side of a boundary. The values found run from 1&apos; to 10&apos; of arc, but values of UP to 20&apos; have sometimes been found, e.g., the widest lines on Fig. 2. These mis-orientations are much less than those commonly found in crystals possessing a lineage structure. When a number of a and white lines occur, running in a roughly parallel direction across the image of a Crystal, the total misorientation corresponding to lines of one color is approximately equal to that corresponding to lines of the other color. The interpretation of the lines as due to low angle boundaries has been checked in a number of ways. Photographs taken with different specimen-to-film distances distinguish lines due to low angle boundaries from effects due to surface relief of the specimen. Normal Laue back-reflection photographs, taken with the beam irradiating an area of the surface showing a number of the lines, show white lines running through each Laue spot. Black lines are set to see by this method. X-ray photographs were also taken, using the set-up described by Lam-one et al.5 when the beam straddles regions giving rise to lines in the Schulz pattern, split reflections are observed within the Bragg spot. The misorienta-tions calculated from the separation of these reflections and that found from the widths of the lines on the schulz technique patterns show good agreement. An exposure was made with Lambot technique of an area of the crystal showing no evidence of low angle

Jan 1, 1956

By Arnt Solbu, Jomar Thonstad

The reaction between CO, and aluminum in cryolite-alumina melts in contact with aluminum has been studied by passing CO2 over the melt. In unstirred melts a homogeneous reaction between dissolved metal and dissolved CO2 was observed. In stirred melts in which convection was induced by bubbling argon through the melt, the dissolved metal apparently reacted mainly with gaseous CO2. The rate of formation of CO increased slightly with increasing depth of the melt, and it did not depend on whether CO2 was passed over or bubbled through the melt. The rate of formation of CO increased with increasing area of the metal/melt interface and with the application of anodic current to the metal. It is concluded that the dissolution of metal into the melt is the rate-determining reaction. THE current efficiency in aluminum electrolysis is determined by the rate of the recombination reaction between the anode gas and the metal: 2A1 + 3CO2—A12O3 + 3CO [1] as originally stated by Pearson and waddington.1 The occurrence of this reaction in cryolite-alumina melts in contact with aluminum was first verified experimentally by Schadinger.2 Thonstad3 has shown that the reaction may proceed further to give free carbon: 2A1 + 3CO— A12O3 + 3C [2] Normally only a few percent of the CO formed undergoes such reduction. The mechanism of these reactions has not yet been clarified. Aluminum, as well as CO,, is soluble in the melt. The solubility of aluminum in cryolite-alumina melts at around 1000°C corresponds to 75 x 10- 6 mole A1 per cu cm,4 while that of CO2 is only 3 x 10-6 mole CO, per cu cm.5 Taking into account the stoichiometry of Reaction [I], the ratio between dissolved aluminum and dissolved CO2 available for