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By John D. Janak

Thank you for inviting me to come here and be your keynote speaker. Texas also thanks you for being included as part of the Rocky Mountain Coal Mining Institute. We'll kind of think of Texas as Baja Rocky Mountains. I've always wondered why coal miners were the only people to go to the mountains in the summer time-and now I know why. The program committee should be given a big hand for selecting this RESORT. And the golf course is stimulating to say the least. This is a very beautiful location. I was asked to talk about CHALLENGES, OPPORTUNITIES and INNOVATIONS as they affect the coal industry. I am going to do that from a Texas perspective. But first, since Texas is the newest state to belong to the Institute, I would like to give you a little background on how our coal industry got started and where we are at today. The vast majority of our coal is called lignite-it has a little lower heating value than most other coals and ranks somewhere between buffalo chips and sub- bituminous. Lignite is found In three geological formations running Northeast to Southwest through South and East Texas. In-place reserves lying within 200 ft. of the surface total 14 billion tons. This slide shows the lignite formations with cur- rent mine operations colored in RED. Mines that are planned to be built in the next 10 years are shown in BLUE. Lignite was used mostly by settlers in Texas during the 1800s. It was used as a fuel to fire locomotives during the Civil War. Between 1900-1930, about 100 mines, mostly underground, were operating in Texas producing lignite for home heating and as a boiler fuel. Here are some slides showing underground access, [lie tipple used to process the lignite, and the underground workings. This is the "BIG LUMP COAL COMPANY" as shown here. The typical underground mine was 100-150 ft. deep and each miner produced 7-10 tons per day-all by hand. In 1926, the Texas Power & Light Company built the Trinidad Power Plant and began using lignite as a boiler fuel. The lignite was mined by the McAlester Fuel Company at the nearby Malakoff Mine. Here are some slides showing a stripping shovel at Malakoff uncovering lignite. The lignite was loaded into railcars in the pit for transport to the power plant. This is a picture of the Trinidad Plant which had two 20 MW units and one 32 MW unit. At the time, Trinidad was the largest power plant in the United States using lignite exclusively as a fuel. Trinidad operated until 1942 when it was converted to natural gas that was sold to the plant for 3 ½ ¢ per MMBT'U. The mine closed after having produced 7 million tons. Lignite was mostly forgotten about until 1953 when Alcoa started an aluminum smelter. Our Company formed a subsidiary called Industrial Generating Company to operate the power plant that furnished electricity to the smelter. We also operated the nearby Sandow Mine that supplied lignite as a fuel to the power plant

Jan 1, 1989

By W. F. Domis, F. von Gemmingen, F. Garofalo

The effect of rain size on the creep behavior of an austenitic iron-base alloy has been studied at 1300° F under conditions of constant stress. The average grain diameter varied between 9 and 190 p (ASTM 10.7-2). The subgrain size and apparent activation energy for creep were not found to depend in any systematic manner on gain size. Grain hozmdary serrations were observed in all specimens tested. The variation of the secondary-creep rate, 2,, with the pain diameter, 1, is given by: es = K(213m + 1 )/l.]; 1, is the grain diameter zohere is reaches a minimum. Results in the literature shoujthat 1,increases as the temperature increases. At low creep temperatures is is therefore proportional to 12, at intermediate temperatures <, exhibits a minimum, and at high creep temperatures is is proportional to 1/1. The dependence ofis on the stress, u, is given by: t, = A" (sinh acrln, a and n show little variation with 1. The dependence of A" on 1 is given by: A" = KA[(21k + 13)/1]. For 1 » >>lmn = 4, and at constant values 01- isat lozu stress levels, the steady-state stress is given by the Hall-Petch relation. The variation of c, with grain size is believed to he associated particularly with grain boundary generation of dislocations which becomes more important with increasing temperatures. SEEMINGLY inconsistent experimental findings have led to a certain amount of confusion concerning the effect of grain size on creep behavior. The confusion is attributed to a lack of test results obtained over sufficiently wide ranges in grain size, stress, and temperature. Experimental results presented in this paper and results available in the literature1-5 show a consistent behavior and lead to a unified concept for the dependence of secondary-or steady-state creep rate on grain size. In accordance with this concept, which is substantiated experimentally, secondary-creep rate should increase with increasing grain diameter at low creep temperatures, leading to greater creep strengths for fine-grained materials. At intermediate temperatures the secondary-creep rate should decrease to a minimum and then increase as the grain size is increased. At high creep temperatures the secondary-creep rate should decrease with increasing grain size, leading to greater creep strengths for coarse-grained materials. Whether a temperature is high or low for creep in a metal or alloy depends primarily on its melting temperature. MATERIAL AND TEST PROCEDURES The material tested was an austenitic iron-base alloy of the following composition (wt pct): C, 0.005; N, 0.017; Mn, 1.26; Ni, 14.21; and Cr, 17.18. Two 15 -lb ingots were forged and hot-rolled to 5/8-in.-diam bars which were then cold-rolled and cold-swaged to a diameter of 0.49 in. These were sectioned into 3-in.-long blanks and heat-treated at various temperatures to obtain different grain sizes. The procedures employed and the results obtained are summarized in Table I. The secondary treatment at 1400° F followed the primary treatment without intermediate cooling to room temperature. This final treatment was employed to minimize various effects arising from heating to different temperatures during the primary treatment, particularly differences in intragranular dislocation structure, segregation of interstitial atoms at grain boundaries, and density of grain boundary ledges. The intragranular dislocation structure was examined by electron transmission metallography after each of the treatments described in Table I. Isolated dislocations and a few tangles were observed but no evidence of subgrains was found after any of the treatments. No grain-size effect was evident on the density and distribution of dislocations. Stabilization of grain boundary structure is particularly important because, as will be discussed later, grain boundaries influence high-temperature creep behavior. Magnetic-permeability measurements after each treatment and

