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By D. L. Martin

The study of cobalt-platinum alloys has been of interest since they represent a class of permanent-magnet material in which the disorder-to-order transformation plays a controlling role. The magnetic properties of alloys in the range 40 to 60 at. pct have been found to be greatly influenced by composition and heat-treatment. The peak properties of 4700 coercive force and 9,000,000 gauss-oersteds energy product were obtained by controlled cooling and aging. These high values combined with ductility and machin-ability give the alloys useful characteristics although their high cost limits their application. THE cobalt-platinum alloys have been of interest in the study of permanent-magnet materials ever since the discovery by Jellinghaus that they had unusually high coerceive-force values.' The high coercive force was associated by Jellinghaus with the disorder-order reaction which occurred in these alloys. This was later verified by Gebhardt and Koster in a detailed study.2 An investigation of the structure, mechanism, and kinetics of the disorder-order transformation and resulting property changes in cobalt-platinum alloys has been in progress for some years. Certain phases of this study related to equilibrium rela- tions, and to the mechanism and kinetics of the ordering reaction have been published previously.3-5 In this paper, the results of the processing and heat-treatment studies on 40 to 60 at. pct CO alloys are presented. The magnetic properties have been found to be influenced greatly by the composition, by the cooling rate from the disordering treatment, and the final ordering time and temperature. Coercive force values, Hc, of 4700 oersteds and energy values, (BH)m, approaching 9,000,000 gauss-oersteds have been obtained by controlled cooling and ordering. PROCESSING OF THE ALLOYS The composition range of interest for permanent-magnet properties centers around the equiatomic composition Copt. In this region the alloys are dis-

Jan 1, 1959

By George F. Comstock

IT has been reported recently1 that the hardenability and toughness of forging steels may be improved appreciably by the use of complex deoxidizers containing titanium, aluminum, and vanadium. In the light of these results, an investigation of similar deoxidizers containing various hardening and grain-refining elements was proposed. These deoxidizers included three manganese-silicon-aluminum-titanium al- [ ] loys with and without boron and calcium, three titanium-aluminum ferroalloys with vanadium, molybdenum and zirconium, respectively, an aluminum-zirconium ferro-alloy, and plain ferroboron. Their approximate compositions are given in Table I, and the results obtained so far in the investigation of their effects on steel are presented in the later parts of this paper. METHOD OF USING DEOXIDIZERS The deoxidizers listed in Table I were used in three series of 0.40 per cent carbon steels, which were melted in a small basic-lined induction furnace and cast in the form of I7-lb. ingots about 2.75 in. square. The basic charge for each heat was 10 lb. Armco iron and 6 lb. of clean low-carbon sheet-steel scrap. When melted, this charge was deoxidized with 15 grams of ferrosilicon, then about 500 grams of pig iron was added to give the desired carbon content. After the pig iron was dissolved, nickel [ ] shot and high-carbon ferrochromium were added if required, and additions of 80 per cent high-carbon ferromanganese and 50 per cent ferrosilicon were made to provide the proper amounts of those elements. Aluminum was added to every heat 2 min. after the silicon, for grain-size control and preliminary deoxidation. One minute later the special deoxidizer was added to the clean bare surface of the molten steel, and 2 min. afterward the steel was poured into the ingot mold, using a hot-top and pipe-preventing compound after pouring to decrease the depth of the shrinkage cavity. The special deoxidizers were used mostly in the form of about ½ to ¾ -in. lumps,

Jan 1, 1942

By L. W. McKeehan

THE occurrence of twins in large ferrite crystals, made by a new process, was reported in a recent note.1 This paper describes a typical case of such twinning and suggests, on the basis of the observed facts, why smooth slip-planes are rarely observed in this metal. METHOD OF PREPARATION The material in. which the crystals here dealt with were grown was made from 1/8-in. Armco iron welding rod containing C, 0.04; S, 0.037; P, 0.003; Si, 0.008, and Mn, 0.02 per cent. This rod was cold drawn into wire about 1 mm. dia. A piece of this wire was supported vertically and was locally heated in hydrogen at atmospheric pressure to about 1400° C. by an alternating current (60 cycles per sec.) of about 35 amp., passed through it between a pair of traveling contacts about 8 cm. apart. The rate of travel for the case in hand was 12 cm. per hr. After some 30 cm. of the length of the wire had been heated and cooled in this manner the whole wire was immersed for a few seconds in dilute nitric acid, not restrained by alcohol. Etching was continued until, ass nearly as could be judged by eye, the original smooth cylindrical surface of the wire was no longer capable of specular reflection. MEASUREMENTS The wire in the etched state was next mounted in a goniometer of special form which allowed the measurement of the spherical coordinates of the normals to any plane surfaces left by the etching. These coordinates were most conveniently a polar distance, ?, from one direction of the wire axis, and an azimuth or longitude, [ø], from an arbitrary prime meridian. The region to be described more particularly is shown at a low magnification in Fig. 1, which gives two different views, differently illuminated to show the spatial relationship of a crystal occupying most. of the part shown and of an inclusion, or rather a series of three inclusions suspected of being twins based on the principal crystal.