the reaction in a saturated melt is about 40. Therefore, as will be shown in the following, the reaction probably mainly occurs between gaseous COa and dissolved aluminum. The dissolved aluminum presumably consists of subvalent ions of aluminum and sodium.4&apos;6 Since the interpretation of the present results is not dependent upon the nature of this solution, the dissolved metal will be designated solely as Al+ in the following. The reaction can then be divided into four steps: A) dissolution of metal, e.g., 2A1 + Al3 — 3A1+ [3] B) diffusion of dissolved metal through a boundary layer; C) transport of dissolved metal through the bulk of the melt; D) Reaction [1]. If dissolved CO, takes part in the reaction, three additional steps embodying the dissolution and transport of CO2 must be added. schadinger2 observed, when bubbling CO2 through the melt, that the rate of formation of CO (in the following designated rfco) did not depend on the distance from the metal surface. The results also indicate that the rate of bubbling did not affect the rfco. When passing CO, over the melt, Revazyan7 found that the loss of metal did not depend on the depth of the melt above the metal or on the flow rate of CO2, and concluded that Step A is rate-determining. In an unstirred melt, however, Gjerstad and welch8 found that the rfCo decreased with increasing depth of the melt, indicating that step C was rate-determining. It thus appears that the rate control of the process depends on the experimental conditions, particularly on the convection. In the present measurements the reaction has been studied in unstirred as well as in stirred melts. EXPERIMENTAL AND RESULTS The experiments were carried out at 1000°C in a Kanthal furnace with a 10-cm uniform temperature zone (±0.l°C). The melts were made up of "super purity" aluminum (99.998 pct), hand-picked natural cryolite, and reagent-grade alumina. In experiments where alumina crucibles were used, the alumina content in the melt was close to saturation (13.5 wt pct9); otherwise it was 4 wt pct. Pure Co2 (99.85 pct) was passed over the melt, and the exit gas was analyzed for CO2 and CO by the conventional absorption method.3 From the weighed amount of CO (as CO2) the rfco was calculated as the number of moles of CO formed per min per sq cm of the surface area of the melt. The amount of carbon formed by Reaction [2] was not determined. As already indicated the rfco is much higher than the rfC, by Reaction [2]. Since the rfC probably is proportional to the rfco, the measured rfco should then the proportional to, but slightly lower than, the total rate of Reactions [I] and 121. In general the scatter of results obtained in duplicate measurements was ±5 to 10 pct, while within a given run a precision of ±3 to 5 pct was obtained. The various crucible assemblies that were used will be described below. Measurements in Unstirred Melts. When carrying out aluminum electrolysis in small alumina crucibles. Tuset10 observed that after solidification the lower part of the electrolyte was gray and contained free metal, while the upper part near the anode was white and contained no metal. One may test for the presence of free metal by treating with dilute hydrochlorid acid.