Jan 1, 1964

By L. F. Mondolfo, B. E. Sundquist

The crystallographic orientation relationships resulting when lead is nucleated from the liquid by Ni, Cu, Ag, and Ge were determined. For each nucleating agent several definite orientatioz relationships were found. These relationships seemed to be controlled by good symmetry relations and low crystallographic disregistry between mating planes. For any given nucleating agent the under colling for nucleation was found fairly constant and independent of the orientation relationship and consequent disregistry. It was also found that, upon re melting and refreezing the Pb, the orientation relationship was changed. These findings prove that crystallographic disregistry is not the controlling factor in heterogeneous nucleation from the liquid. The results of this investigation tend to confirm the theory presented in a preceding paper that heterogeneous nucleation starts with the formation of an adsorbed layer of nucleated metal on the nucleat-ing impurity. Evidence is given that cavities in the nucleating agent act as centers of nucleation. IT has long been known&apos; that solid extraneous particles are active in catalyzing phase transformations that occur in a system, particularly condensation and crystallization. It is well established that these heterogeneities act as catalysts by providing surfaces upon which nuclei of the precipitating phase can form with activation energies smaller than those required for homogeneous nucleation. Numerous investigations have shown that in this process of heterogeneous nucleation: a) the nucleus forms with one, or several, definite crystallographic orientation relationships with the nucleating phase2-4 and b) that there is a small range of undercoolings or super saturations characteristic of the nucleation of a given solid on a given Substrate.5-10 Turnbull and vonnegut11 have developed a theory based on theories developed by Volmer12 and Turn-bull and Fisher1= for heterogeneous nucleation from gases and liquids, that relates the super saturation or undercooling required for nucleation to the dis-registry between the lattices of the nucleus and the nucleating agent. This theory predicts that nucleation should occur with the orientation relationship between the nucleus and nucleating agent that minimizes the disregistry. Further, it predicts that the undercooling or super saturation necessary for nucleation should be a function of the disregistry. Numerous investigations have dealt with the orientation relationships resulting from the condensation of vapors onto crystalline solid substrates2,3 and a few with the nucleation of one phase by a second phase in solidification4,14. Others have dealt with the supersaturation8-10 and undercooling5-7 associated with nucleation in condensation and solidification respectively. However, there is virtually no report that gives both of these factors for the same system. In this investigation a study was made of the undercoolings and orientation relationships resulting when Pb is nucleated from the liquid by Ni, Cu, Ag, and Ge. It was the purpose of this investigation to check the Turnbull-Vonnegut theory, i.e., the importance of crystallographic disregistry between nucleating catalyst and nucleated metal. The results indicate that disregistry is not an important factor in nucleation and that the nucleation process is probably somewhat more complex than current theories suggest. EXPERMENTAL PROCEDURE Small single crystals of nickel, copper, silver, and germanium were prepared from materials of four to five nines purity, and the Pb used was also 99.999+ pet pure. Cu and Ag single crystals were prepared by sealing small chips of Cu or Ag in an evacuated quartz capsule and heating the capsule at 2000°F for 1 hr before cooling. Nickel crystals of 200 diam were also prepared in evacuated quartz capsules, but melting was done by heating the capsules in an oxy-acetylene flame for a few minutes. These spheres were invariably polycrystalline so