Jan 1, 1928

By John B. Baker, Bernard B. Betty, H. F. Moore

Fox several years there has been in progress in the Materials Testing Laboratory of the University of Illinois an investigation of creep and fracture of lead and lead alloys. In the course of this investigation it has been shown that the phenomenon of creep occurs in part at the grain boundaries of lead and lead alloys. To study the occurrence of creep and the development of fracture within crystalline grains, two series of tests of single crystals of lead have been carried out. The first of these, a preliminary series, by Mr. Betty, has been described.1,2 The second, pursued by Mr. Baker for his doctoral dissertation, was carried out under the direction of Professor Moore, with the assistance of Prof. G. L. Clark in the X-ray work, and the cooperation and advice of Mr. Betty. This paper is based on the test data obtained in this second series. Single crystals of a very pure commercial lead have been prepared, some of them tested to measure creep, others tested to fracture under long-continued steady load, and still others tested under cycles of repeated tension. An interpretation of the test data of these single-crystal tests is offered, which is a combination of parts of several well-known theories. SPECIMENS The single-crystal specimens were made from a piece of very pure commercial lead sheathing. A spectroscopic analysis of one of the single crystals showed the presence of 0.005 per cent Bi, 0.0001 per cent Cu and 0.0003 per cent Ag. Preparation.-The Bridgman method of casting single-crystal speci¬mens was used.3 The specimens were cast to the shape and size shown in Fig. I (dimensions in Fig. 4c) in a duralumin mold. Molten lead does not stick to duralumin. Fig. 1 shows the mold and the blast flames for heating. After the mold had been heated to the temperature of molten

Jan 1, 1938

EdgaR S. Cook, Pottstown, Pa.:—Many friends and acquaintances seem to be under the impression that the Warwick Iron & Steel Co. received a' license from Mr. Gayley, free of cost, as an inducement to adopt the process. This impression is not correct, since the license was paid for, and I think it was the first payment that Mr. Gayley received for the use of his process. As president of the Warwick Iron & Steel Co., I am responsible for its earnings, and with only the experience at the Isabella furnaces as a guide, the directors of the company considered that there was a great risk in expending the large sum of money required for the plant. They, however, acted favorably upon my recommendation, and to this extent I am responsible for the installation at the Warwick furnaces. I made the best agreement possible with Mr. Gayley, and naturally our company received certain advantages. It will be contrary to all experience if subsequent plants do not show some improvements and economies in construction. It is to our indirect benefit that all subsequent licenses granted by Mr. Gayley should be charged at a much higher rate than we paid; and I trust that he will see to it that all such licenses granted, especially to companies making merchant iron, shall be at a maximum figure. The Warwick Iron & Steel Go. is not interested in any way in exploiting the merits of the Gayley dry-blast process; on the contrary, looking at the subject from a narrow and selfish standpoint, it is to the advantage of our company that no merchant blast-furnace competing with our iron-product should be equipped with a dry-blast plant. There is a clause in the contract with Mr. Gayley, whereby our company agrees to furnish him with all the data derived from the operation of the dry-blast plant, and that he or his

Jan 1, 1909

By William R. Webster

I have continued the investigation of the Pottstown Iron Com pany's basic Bessemer keel plates on the line referred to in my paper of last October (Trans., xxi., 766)) and have added a study of the hardening effects of sulphur, which were not taken into account at that time. The results are so encouraging that I now give them in full. For some months we have graded all the steel at these works by the table given in my former paper, and checked the grading by the forging-tests as described in the paper of Mr. Joseph Hartshorne, read at the same meeting (Trans., xxi., 748). The steel thus graded was bloomed for the plate orders. Then one slab was rolled into a plate for the order, and a tension-test was made of this plate. By the result of this tension-test we were guided in rolling the balance of the heat. Out of several hundred heats graded in this manner, 95 per cent. met the requirements of the orders in every respect, and were accepted; but these results will no doubt be improved upon, when the influence of sulphur is also considered.. The hardening effect of sulphur seems to be about 500 pounds per each .01 per cent. of increase. In the table accompanying the pres ent paper, the ultimate strength with .06.5 per cent. sulphur agrees with the old table where sulphur was not considered; that is, for all steels with less than .065 per cent. sulphur we now get lower re sults, and for those with more sulphur, higher results. Making this allowance for sulphur, the assumed ultimate strength of a 3/8-inch plate of pure iron is reduced from 38,000 pounds per square inch to 34,750 pounds. With this as a basis, I have constructed my new table, giving each of the elements, carbon, phosphorus and manganese the same hardening effect as before, to wit : Carbon is credited with a constant effect of 800 pounds per each, 0.01 per cent. Phosphorus shows greater effect in high-carbon than in low-carbon steels. For 0.07 and 0.08 C, it has about the same effect as carbon, that is, 800 pounds for each .01 P. This increases to 1500 pounds per .01 P in 0.15 C steel, or nearly twice the effect of carbon. This