Jan 1, 1969

By R. Maddin

IN analyzing the relation between the orientation of new grains and that of the deformed matrix of axially extended and recrystallized single crystals of face-centered cubic metals, a two-stage rotation process" is generally used where the first rotation is made in order to account for an "adjustment of orientation to the environment of strain."&apos; It has been argued that in spite of the difference of orientation, which may amount to as much as 12" (in a brass),&apos; between the octahedral plane as observed in the parent lattice and in the recrystallized grain, it is believed to be a common plane in the sense that it constituted the nucleus in the parent strained crystal from which the new grain grew.&apos; A possible source of the deviation in orientations of a common pole in the new grain and that of the deformed single crystal matrix from which it has grown may be found in the distribution of strain resulting from the plastic deformation. It might be expected in view of the incongruent nature of shear&apos; that the perfection of the octahedral plane along which glide has occurred is disrupted and that this disruption constitutes the strain from which nuclei of new grains can grow during recrystallization. Evidence for the existence of strain along glide planes was first detected by Taylor" in 1927 and substantiated by Collins and Mathewson&apos; in 1940. In their investigations, however, the deformed single crystalline specimens (aluminum) were cut mechanically along the glide planes followed by mechanical polishing. X-ray exposures (glancing angle) of only 8 min with filtered radiation were used. It was later shown&apos; that this type of surface preparation did not remove with all certainty the mechanically disturbed surface. It was felt that a re-investigation of this phenomenon using more refined techniques might reveal a more correct extent of the strain resulting from the deformation which might correlate the deviation of the common pole of the recrystallized grain with the acting slip plane of the matrix crystal. In accordance with these thoughts, a single crystal of a brass (70/30 nominal composition) M in. in diam x 5 in. long, tapered as in previous experiments,&apos; was extended and carefully documented with respect to elongation and shear. Disks about % in. thick paralle&apos;l to the primary slip planes were cut from the specimen by means of an etch cutter." These disks represented volumes of the specimen which had been extended 0, 5, 10, 15, and 20 pct. Copper Ka monochromatic radiation was obtained by reflecting 35,000 v copper radiation from the c-cleavage face of a pentaerythritol crystal. The monochromatic radiation was collimated and led on to the disk set at the proper 0 angle for reflection from the primary (111) planes. The monochromatic beam was aligned in a plane containing the active slip direction. Following a 10 hr exposure at the theoretical Bragg angle, the disk was reset at 0 + 1°, 0 — 1", 0 + 2", 0 — 2", etc., until no Bragg reflection was obtained. The disk was then rotated 90" about its polar axis, and the same X-ray procedure was used. The results are shown in Table I. It may be seen from the results in Table I that the plastic deformation (20 pct elongation) produces fragments of the glide plane which are rotated or tilted as much as 25 " from the normal position on a purely block slip model. In addition to the large variation in 0 angle in the slip direction, there is a variation in 0 as much as 20" in the direction at right angles to the direction of slip, i.e., <110>. In view of the results shown, it may now be argued that the strain distribution finds its origin in the incongruent nature of the slip process.&apos; The use of the two-stage rotation process seems valid in attempting to explain the relation between the orientation of recrystallized grains and the matrix from which they have grown. Acknowledgment This work was sponsored by the ONR under Contract Number N6 onr 234-21 ONR 031-383. The author would like to thank N. K. Chen for reading and correcting the manuscript. References &apos;R. Maddin, C. H. Mathewson, and W. R. Hibbard, Jr.: The Origin of Annealing Twins. Trans. AIME (1949) 185, p. 655; Journal of Metals (September 1949). &apos;J. A. Collins and C. H. Mathewson: Plastic Deformation and Recrystallization of Aluminum Single Crystals. Trans. AIME (1940) 137, p. 150. eN. K. Chen and C. H. Mathewson: Recrystallization of Aluminum Single Crystals After Plastic Extension. Unpublished. 4 C. H. Mathewson: Structural Premises of Strain Hardening and Recrystallization. Trans. A.S.M. (1944) 38. :&apos;C. H. Mathewson: Critical Shear Stress and Incongruent Shear in Plastic Deformation. Trans. Conn. Acad. of Arts and Science, (1951) 38, p. 213. "G. I. Taylor: Resistance to Shear in Metal Crystals, Cohesion and Related Problems. Faraday Soc. (1927) 121. &apos;R. Maddin and W. R. Hibbard, Jr.: Some Observations in the Structure of Alpha Brass After Cutting and Polishing. Trans. AIME (1949) 185, p. 700; Journal of Metals (October 1949). &apos;R. Maddin and W. R. Asher: Apparatus for Cutting Metals Strain-Free. Review of Scientific Instruments (1950) 21, p. 881.