Jan 1, 1962

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

The effects of increasing hydrogen content, introducing a notch, and changing the strain rate on properties of titanium and one of its alloys were investigated over a range of testing temperatures from —196° to 200°C. Both high purity and commercial purity A-55 titanium were used as representative a materials, while a commercial Ti-8 pct Mn alloy was used for an a-P alloy. It was found possible to analyze the data, using the ductile-to-brittle transition temperature concept. Increasing hydrogen, the presence of a notch, and increasing the testing speed raised the transition temperature for the a materials. The presence of hydrogen and notches raised the transition temperature of the a-B alloy also. However, increasing the testing speed generally decreased the transition temperature of the a-p alloy. IN previous papers, the authors have shown that hydrogen is most detrimental to the notch-bend impact toughness of a-titanium&apos; and to the tensile ductility of a-B titanium alloys.&apos; These general effects have been confirmed by Kessler and co-workers," and by Kotfila and Erbin." Kessler showed that the slower strain rate in notch-rupture tests was a more sensitive measure of hydrogen embrittle-ment of a-B alloys than the tensile test. In the present paper the authors cover, with tensile and notch-bend tests, the effect of testing speed, notches, and testing temperature on hydrogen em-brittlement. High purity and commercial purity titanium, examples of u materials, and a commercial a-,f3 Ti-8 pct Mn alloy were investigated. The purpose of the investigation was to correlate the factors producing embrittlement. Materials The high purity titanium for this investigation was obtained by arc-melting crystal bar from Foote Mineral Co. into 1 Ib ingots. As-cast hardnesses for these ingots ranged from 60 to 90 Brinell. The arc-melted ingots were forged to % in. diam rods at 1470°F. These rods were swaged to & in. diam at room temperature prior to machining of the specimens for hydrogenation and testing. The commercial A-55 titanium and the Ti-8 pct Mn alloy were obtained from Rem-Cru Titanium Inc., as % in. diam rod. The A-55 titanium was hot swaged to 1/4 in. diam at 1300°F prior to machining of the specimens for hydrogenation and testing. The a-p C-11OM alloy was hydrogenated prior to hot swaging to 1/4 in. roc1 at 1300°F. Hydrogenation prior to fabrication permitted testing of the a-P alloy in the equilibrated and stabilized condition. The equilibration and stabilization treatment used was an air anneal for 1 hr at 1300°F, followed by furnace cooling to 1100°F and then air cooling. Hydrogenation was done in a Sieverts apparatus described previously.&apos; The hydrogenation treatment consisted of heating for 1/4 to 1/2 hr at 820 °C in purified hydrogen, slow cooling to 680"C, holding 1 hr for homogenization, and rapid cooling to room temperature. Intended hydrogen levels for the a-tita-nium materials were 0.05, 0.5, 1.0, 1.5, and 2.0 atomic pct—about 15 to 430 ppm. For the Ti-8 pct Mn alloy, the intended hydrogen levels were 0.05, 0.5, 1.0, 2.5, and 5.0 atomic pct—about 15 to 1100 ppm. The material for the 0.5 atomic pct level of hydrogen was vacuum annealed prior to hydrogenation to increase the accuracy of the addition. Vacuum annealing to remove hydrogen consisted of heating for 6 hr at 820°C, and resulted in a hydrogen content of about 10 to 15 ppm. When hydrogen contents were above 0.5 atomic pct—100 ppm—the hydrogen was added without prior vacuum annealing.