Jan 1, 1894

By M. J. Blackburn

The phasal equilibria in TI':Al alloys has been studied Ry transmission electron microscopy, electron diffraction, and X-ray diffraction. It is shown that three-phase fields exist below the transformation, viz.: a disordered hexagonal solid solution a; an ordered hexagonal phase based on Ti3Al, aa; and a two-phase region. (a + (YZ) , occurring between the single-plzuse fields. The size. disiribution, and morphology of- the a, phase in the two-phase region is shown to be dependent upon the alloy composition and heat treatement. The ordering process in the a, phase leads to the formation of anliphase domain boundary networks; the contrast and stability of these networks is shown to be dependent on alloy composition. A new and relatively simple phase diagralil for the systemm is constructed. The phasal equilibrium at the titanium-rich end of the Ti:Al system has long been the subject of considerable controversy. crossleyl has recently reviewed the phase diagrams that have been advanced for the system and in his turn proposed yet another one. There would seem to be general agreement that a phase exists at a composition at or near Ti& with an ordered hexagonal DO,,-type structure. However, several other phases have been proposed; for instance, Ence and ~ar~olin's' diagram includes two phases, Ti2A1 and Ti3A1, in the region up to 25 at. pct Al. The position of the proposed phase boundaries varies over a considerable compositional and temperature range, a point graphically illustrated in Fig. 1 of Crossley's paper.' It is perhaps germane to briefly examine the techniques used by other workers in the establishment of the phase structure. These fall into three categories: 1) X-ray diffraction, the only limitation of which is the rather low intensity of superlattice reflections in this system.3 Thus, superlattice reflections become increasingly difficult to detect in the more dilute aluminum alloys. 2) A considerable amount of optical microscopy has been performed"2'4 and it will be shown in a later section that many of the obscure mi-crostructures that have been observed can be attributed to hydrogen contamination. It is concluded, therefore, that such observations should be interpreted with considerable care. 3) The variation of some physical property with aluminum content has been measured.5"7 These methods are a useful indication of the existence of a transformation, but are usually insufficient in themselves to identify the transformation. The results using these techniques will be considered in more detail in the discussion. In this paper, the phase structure of alloys containing up to 25 at. pct A1 has been studied by transmission electron microscopy and X-ray techniques, and the results are used to generate a new and relatively simple diagram for the titanium-rich end of the Ti:Al system. EXPERIMENTAL A series of alloys containing 5.05, 10.16, 13.39, 13.99, 14.40, 20.83, and 25.05 at. pct A1 were obtained in the form of hot-rolled sheet 0.02 in. thick. These alloys contained 0.10 to 0.15 pct 0. Thirty-gram arc-melted buttons were prepared from iodide titanium and 99.99 A1 which contained 16.1, 16.9, 18.2, 19.0, 21.6, 22.2, 23.0, and 23.9 at. pct A1 and had an average oxygen content of 0.03 pct 0. The differences in oxygen content did not appear to influence the nature of the phase transformations which were found. Oxygen content may affect the temperature of these transformations, but insufficient samples of the high-purity alloys were examined to answer this question. The heat treatment of alloys was performed in dynamic atmosphere and vacuum furnaces or in helium -filled silica capsules. A special vacuum furnace was constructed to provide a high quenching rate in which rates of 4000°C per sec were obtained using water as the quenching medium. As pointed out by Crossley,' it is important to avoid heat treatment in the a - [} phase field as the resultant segregation of the alloy into the two phases containing different amounts of aluminum can persist through subsequent treatments leading to ambiguous results. It will be demonstrated later that step cooling of specimens from the a phase region can also lead to anomalous effects. Thus, all solution treatments were carried out in either the a or 3 phase fields followed by water quenching and subsequent isothermal annealing at various temperatures. X-ray analyses were performed on a diffractometer on fine-grained bulk specimens. The value of long-range order parameter, S, wa_s calculated from the integrated intensity of the (1211) reflection. In general, the intensity of the (1011) superlattice reflection was compared with that of the (2021) fundamental reflection to correct for experimental differences between measurements. Thin foils for electron microscopical examination were produced by electropolishing using the technique described in an earlier paper.8 Dark-field techniques were employed to a large degree in this investigation using the gun-tilt method. Finally it should be noted that the lattice parameters of the D01,-type superlattice are approximately related to the disordered hexagonal phase parameters by Crf - c, and 2ad - a, where the subscripts s and d refer to the ordered and disordered unit cells, respectively.