Jan 1, 1953

By D. P. Pope, T. Vreeland

Observations of dislocations in zinc using Berg-Barrett X-ray micrography confirm the validity of a dislocation etch for (1010) surfaces. A technique for measurement of the depth in which dislocations can be imaged in X-ray micrographs is given. This depth on (0001) surfaces of zinc was found to be 2.5 µ using a (1013) reflection and CoKa radiation. BUCHANAN and Reed-Hill (B & RH) have recently questioned the ability of a dislocation etch to reveal all of the basal dislocations which intersect (1010) surfaces in annealed zinc crystals.&apos; This etch was developed by Brandt, Adams, and Vreeland who conducted a number of different experiments to check its ability to reveal dislocations.2,3 B & RH prepared (0001) foil specimens for transmission electron microscopy from annealed crystals and observed dislocation densities of about l08 cm per cu cm in the foils, while the etch indicated densities of the order of l04 cm per cu cm in their annealed crystals. As this etch has been used in a number of studies of dislocations in zinc, it is of considerable importance to reassess its validity in the light of the B & RH results. The X-ray work reported here was undertaken to check the ability of the etch to reveal dislocation intersections on (1070) surfaces of zinc. The X-ray technique was chosen for this check because it could be applied to the as-grown crystals with a relatively small amount of specimen preparation. We believe that the possibility of accidental deformation in preparation of the bulk specimens is considerably less than that for thin foil specimens suitable for transmission electron microscopy. Unfortunately, basal dislocations are not visible on Berg-Barrett topo-graphs of (1010) surfaces, which are the surfaces on which the etch is most effective. Therefore, a one-to-one correspondence between the etch and X-ray observations could not be made. Basal dislocations near (0001) surfaces have been observed by Schultz and Armstrong4 using the Berg-Barrett technique, but they did not report the as-grown dislocation density observed in their crystals. We have applied the X-ray technique in this study to surfaces oriented from 1 to 2 deg of the (0001) to determine the basal dislocation density, and have compared this density with that observed using the etch on a (1070) plane of the same crystal. The X-ray observations permit determination of the depth in which basal dislocations can be observed under the diffracting conditions used. SPECIMEN PREPARATION High purity zinc crystals are very soft, so a good deal of care must be exercised in the preparation of observation surfaces. As-grown crystals approximately 2.5 cm in diam and 20 cm long were acid cut into 1.25 cm cubes. A thin slab was cleaved from an (0001) surface to produce an accurately oriented reference surface on the specimen. Some of the cubes were examined in the as-machined condition while some were annealed in argon at 410°C for 2 hr. Heating and cooling rates were less than 2°C per min. Some of the specimens were scratched on a (0001) surface with a razor blade to produce fresh dislocations. Approximately 2 mm of material was acid lapped from one face of a cube to produce a surface oriented between 1 and 2 deg from the basal plane and parallel to the [1210] direction. A (1070) surface was also acid lapped. The lap used a 1 to 3 pct solution of HN03 in water to saturate a soft cloth which was backed by a stainless steel plate. The cloth was moved over the crystal surface at a rate of 20 cm per sec while a normal force of about 4 g was maintained between the cloth and the specimen. As-lapped surfaces were examined as were surfaces which were chemically and electrolytically polished after lapping. The small angle between a lapped surface and the (0001) plane was measured to 0.1 deg using a Unitron microgoniometer microscope (the cleaved surface was used as a reference in this measurement). The microscope was modified so that the intensity of reflected light could be continuously monitored on a meter. This modification produced nearly a ten-fold increase in the reproduceability of orientation readings. OBSERVATIONS The Unitron Microgoniometer observations indicated that the lapped surfaces had a terraced structure with the terraces quite rounded and spaced about 0.1 mm in the [1010] direction. The maximum change in slope between terraces was 0.25 deg, indicating a terrace height of about 0.1 µ. A Unitron measurement of the average angle between (0001) and a lapped surface was checked by micrometer measurement of the specimen and found to agree within 0.1 deg. The Berg-Barrett micrographs using (1013) reflections and CoKa radiation5 revealed subboundaries, short dislocation segments, spirals, and loops near the surfaces which were oriented from 1 to 2 deg of the (0001). Micrographs of surfaces prepared by lapping appeared very similar to those of the chemically and electrolytically polished surfaces. The loops and spirals were not extinct in (1013) or (0002) reflections, indicating that they have a nonbasal Burgers vector. Extinctions of the short, straight dislocations indicated that they belonged to an (0001)(1210) system. Fig. 1 is an example of a micrograph which shows a subboundary, and dislocation segments which are pre-