Jan 1, 1957

By H. H. Kellogg, T. R. Ingraham

Three anhydrous zinc sulfates have been identified. They are: ZnSO,(a), stable below 1007°K; ZnS04(/3), stable above 1007OK; and ZnO.ZZnSO,. The decomposition pressure of each sulfate has been measured and the following relations calculated from the results: The measured data have been combined with the known themzodynamic properties of ZnS, ZnO, Zn, SO,, and SO, to yield univariant and bivariant phase diagrams for the system Zn-S-0. The application of these diagrams to problems of roasting zinc concentrates is discussed. PRESENT knowledge of the equilibrium chemistry of the system Zn-S:O, so essential to scientific control of zinc-blende roasting, is deficient in several respects. A basic sulfate of zinc has been reported by many investigators, but its composition is in doubt and its thermodynamic properties have not been measured. Our scanty knowledge of the properties of the normal sulfate at roasting temperatures is based on old and inexact studies. A crystal transformation in the normal sulfate, involving a sizable heat effect, has been noted by several investigators but has never been quantified. The studies reported herein were designed to fill these gaps in knowledge and to make possible a reasonably complete thermodynamic description of the system Zn-S-0 at roasting temperatures. The results make possible a far more exact understanding of zinc roasting chemistry than was hitherto possible. EXPERIMENTAL The principal experimental technique employed was the measurement of the total gas pressure developed from decomposition of either ZnSO, or ZnO2ZnS0, in a closed system. The apparatus employed was essentially the same as that described by Warner and lngrahaml and Flengas and tngraham.&apos; The unusual feature is a flexible Pyrex bellows used to separate the reaction gas mixture (S03, SOz, and 02) from the mercury in the manometer and thus prevent corrosion of the mercury by SO3. The bellows operates without evidence of hysteresis and, barring accidents, may be used for several months. The response of the bellows varies from manometer to manometer, but is generally of the order of 0.6-cm displacement for a l-cm change in pressure. The response for all manometers has been linear over the range 0 to 1 atm. To prevent condensation and polymerization of sulfur trioxide, the bellows-manometer was maintained at 100.0" * 0.5" by a circulating bath of silicone oil. The connecting tubing between the manometer and the furnace was maintained at 100.0" * 0.2"* also, with a stirred air bath. The open end of the manometer was connected with a chamber which was maintained at a known pressure. The pressure could be varied so that readings of the height of the mercury column, measured with a cathetometer, could be made with both rising and falling mercury column. By using the average of the readings, any error due to sticking of the mercury column was minimized. The sample was placed in a 2-in.-long platinum boat formed into the shape of a half-cylinder. The sample was prepared as a fine powder and pressed against the inner wall of the platinum boat. A silica thermocouple well, covered with a platinum sleeve, was placed lengthwise along the center of the boat. The temperature of the sample was read on a calibrated Pt-10 pct Rh theirnocouple. The temperature profile of the furnace was constant within ± 0.2 C over the length of furnace occupied by the sample. The horizontal furnace used to contain the sample and the quartz reaction tube was electrically heated, with the control thermocouple placed 1/4 in. from the windings. A Brown Pyro-O-Vane temperature controller with a 3-sec response time was used to maintain the furnace temperature. Before beginning a run, the apparatus, including the bellows manometer, was thoroughly washed in sib with acid and distilled water to remove any

Jan 1, 1963

By D. R. Uhlmann, T. P. Seward, K. A. Jackson, J. D. Hunt

microscopic ohservations on alloys of organic trzaterials show that dendrite arms can melt off under normal conditiorzs of growth. This occurs because of the interactiorz of&apos; heat and matter fluxes during dendritic growth. The re melting occurs where the den-drite arms are joined onto the main deizclrite sterrz. Many detached crystals can be produced in this fashion. It is postulated that this remelting phenornenon occurs in metal alloys, giving rise to the equi-axed region in castings. Experiments peyformed orr castings of transparent materials support remelting as a primary source of detached crystals. Ob~ervations an equiaxed tones in metal castings are discussed in terms of this and other mechanisms. It is concluded that the partial remelting of dendrites is on important mechanisnl for producing the equiaxed regions in castings. THE freezing of a casting can be divided into three regions: a chill zone formed near the mold wall, a columnar region, and a third region, at the center of the casting, which is called the equiaxed zone. The origin of the grains that comprise the equiaxed region is the subject of this paper. We will first outline the mechanisms which have been proposed to account for the origin of the equiaxed region and discuss some recent experiments which cannot be explained by these theories. We will then present some microscopic observations of dendritic growth which have led us to conclude that the equiaxed zone in castings can arise from partial remelting of dendrites. This proposal is supported by observations on transparent castings. Finally, we will discuss several observations on metal castings which could not be explained previously, and which can be accounted for by the present proposal. Previous Mechanisms. Winegard and Chalmers3 pointed out that the molten central region of an ingot could be constitutionally supercooled, because of the solute layer at the growing interface. In this supercooled region, nucleation on particles could occur, giving rise to the equiaxed crystals. Another mechanism has also been suggested,4y5 that the nuclei originate in the chill zone then float or are carried by convection to the center of the casting, where they grow to produce equiaxed crystals. In this case, all the crystals nucleate immediately on casting, so this mechanism will be termed "big-bang" nucleation. Walker&apos;s Experiments. J. L. Walker has made observations on the solidification of nickel and Ni-Cu alloys which cannot be accounted for by either of the above mechanisms. In studying the grain size resulting from freezing of nickel at various undercoolings, walker6 found that at large undercoolings the grain size was small, due to mechanical nucleation, as discussed by walker7 and Horvay.&apos; At small undercoolings, the grain size was large, and the growth dendritic. In Ni-Cu alloys, however, for initial undercoolings starting from just below the melting point and extending for a hundred or so degrees of undercooling, fine grains were also observed. Samples were undercooled 200 Centigrade degrees without nucleating, and were then heated 130 Centigrade degrees so that the undercooling was 70 Centigrade degrees, and nucleated. The samples had a small grain size, indicating multiple nucleation. There were no heterogeneous nuclei in the liquid which could operate at the temperature of growth. Constitutional supercooling could not have been greater than the supercooling of the initial melt, since the temperature rose as the freezing continued. walker -as also shown that a Ni-Cu alloy which can be undercooled to below its solidus will produce typical columnar and equiaxed regions when cast into a cold mold. This alloy could not reach a temperature below its solidus by constitutional supercooling. It could not, therefore, have nucleated heterogeneously. Neither the big-bang mechanism nor the Winegard-Chalmers mechanism can account for the fine grain