Jan 1, 1968

By John Wulff, David A. Stevenson

The solubility of iron and cobalt in liquid lead, the solubility of chromium in liquid tin, and nickel in liquid silver were determined up to 1300°C in an atmosphere of hydrogen. Liquid samples were taken at different temperatures and analyzed. The data obtained were plotted to show the relationship between log mole fraction of solute and the inverse of the absolute temperature. Resulting values for the differential heat of solution (AH) and the excesspartial molar entropy (S)are: for the iron-lead system = _24,200 cal per mole and AT = 5.0 e.u. for the a phase, and AH = 18,300 and S = -0.1 e.u. for the y phase; for the cobalt-lead system AH = 16,500 cal per mole and AS =0.7 e.u.; for the chromium-tin system AH = 15,600 cal per mole and AS = 8.5 e.u.; for the nickel-silver system AH =18,000 cal per mole and AS = 4.0 e.u. RECENT developments in coating, brazing, and heat transfer have focused attention on specific cases of solid-liquid interaction in metal systems, particularly those involving dilute liquid solutions. One fundamental quantity of interest in such systems is the equilibrium phase distribution between solid and liquid phases. In any effort to fully understand such interactions, one must be able to describe the equilibrium state precisely. Furthermore, in order to develop genera! relations for such systems, one must know the equilibrium state in a number of different cases. This investigation was devoted to a study of the equilibrium phase distribution in four binary systems: solid iron-liquid lead; solid cobalt-liquid lead; solid chromium-liquid tin; solid nickel-liquid silver. The iron-lead system was previously studied by Shepard and parkman' and later by Fleischer and Elliott2 with differing results. Both investigations were carried out by sampling the saturated liquid, and analyzing it chemically. The cobalt-lead system was previously reported by Pelzel,3 who noticed no discontinuity near the transformation. A limited investigation of the chromium-tin system was made by Wlodek and wulff4 using a weight loss method. This work was done in conjunction with the development of a process for coating molybdenum with chromium from tin solutions. To more fully under- stand the kinetics of the process, a more accurate determination of a solubility was desirable. No significant data were found in the literature on the nickel-silver system. Data on the latter system were, however, relevant to the investigation of the corrosion kinetics of copper-nickel alloys in liquid silver as carried out by Harrison and wagner,5 EXPERIMENTAL APPARATUS AND PROCEDURE Of the techniques available for the study of such systems the most effective appears to be that of liquid sampling,2,6,7 which is the method used in the present investigation. A schematic diagram of the sampling furnace is given in Fig. 1. Large pieces of solute metal, in excess of saturation solubility, were added to 200 g of the solvent metal, and the entire charge placed in an alundum crucible. Analytical reagent or materials of chemically pure grade were used in all investigations. The crucible was contained in a zircon muffle tube positioned vertically in the uniform hot zone of a Globar resistance furnace. The tube was provided with a number of ports which permitted sampling at temperature and in controlled atmospheres or vacuum; the ports were also useful for evacuation and introduction of gases as well as for thermocouple measurements. A chromel-alumel thermocouple Sheated in a porcelain tube was used for temperature measurements. A purified hydrogen atmosphere was employed in all experiments reported in this paper. The hydrogen was purified by passing it first over hot copper gauze to remove oxygen and then through a molecular sieve immersed in

Jan 1, 1962

H. 0. Hofman, Boston, Mass. (communication to the Secretary*) :—The experimental demonstration by Professor H. Ries, of the fact that a mixture of clay and finely-ground flux will melt more readily than one in which the flux is less fine and therefore less intimately mixed, is very striking, and will be appreciated especially by those who have to discuss, before classes of students, fusions on a small or a large scale. The statement, that I " rather disputed" the influence of size of flux-particles on the ease with which fire-clay mixtures fused, is an erroneous inference from the paper written by Mr. B. Stoughton and myself in 1898.' We did not undertake to study the influence upon fusibility of the sizes of the particles, either of clay or flux. What we did try to find out was, whether the common practice of finely grinding raw or burnt clay, or a mixture of the two, before testing with Seger cones for resistance to heat and to fluxes, xould give the same results as if the materials were tested just as they were going to be