Jan 1, 1970

By A. Grant Elliot, H. W. Lavendel

qualitative picture has been developed to describe the oxidation behavior of TaSi2-coated tantalum and CbSi2-coated columbium. These systems have a significantly lower inherent oxidation resistance than MoSi2-coated molybdenum does. This stems primarily from the fact that Ta2O5 and Cb2O5 are nearly as stable thermodynamically as SiO2, whereas MoO2 or Moos are not. Further, diffusion of silicon in the Ta- and Cb-Si system is considerably slower than in the Mo-Si system. These ,factors prohibit the mechanism of selective oxidation of- silicon which accounts for the oxidation resistance 01- MoSi2-coated molybdenum. The silicide can be stabilized by adding suitable Modifiers which increase the thermodynamic stability of the silicate formed during oxidation. Modifiers, such as aluminum, can be inroduced into solid solution in the coating. in controlled amounts through proper selection of the source in the pack cementation process of coating fov~rzatiorz. Addition of aluminum to TaSi2, coatings on tantalum was effective in moderately increasing the oxidation resistance. EXTENSIVE experimental work and analysis have established the nature of the oxidation behavior exhibited by MoSi2- and MoSi2 -coated molybdenum-base alloys, and defined the conditions for maximum protection against oxidation of the substrate.&apos;-* The oxidation resistance of MoSi2 in the temperature-pressure range of 1100°C-PO2 > 10-5 atm to 1900°C— PO2 > 10-1 atm is due to the formation at the surface of a continuous film of SiO2 which results from selective oxidation of silicon. Under the prevailing kinetic conditions, this film is stable toward the molybdenum silicide with which it comes in contact. Initially molybdenum oxidizes also, but it forms volatile species. SiO2, however, nucleates and grows as a condensed phase. Once a continuous film of SiO2 has formed, the oxidation rate falls to that observed for the oxidation of pure silicon indicative of diffusion through the oxide film as the rate-controlling mechanism. This oxidation behavior is of course highly dependent upon temperature and oxygen pressure. Bartlett and Gage13 and Bartlett, McCamont, and Gagelb define precisely this dependence in terms of the oxygen partial pressures and silicon diffusivities required to support a stable SiO2 film. At low temperatures (near 500°C—the "pest" region) silicon diffuses too slowly to be selectively oxidized. Hence, molybdenum and silicon oxidize readily in proportion to their stoi- chiometry. At high temperatures and low pressure, SiOz dissociates to form volatile SiO(g), and a protective film cannot be maintained. Application of the MoSiz/Mo system is limited to temperatures below 1900oC, the eutectic between MoSi, and MO5Si3.5 The oxidation behavior of MoSi2-coated molybdenum is essentially the same as that outlined above with the exception that the MoSi2 is not in equilibrium with the molybdenum substrate. At the temperatures under consideration silicon will diffuse rapidly into the molybdenum eventually converting the coating to MosSi3.4 The rate constant for subsequent decomposition of Mo5Si3 into Mo3Si plus silicon, and/or the diffusivity of silicon through Mo3Si then becomes low enough to allow active oxidation of both molybdenum and silicon with subsequent degradation of the specimen. A stable silica film can be formed but at temperatures and/or oxygen partial pressures higher than those required with MoSi2 present as a source of si1icon.l, 4 Because of the similarity between the silicides of molybdenum and those of columbium and tantalum one would expect similar oxidation behavior for coatings in the respective systems. This is not entirely the case, however, as shown by the experimental results reported herein. Regarding tantalum and columbium disilicide coatings on tantalum and columbium substrates, respectively, the oxygen arriving at the surface of the coating partitions itself nearly equally between the metal and the silicon, and a two-phase oxide layer (Me2O5 plus SiO2) is always formed. The diffusion of silicon in the tantalum and columbium silicides is relatively slow, compared to that in the molybdenum silicides, which further enhances this equipartitioning of oxygen. Thickening of the coating during service by inward diffusion of silicon into the substrate is correspondingly slow, and the effective thickness of the coating at the roots of cracks and defects is only slightly changed providing high probability for premature coating failure. Furthermore, the SiO2 glass that is generated is not thermodynamically stable with respect to the coating. The metal silicide tends to reduce the SiO2 liberating either free silicon or SiO. The situation can be improved by suitably modifying the coating such that the stability of the protective glass which is generated during service is increased. Thus, selective oxidation of silicon and the modifying agent will occur, and the silicide coating will not tend to reduce the oxide layer. Modifying agents can be introduced into the coating by the pack cementation process. Using sources containing the modifier at controlled chemical potentials allows control of the coating composition. Partially substituting aluminum for silicon in TaSi2 coatings by forming a Ta(Si,Al)2 solid solution was effective in moderately increasing the oxidation protection.

Jan 1, 1968