Jan 1, 1967

By E. W. Dewing

The nature of solid solutions of sodium in non-paphitic carbon at temperatures near 1000°C has been investigated by an electrolytic technique. The activity coefficient is found to vary strongly with the heat-treatment temperature of the carbon, and an analysis of the energy terms involved suggests that this is due to variations in the Fermi level. The diffusion coefficient for sodium is in the range implying that the sodium atoms (or ions) are not bound to specific sites on the carbon, in agreement with lack of evidence for specific compounds in the activity -composition curves. In the light of These results phenomena occurring in aluminum reduction cell linings are dis-cussed. It is concluded that sodium migrates by diffusion through the carbon lallice and not the pores, and that A14C9 is formed within the lining hy The excess of NaF invariably found in used linings is formed by this reaction and by air oxidation: There has recently been much interest in the swelling of carbon which occurs when it is made cathodic in an aluminum electrolysis cell, and there is general agreement that the phenomenon is due to the penetration of sodium atoms, derived from the reaction on the carbon lattice. (NaF and AlF3 are constituents of the fused-salt electrolyte.) The low-temperature lamellar compounds of potassium with graphite are well-known, and one compound between sodium and graphite has been reported.4 There is, however, virtually no information on the basic chemistry of the interaction of sodium with nongraphitic carbon at high temperatures, although Dell3 has made some fundamental studies of rates of penetration. At the time the present work was carried out these were not available. Rapoport and samoilenkol had measured rates of physical expansion in a dilatometer, using the fractional increase in length of a carbon specimen after electrolysis in a cryolite bath for 2 hr as an index of susceptibility to cathodic swelling. Work here with a similar apparatus showed that expansion (of a 1.5-in.-diam cylindrical specimen) ceased in less than 20 hr, and that the final expansion was much more reproducible than the value at some intermediate time. This suggested that an equilibrium was being set up, and that a thermodynamic approach was required. The results obtained are not as accurate as had been hoped, but they are the only ones of their type available and have enabled useful conclusions to be drawn. The experimental work was divided into two parts: an investigation of the activity-concentration diagram for sodium in carbon, and a rough determination of the diffusion rate. For the former, most of the experiments were made with petroleum coke even though this is not a form of carbon used in cell linings. It has the advantages, however, that it is a homogeneous material, that it is low in ash, and that its structure is reasonably well understood. Anthracites and coal cokes gave results of the same type as obtained with petroleum coke, but the reprodu-cibility from specimen to specimen was extremely poor. EXPERIMENTAL 1) The Activity-Composition Diagram for Sodium in Carbon. The petroleum coke was ground, pressed at 40,000 psi into plates 19 by 9 by 2 mm without added binder, and heat-treated. The sodium activities were established by an electrolytic technique. The carbon was made anodic in a cryolite bath with an aluminum cathode, and a controlled potential, E, applied so that the sodium activity at the anode was given by ln Na = 1n asa - EF/RT [21 where as, is the sodium activity generated by Reaction [I]. The relative activity is sufficient for many purposes and is simply given by The value of Na not at present known, but when the thermodynamics of the Na-A1 system have been worked out it can be derived from the equilibrium