Jan 1, 1904

By D. Turnbull, J. H. Hollomon

THERE is a large body of evidence'" indicating that solidification during the liquid-solid transition is usually induced by heterogeneities present in the liquid. By dispersing liquid metals into small droplets, the impurities responsible for catalyzing solidification are isolated within a small number of these droplets. The effect of the foreign body therefore is restricted to a single drop by this technique. Thus upon cooling below the melting temperature, solidification is initiated by homogeneous nucleation in the majority of the droplets that do not contain impurities. In the case of solidification of liquid metals, the activation energy for nucleation is so great that its rate changes by orders of magnitude for a change in temperature of only several degrees centigrade.' Effectively homogeneous nucleation occurs at a critical temperature upon continuous cooling. Thus by microscopic observation of single particles during cooling, a temperature at which the rate of homogeneous nucleation becomes sensible can be determined.3 since at the temperatures at which nucleation occurs in the absence of impurities the rate of crystal growth is extremely rapid, the temperature at which the entire particle solidifies is very nearly the temperature at which the nucleation of the solidification occurs. Thus for liquids that freeze at high temperatures the onset of nucleation can be established by simply observing the temperature at which the marked heat evolution and increase in brightness of the particle occur. For liquids that freeze at lower temperatures the onset of nucleation can be determined by a rumpling and change in shape of the particle resulting from its solidification. The microscopic technique for observing the solidification of small particles has already been described." In earlier papers the nucleation of solidification of pure metals 5,6 and of alloy systems7 showing complete liquid and solid solubility have been described. In the present paper, the observations are extended to a simple eutectic system (Pb-Sn) where the possibility of the formation of two solid phases exists. Metals for the investigation were obtained from the American Smelting and Refining Co. in the form of pure lead and pure tin, 99.8 and 99.9 pct purity, respectively. An ingot of each of the pure metals was made into shot by heating the metals at a temperature about 50 °C in excess of the melting point and pouring the liquid slowly into a container of water at 15°C. Samples of the shotted pure metals were weighed out to make alloys containing 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, and 90 atomic pct Pb. Samples of each alloy were then melted in separate beakers. Each melt was poured through a pyrex funnel into a cylindrical mold (% in. ID). The casting solidified in 10 to 20 sec. The inside of the mold as well as the funnel through which the metal was poured were coated with graphite to eliminate adherence of the metal. Analyses were performed on some of the compositions and are given in Table I. The compositions also were checked for these samples and for those that were not analyzed by determining the spread between the liquidus and the solidus upon melting the small metal particles. These measurements agreed as well with the nominal compositions as the analyses listed above. Results The results of the supercooling experiments for the several alloys are summarized in Table II and plotted on the constitution diagram in Fig. 1. Data for the pure lead and pure tin were taken from earlier investigations. The values for the maximum supercooling of the several alloys are the average of several determinations on a number of drops of each alloy. The maximum value in any determination was within about 2 pct of the average. For the alloys containing from 20 to 60 atomic pct Sn, inclusive, two marked changes of the surface structure were observed upon cooling. At the higher temperature, after the first appearance of the solid phase it continued to grow slowly at a constant temperature and then stopped. At the lower temperature the alteration of surface structure was abrupt. For the alloys containing from 70 to 95 atomic pct Sn, inclusive, an abrupt change in surface structure was observed at a single critical temperature.

Jan 1, 1952

AlFred JamEs," London, Eug.:—I thank you, gentlemen, for Sour kind invitation to address you. It is a very great pleasure for me to be here at your annual meeting, and, although I have been a member since 1894, this is the first opportunity I have

Jan 1, 1909

By L. S. Darken, H. A. Wriedt

An investigation has been made of nitrogen absorption by the lattice defects in a low-carbon steel afte~ Plastic deformation. Specimens in which defects were distributed by various combinations of cold rolling and vacuum heat treatment were equilibrated with controlled ammonia + hydrogen mixtures at 300° to 450°C to study the relation between the solubility and the thermodynamic activity of nitrogen. The results are interpreted in terms of nitrogen being absorbed upon two different types of defect sites, called A sites and B sites. The concentrations of these sites are calculated for specimens with various histories of straining and annealing; and the thermodynamic relations descrihing the equilibrium distribution of nitrogen among the A, B, and ordinary interstitial sites in ferrite are evaluated as follows: THE generalization that the solute atoms in a solid solution interact with imperfections in the solvent lattice is now universally recognized and the subject of an extensive literature. All types of imperfections—point, line, or surface—exhibit these interactions, but the relative importance of each type depends upon its concentration, the strength of its interaction with the particular solute atom, and whether the interaction is attractive or repulsive. The strength and sign of the interaction vary with the vectorial displacement of the solute atom from the imperfection in the crystal. The concentration of lattice defects increases during plastic deformation and the effect of the imperfections upon the solute atoms is usually perceived only after cold work or irradiation. Two experimental methods have previously been used to observe the effects of interaction between nitrogen atoms and lattice imperfections in a iron. Internal friction, which was first used for this purpose by Dijkstra,1 has been applied more often than the electrical-resistivity method of Cottrell and Churchman.2 The method of the present investigation has not been used before.* Uniform specimens of steel with a metastable defect structure are produced by cold rolling and subsequent heat treatment below the recrystallization temperature. Variations in the defect structure are obtained by varying the amount of strain and the heat-treatment conditions. The specimens are then saturated with nitrogen at moderately elevated temperatures in ammonia + hydrogen mixtures having various thermodynamic activities of nitrogen below saturation with Fe4N. From the nitrogen contents of analyzed samples, the metastable equilibria of interactions between the defects and nitrogen can be established and the concentration of sites for nitrogen atoms in the lattice defects calculated. A steel was used in the present experiments instead of purified iron or iron alloys because the amount of nitrogen absorbed at defects is larger in the steel over a much wider range of experimental conditions and could therefore be measured more accurately. The effect of alloy composition is discussed in Part II of this paper; it is sufficient to say here that impurities and phase heterogeneity in ferritic alloys favor the generation and/or retention of larger defect concentrations during plastic deformation and annealing at 300° to 500°C. MATERIALS AND EXPERIMENTAL PROCEDURE The experimental specimens were prepared from stock of a low-carbon steel, which will be called "X steel" here, with the composition: C, 0.12 pct; Mn, 0.43 pct; P, 0.010 pct; S, 0.034 pct; Si, 0.007 pct; As, 0.086 pct; Cu, 0.022 pct; Ni, 0.009 pct; Cr, 0.003 pct. The stock was all from a single ingot made by the basic open-hearth process, which was hot-rolled to strip 0.080 in. thick.. This hot-rolled strip, given the code designation "XH", was the starting material for preparing a series of cold-rolled sheets. The latter are designated "XC27",