Jan 1, 1963

By S. B. Twiss, P. R. Basford

The relationship between areas of iron powders, briquettes, and sintered compacts and tensile strength has been determined. It has been found necessary to distinguish between two types of areas which exist in such powders—a macroscopic area due to the shape and size of particles and a microscopic area due to pores and cracks in the surface. Only the macroscopic area, specifically the area due to particle irregularity, contributes to tensile strength; the microscopic area cannot be forced into contact with adjacent particles ond does not participate in bond formation. Of the two methods of area measurement employed in this study—permeability to liquids and gas-phase adsorption—only the former is useful for determining the roughness factor. A measure of this roughness, (area measured by permeability to liquid) -f- (orea of powder with the same size distribution, but made up of spherical particles), is shown to be uniquely related to tensile strength at constant density. The other important factors in determining the strength of sintered-metal compacts are the density and presence or absence of surface oxide. THE manufacture of metal parts by the process of powder metallurgy is an important and rapidly growing industry. Progress has been rapid and continuous, largely because of the excellent research in the field. Nevertheless, the process remains inherently complex and empirical. Several investigators have shown that the properties of the final compact must depend on many variables; namely, shape,&apos; size distribution,"-" nd compositiona of the original particles, the pressure necessary to compress to the desired density, the density of the compact, the time and temperature of sintering, and so on. Through the application of some new techniques to the study of powders and compacts, and the correlation of a number of observations of known variables, the present paper attempts to clarify and simplify the underlying theory of the powder-metallurgy process. Any theory must start with the obvious fact that the strength of a compact, its most useful property, is due to the formation of welded areas between adjacent particles, and attempt to deduce what effect other variables will have on (a) the area and (b) the intrinsic strength of these welds. Such welded areas can be demonstrated by electron micrographs, as in Fig. 1. It was believed that (a) could be most directly studied by means of surface-area measurements on the original powders and on the compacts made from them; the area decrease should be related closely to the welded area. A representative group of eleven iron powders from commercial sources, and made by a variety of processes, was chosen for this study. In addition to the surface-area measurements, correlations were established between the tensile strength and all the known variables which might possibly affect it. The results are quite unexpected. They indicate that the situation is much simpler than the authors had anticipated. The strength of the sintered compact is determined, indeed, by no more than three variables; viz., the irregularity of the original particles, the density of the compact and, in exceptional cases, the amount of surface oxide. All three had been recognized previously as having some effect on the tensile strength, but in the absence of the special techniques and interpretations to be developed here, there could be no suspicion that they were the only relevant variables. Materials and Methods Material—All the iron powders were commercial products obtained from the Amplex Division of Chrysler Corporation. Powders A, B, C, and J were very pure electrolytic iron. Powder D was made from oxidized scrap reduced by heating with an excess of cast iron. Powder E was a high-grade iron ore reduced by hydrogen. Powder I was prepared by atomizing molten cast iron in an air blast, quenching the droplets in cold water, and crushing the coarse powder. Mill scale (oxide) is added and the mixture heated to reduce the high carbon content. The other powders were all prepared by reduction of iron oxides, such as mill scale. They

Jan 1, 1959

By W. C. Hagel, J. H. Westbrook

Usittg a sectioning technique with Agl10 as the tracer, the diffusion of silver in silver-excess (45.8 at. pct Mg), near-stoichiometric (49.8 at. pct Mg), and magnesium-excess (52.0 at. pct Mg) cylinders of CsCl-type AgMg was determined from 500" to 700°C. Diffusion coefficients conform to the expression D = Do exp (-q/RT) where the respective Do values are 1.53, 0.280, and 0.134 sq cm sec-I and the Q values are 41.3, 40.6, and 38.0 kcal g-atom-&apos;. Lnttice-parameter and density measurements were performed on a more numerous assortment and wider range of compositions. Substitutional defects were found on both sides of stoichiometry. Activation energies for other rate processes in these alloys show related trends with changing composition, although silver may not be the rate-detemining species. KNOWLEDGE of diffusion coefficients is necessary for a quantitative understanding of the many rate processes (e.g., grain growth, precipitation, sintering, oxidation, or mechanical deformation) occurring in solids. Although these data are available for most metals and common alloys, they are quite limited for intermetallic compounds—a group of materials whose unique physical and mechanical properties are presently attracting great interest. From a fundamental viewpoint, diffusion in intermetallic compounds also offers several engaging aspects owing to: their ordering, the possibility of introducing large, stable concentrations of lattice defects, and the variety of bonding types and crystal structures which can be found. In the case of CsC1-type compounds, some previous work has been directed at examining the role of vacancy defects by changing their concentration compositionally. The diffusion of Co60 was measured in 0 NiAl1- and in P COA., Except for the results of Smoluchowski and Burgess, isothermal diffusion coefficients were found to pass through a minimum at the stoichiometric composi- they decreased sharply on what was reported by Bradley and co-wrkers&apos; to be the vacancy-rich (aluminum excess) side of stoichiometry. This investigation of the diffusion of Agl110 in AgMg was undertaken both as an adjunct to a concurrent study of its deformation behavior and for the purpose of obtaining information on the influence of lattice defects and temperature on diffusion in another CsC1-type intermetallic compound. Bcc AgMg remains ordered up to and melts congruently at 820°C. Solubility limits at 300°C are about 41 at. pct Mg and 53 at. pct Mg. It is one of the Hume-Rothery electron compounds with a 3/2 electron-atom ratio. Previous investigations of its properties include hardress,&apos; tenile,&apos;-&apos; electrical reistivity, and thermodyna-mic1&apos;,14 studies. Indications of a high bonding strength may be found in the large heat of mixing1&apos; and in the 6-pct vol contraction on compound formaticp, as calculated using atomic radii of l.40 and l.55a for Ag and Mg. EXPERIMENTAL PROCEDURE Alloys were prepared by the induction melting of selected fine silver (99.95) and low-iron magnesium (99.95) in magnesia crucibles under 1 atm of A. Supplied by the Handy and Harmon and Dow Chemical Cos., respectivelv. Melts were poured under argon into graphite molds providing 1 1/8-in.-diarn. by 4-in.-long ingots. These were homogenized in evacuated and argon-filled fused-silica capsules by heating for 16 hr at 750&apos;. Three 1 in.-diam. by 3/4-in.-long cylinders were machined from the mid-portion of each ingot for diffusion measurements. Three alloys, analyzing 45.8, 49.8, and 52.0 at. pct Mg were taken as representing the extremes of interest, with 49.8 at. pct Mg being very close to the stoichiometric composition of 50.0 at. pct Mg.

Jan 1, 1962

By R. O. Williams

It is shown that Ni3Al precipitates homogeneously from nickel-rich alwminum alloys as plates on the (100) planes. Prior to actual precipitation a process occurs which is believed to be one of increasing short-range order. After precipitating the Ni3Al plates enlarge through competitive growth. Discontinuous precipitation can occur simultaneously with the above processes. Recent ideas of the origin of precipitation strengthening appear adequate to explain the hardness changes. REMARKABLY little appears to be known about the precipitation process in Ni-Al alloys in spite of their technical importance. This investigation originated to supply additional information about precipitation in general, this system in particular. Information on the structures and kinetics have been obtained through the use of hardness, X-rays, microscopy, calorimetry, and resistivity on high-purity alloys. PROCEDURES Six alloys, Table I, were prepared by melting carbonyl nickel and high-purity aluminum in alumina crucibles in vacuum and casting into 1-in. graphite molds. All rods were homogenized at least once at 1300°C for 24 hr prior to swaging and this was repeated on the first three alloys after 75 pct reduction. Alloy 4 could be reduced only 10 pct at 1000°C (probably in two-phase field) prior to fracture but 1/4-in. samples quenched from 1100°C were readily reduced cold. Alloy 5 was reduced 15 pct cold but failed on the next pass while alloy 6 of essentially the same aluminum content failed inter-granularly without apparent flow up to 1000°C. The alloys were heated in hydrogen at the elevated temperatures and formed thin, coherent aluminum oxide coatings which provided excellent oxidation resistance at lower temperatures. However, freshly prepared surfaces showed considerably less resistance at 500"to 700°C in air and apparently resulted in internal oxidation. As a consequence, low-temperature agings were carried out in evacuated tubes. RESULTS The isothermal hardening behavior of these alloys at 500"and 565C is given in Figs. 1 and 2. These results were obtained from samples cold worked 75 pct, recrystallized at 1000°C (1100°C for the 7.8 pct Al) and quenched in water. This recrystallization was used to give smaller grain sizes so as to obtain more uniform hardness values and the points represent an average of five readings. The electrical resistivity was measured on 1/16-in. wires quenched from 1000°C during aging at 495°C to give Fig. 3. The energy release and its rate are given in Fig. 4 for the 6.9 pct Al alloy during aging around 500°C. Inasmuch as this was a single run, its accuracy is not known but certainly the general shape and magnitudes are correct. The method used to obtain these results is described elsewhere.&apos; Data for the aging at 600°, 700°, and 800°C of these alloys cold worked 50 pct are given in Fig. 5. Supplementary information from microscopy and X-ray diffraction have been included to indicate recrystallization, discontinuous precipitation and the appearance of superlattice lines from the Ni3Al. The hardness of these alloys as annealed, aged, cold worked, and cold worked and aged is given vs composition in Fig. 6. Those samples which were isothermally aged, Figs. 1 and 2, were reaged at 532°C and at successively higher temperatures for the indicated times to give the data of Fig. 7. These results as well as certain others, support the idea that the level of hardness reached for temperatures above 600°C are equilibrium values more or less independent of path. This being the case, the breaks in the curves would be the complete solution of the Ni,Al. The electrical resistivity versus temperatures for some of these alloys, both aged and unaged, is given in Fig. 8 along with those data from heating slowly (10 deg per day) to high temperatures. Interesting points include the lowering of the Curie temperature (the change in slope), the lack of any indications of a solubility limit and the large temperature coefficient for the Ni3Al. A slight break for Ni3Al around 100C shows up but this is not a Curie temperature as Ni3Al is not ferromagnetic down to -190°C. Metallographically both the nickel-rich solid solution and the Ni3Al appear very much like pure nickel. Profuse twin boundaries are present both