Jan 1, 1965

By Sidney G. Parker, Jack E. Pinnell

Cubic ZnSe crystals have been grown with HCl, HBr, and I, as chemical transport reagents. The growth of large, well faceted crystals is in the order HCl < HBr < I, with some produced by I, transport being 1 cm on an edge. ZnSe:I crystals showed no strain in cross polarized light and were homogeneous as determined by electron microprobe. These ZnSe:I crystals had a mobility at 25°C of about 300 sq cm per v-sec and contained 103 dislocations per sq cm; further, these crystals were pure cubic and showed both photolumi-nescence and photo conductance. Doping was attempted during crystal growth. ZnS and Zn (S,Se) crystals were also grown by I, transport. ZnSe crystals have been grown by most of the common techniques.1"6 Of these, chemical vapor transport as developed by Kaldis2 showed promise of producing high perfection, cubic ZnSe. With chemical transport, crystals can be grown far below the transition temperature for conversion of cubic to hexagonal structure. A small temperature gradient between source and growth region tends to allow near equilibrium growth, which should lead to good crystalline perfection. Because it is necessary to form volatile compounds, halogens or their compounds are extensively used as transport agents. HCl, HBr, and I, were compared as transport agents for growth of ZnSe crystals. Doping during crystal growth was attempted. ZnS and ZnSxSe1-x crystals were also grown by chemical transport. Electrical and optical properties of the crystals were examined. EXPERIMENTAL Fig. 1 is a sketch of the growth apparatus, which was a modification of Kaldis&apos;. A quartz rod which butted against the seed crystal served as a heat sink to promote growth only on the seed. Initially, crystal growth was attempted with ZnSe prepared by wet chemical methods. Because such a material contained oxides and selenates, HC1 reacted with these oxygen compounds to form H2O and no ZnSe transport occurred. Further, this ZnSe contained about 10 ppm Cu plus other impurities. High purity ZnSe, containing small amounts or no oxygen compounds, was prepared by reaction of H2Se with zinc vapors at 600° to 800°C in an atmosphere of palladium diffused H2.7 The ZnSe thus produced was usually copper free and contained only 1 ppm by weight of magnesium as determined by emission spectrographic analysis. G.E.&apos;s electronic grade ZnS, which had about 10 ppm metallic impurities, was used without further treatment. ZnS-ZnSe charges were prepared by mixing the two compounds together, then sintering 24 hr at 1100°C in an H2S ambient. The gases, HBr and HC1, were commercial grade, of 99.9 pct purity, while the I2 was 99.999 pct pure. The single crystal seeds with (111) faces for growth were mechanically held in place by sealing the outer quartz tube to the growth tube. After the charge was introduced, the system was outgassed at l0-5 torr while heated to 500°C. The desired quantities of transport reagents were then sealed off in the system, which had been cooled to 25°C. The growth tubes were inserted into a furnace with the desired temperature and thermal gradient. The system was allowed to cool for 1 to 12 hr from growth temperatures of about 850" to 25°C. The tubes remained stationary during crystal growth. HCl CHEMICAL TRANSPORT GROWTH Preliminary runs with HC1 had a temperature gradient of 100° to 200°C and no seed or heat sink. Only small crystals were obtained in these experiments as

Jan 1, 1970

By Frederick Bacorn

THE paper of Reno H.. Sales on Ore Deposits at Butte, Mont.,&apos; is a careful and painstaking work, an important contribution to the literature of the subject. As is almost inevitable in a work of such magnitude, a few misstatements occur; and some of these I shall endeavor to point out. Mr. Sales has also fallen into error, as I think, in the application of his theory of ore deposition; and while the modification which I venture to suggest is a minor one geologically, it is of great economic importance. I refer to Mr. Sales&apos;s idea of an outward migration of mineralizing solutions from a supposed central copper zone. In order that I may make myself plain, I must first epitomize the theory as a whole, which I understand to be this: All of the Butte ore deposits (save those along the Continental fault, not herein considered) are derived from solutions of magmatic origin, which, at the beginning of their ascent from a great depth, were, acid in reaction, hot, and were carriers of copper, zinc, manganese and other metals. As they departed from their point of origin they lost heat, and, because of reactions with the wall rock, became more and more alkaline. The metal deposited from these solutions in their hot condition was principally copper; and, as they cooled, they deposited less and less copper and more and more manganese and zinc, until the copper practically disappeared. With this theory in general I have no fault to find, nor have I, it must be stated, the qualifications necessary to enable me to pass upon it critically; but it seems to me to be reasonable and probable, and is one which I am quite willing to accept.

Jan 8, 1914

By E. A. Gulbransen, K. F. Andrew

THIS paper. will present the results of our studies on the kinetics of the gas phase reactions of co-lumbium and tantalum with O2, N2 and H2. Studies on zirconium and titanium have been previously reported.9,11 Due to their high melting points and their many excellent physical and chemical properties, colurn-bium and tantalum have been finding their places as useful metals in science and industry. Chemically the metals are very inert to gas and liquid phase corrosion at room temperature. However, at moderate temperatures of 250°C and higher the metals react readily with oxygen and hydrogen. It is of interest to study the gas phase reactions of these metals for the following reasons: (1) to compare the rates of the several reactions with those of other metals and to correlate the rate data with theory and structure predictions, (2) to add basic information on the practical difficulties of the reduction, refining and working of columbium and tantalum, (3) to anticipate new uses for the metals and (4) to understand the role that the metals play as components in high temperature alloys. Literature Survey A number of papers exist in the literature on the gas phase reactions of columbium and tantalum with O2, N2 and H2; however, only fragmentary data have been reported on the kinetics of these reactions. Although the free energy of formation of the oxide Ta2O520at 25°C has been determined and some thermodynamic work has been reported on columbium and its oxides, the data are not sufficient to make equilibria calculations at elevated temperatures. Oxidation: 1. Kinetics: The rate of oxidation of columbium and tantalum has been studied by McAdam and Geil23 using the interference color method. Tantalum is reported to oxidize more slowly than columbium, zirconium and iron. The amounts of oxidation of columbium after 20 hr in air for several temperatures are reported by the Fansteel Metallurgical Corporation.36 Columbium starts to oxidize in air at about 200°C. The oxide is said to be adherent and prevents further oxidation until the temperature is raised. Columbium is reported not to become brittle on heating in air for short periods like tantalum because the oxide film prevents further reaction. The columbium oxides dissolve into the metal when heated in a vacuum at temperatures between red heat and 1200°C. Above 1200°C the oxides are reported to evaporate. Columbium, in the oxide free state, is an active getter in vacuum tubes. 2. Preparation and Structure: G. Grube, O. Kuba-schewski and K. Zwiauer15 have studied the decomposition of Cb2O5 in argon. They find that CbO2 is formed slowly at 1150° and rapidly at 1300°C. Cb2O5 can be reduced to CbO2 by moist H2. The reduction of this dioxide to the lower oxides is rapid. By varying conditions CbO2, Cb2O3, CbO and Cb2O can be formed. CbO2, CbO and Cb2O have independent lattices while Cb2O3 is a stoichiometric mixture of CbO and CbO2. In a later paper O. Kuba-schewski" has shown that CbO is cubic and that CbO2 has a rutile type of lattice. The most exhaustive work on the oxides of columbium is that of G. Brauer.8 The number and constitution of the solid phases in the binary system Cb-O were investigated by the preparative, analytical and X ray methods. He indicates that only the oxides Cb2O5, CbO2 and CbO exist with limited regions of homogeneity. The solid oxide Cb,O, exists

Jan 1, 1951

By AIME

Generally speaking, the mining industry had a good year in 1948 with most mineral products being produced in record quantities for peacetime standards. The big boys-iron and steel, coal, and petroleum-indicated the industry-wide trend by surpassing 1947 production figures. Although exploration and expansion are being pushed aggressively in all branches of the industry, there is a pronounced trend to engineering and research directed at cutting production costs, improving the product, and finding new markets. These improvement campaigns are making headway; in the bituminous coal industry, 5.43 tons per man employed is the new production record; 83 million tons of iron ore were unloaded at lower Lake ports, breaking another peacetime record; magnesium, due to improvement in manufacturing techniques, now competes on the market with aluminum.

Jan 1, 1949

By Bruno KERL

THE list of deaths reported during the year 1905 comprises the following names (the figures in parentheses indicating the year in which the persons named were elected to membership:- Honorary Member.-Dr. Bruno Kerl. Members and Associates.-Charles Christy Adams (1903), John Wesley Anderson (1898), William Burton Barber (1901), Thomas A. Bennett (1900), Luke W. Bryan (1901), Edwin S. Daugherty (1905), William Scott de Camp (1875), George H. Eldridge (1889), B. W. Frazier (1871), John Broome Guinn, Jr. (1897), Dana C. Irish (1900), Harry Hugh Lee (1899), William Alfred Lindsay (1902), Roland C. Luther (1884), James MacNaughton (1890), Gordon McLean (1899), Herbert Holmes McNamara (1902), August R. Meyer (1886), William Orr (1897), William J. Parker, Jr. (1898), Joseph Phillips, Jr. (1895), Charles O. Ripley (1902), Emmerich J. Schmitz (1883), Ludwig Philip Seeger (1900), Jacob Johnston Sperry (1900), Gustavus H. Stoiber (1902), William L. Study (1905), Robert Macnair Wilson Swan (1900), Richard Henry Terhune (1886), Joseph Thiry (1892), John N. Tisdale (1903), Alfred Isham Totten (1897), Walter H. Virgoe (1902), Charles H. Wellman (1890), Harvey L. Williams (1903). Of these, Dr. Bruno Kerl and Prof. B. W. Frazier have been made the subjects of special Biographical Notices in the Bi-Monthly Bulletin 1 the former in No. 4, July, 1905, p. 743, and the latter in No. 5, September, 1905, p. 1097. Concerning the remainder of the list, the following paragraphs comprise such information as could be obtained by the Secretary. Charles Christy Adams, who had been a member of the Institute since 1903, died in Johannesburg, South Africa, August 31. 1905. He was born in New York City, July 13, 1849, and received his technical training at the Colorado State School of

May 1, 1906

By E. I. Larsen, A. S. Doty, F. R. Hensel

The alloy under discussion is a Pig. I shows results of heat-treating tests nickel-silicon bronze and is one of many on two typical nickel-silicon bronze castings age-hardening or precipitation-hardening of the type on which the observations were copper-base alloys. The hardening constituent is a nickel-silicon compound.l The quenching temperature necessary to produce hardening by a subsequent aging treatment is a function of the composition and extends from about 700°C. to 950°C.; the aging temperature range extends from 4000 to 600°C. The work carried out by the authors of this paper was confined to cast alloys having compositions within the ranges of: 1.5 to 3.00 per cent Ni; 0.4 to 0.75 per cent Sj: balance. comer. made. A quenching temperature of 750°C. produces almost as high a hardness on subsequent aging as do quenching temperatures of 850&apos; and 900°C. Several foundries have spent years of active and intelligent effort in trying to control the casting and heat-treating variables of nickel-silicon bronzes and finally gave up the attempts because of the inconsistencies of results.2 This undesirable characteristic was not manifest in the ultimate hardness or conductivity but primarily in tensile strength and ductility, as shown in Table I. The variation in tensile properties was often much greater than that existing on the alloys

Jan 1, 1941

By T. H. Courtney, G. W. Pearsall, J. Wulff

The mechanism, of the decrease in transition temperature of Nb3Sn was studied. Presintered Nb3Sn powder compacts were heated in a dynamic vacuum at elevated temperatures. Loss of tin resulted from these heat treatments and transition temperature as a function of tin loss was discontinuous at a critical value of tin loss. In general, decreases in transition temperature were correlated with deviations from AS a class, the A15 structure-type (also known as Cr3O or ß W) compounds have the highest superconducting transition temperatures.&apos; In this class are stoichiometry and presence of vacancies in niobium sites. The effect of vacancy distribution on the physical properties of Nh3Sn is considered. It is concluded that the close-packed atomic A chain in the A3B A15 structure must be preserved both in coutinuity and direction if good superconducting properties are to he obtained. tempting to associate these high transition temperatures with the most unique crystallographic feature of the A3B structure: the three close-packed, orthogonal chains of A atoms.&apos;0"&apos; There are at least three principal mechanisms by which the perfection of these "A-atom chains" could be interrupted: changing stoichiometry, inducing disorder, or introducing vacancies. Departures from stoichiometry in either direction in V3Ga lower the transition temperature.7&apos;8 In niobium-

Jan 1, 1965

By A. S. Doty, E. I. Larsen, F. R. Hensel

The alloy under discussion is a Pig. I shows results of heat-treating tests nickel-silicon bronze and is one of many on two typical nickel-silicon bronze castings age-hardening or precipitation-hardening of the type on which the observations were copper-base alloys. The hardening constituent is a nickel-silicon compound.l The quenching temperature necessary to produce hardening by a subsequent aging treatment is a function of the composition and extends from about 700°C. to 950°C.; the aging temperature range extends from 4000 to 600°C. The work carried out by the authors of this paper was confined to cast alloys having compositions within the ranges of: 1.5 to 3.00 per cent Ni; 0.4 to 0.75 per cent Sj: balance. comer. made. A quenching temperature of 750°C. produces almost as high a hardness on subsequent aging as do quenching temperatures of 850&apos; and 900°C. Several foundries have spent years of active and intelligent effort in trying to control the casting and heat-treating variables of nickel-silicon bronzes and finally gave up the attempts because of the inconsistencies of results.2 This undesirable characteristic was not manifest in the ultimate hardness or conductivity but primarily in tensile strength and ductility, as shown in Table I. The variation in tensile properties was often much greater than that existing on the alloys

Jan 1, 1941