Jan 1, 1960

By E. J. Rapperport, E. D. Levine

The boundaries of the (a +ß) field in the Al-Li system were determined between 150°and 550°C utilizing quantitative metallography and lattice-parameter measurements. The solubility of lithium in aluminum decreases from 12.0at. pct Li at 550°C to 5.5 at. pct Li at 150°C. P Al-Li is saturated with aluminum at 45.8 at. pct Li and has this boundary value constant over the temperature range 150°to 550°C. THE solid solubility of lithium in aluminum has been determined by several investigators, 1-6 but, as shown in Fig. 1, there is little agreement among the various determinations. The earliest investiga-tions&apos;-&apos; are suspect because of the use of impure materials. Although high-purity materials were employed in more recent work,4&apos;5 the experimental techniques may have led to contamination of the specimens. Probably the best work has been that of Costas and Marshall,6 who obtained close agreement between results obtained by two independent phase-boundary techniques: electrical resistivity and mi-crohardness. No detailed studies of the solubility of aluminum in the bcc ß phase, Al-Li, have been reported. Cursory investigations1,2,6 have indicated only that the (a+ß) -p boundary lies between 40 and 50 at. pct Li and is relatively independent of temperature. The present work was undertaken in order to provide an independent check on Costas and Marshall&apos;s determination of the solubility of lithium in aluminum, to extend knowledge of this solubility limit to temperatures below 225°C, and to make an accurate determination of the solubility of aluminum in Al-Li. EXPEFUMENTAL Alloy Preparation. In view of the difficulties encountered in previous investigations of the A1-Li system, close attention was paid to the use of methods of alloy preparation and treatment that would minimize contamination. Aluminum sheet (99.99 + pct Al) was vacuum-induction melted in a beryllia crucible to remove hydrogen. Lithium (99.9 pct Li) was charged with pre-melted aluminum into a beryllia crucible, in a helium-filled drybox. The crucible was sealed in a Vycor tube and transferred from the drybox to an induction furnace. Melting of alloys was performed by induction heating in a helium atmosphere. Solidification was accomplished by means of a suction apparatus, shown in Fig. 2, in which the alloy was forced by changes of pressure into a 3/16-in. inside diam closed-end beryllia tube. This technique produced rapid solidification of a small portion of the melt, resulting in alloys with a high degree of homogeneity. Typical lithium distributions are presented in Table I. Transverse sections 1/8 in. long were cut from the alloy rods, and each section was split in half longitudinally. One half of each section was analyzed for lithium, and the opposing halves were employed for phase-boundary determinations. Lithium contents were determined by flame photometry with an accuracy of 1 pct of the amount of lithium present. Thermal Treatments. Homogenization and equilibration heat treatments were performed in electrical-resistance furnaces with temperatures controlled to ± 2OC. Calibrated chromel-alumel thermocouples were employed to measure temperature. Homogenization was performed in helium-filled l?yrex tubes for 1 hr at 565°C. The encapsulated specimens were then transferred directly to furnaces maintained at lower temperatures for equilibration. Equilibration times were 2 hr at 550°C, 8 hr at 450°C, 27 hr at 350°c, 90 hr at 250°c, and 285 hr at 150"~. These times were chosen on the basis of conditions employed by previous investigators. Alloys were quenched from the equilibration temperatures by breaking the capsules into a silicone oil bath. By performing all possible operations either in sealed capsules or in a helium-filled drybox, the specimens were given minimum exposure to the atmosphere. Quantitative Metallography. Metallography of Al-Li alloys is difficult because of the atmospheric reactivity of the ß phase. It was found possible, however, to prepare surfaces of good metallographic quality by preventing contact with moisture during preparation. Grinding through 4/0 paper was performed in the drybox. The specimens were then transferred under kerosene to the polishing wheel. Three polishing stages were employed: 25-p alundum with kerosene lubricant on billiard cloth, 1-µ diamond paste on Microcloth, and 1/4-p diamond paste on Microcloth. Between stages the samples were cleaned by rinsing in trichloroethylene and buffing

Jan 1, 1963

By W. C. Hagel, H. J. Beattie

Seven austenitic alloys of varions base compositions and minor-alloy additions were solution-treated, aged systematically between 1200oand 1800oF, and examined by X-ray and electron metallography. Intragranular preczpitations of µ, Laves, s, ?&apos;, Ni3Ti, and x phases were observed as a function of composition and aging time and temperatwre. Phase solubility limits were detevtnitzed within 100Fo intervals. These inter metallic compounds fall into two distinct general classes, and whichever class predomznates depends on base composition. It has become increasingly evident that multicom-ponent austenitic alloys are well characterized by their precipitation processes. Since certain groups of elements act as one, the relationships among these processes are reasonably simple; complete identification of such processes is usually attainable by a systematic aging study with a combination of techniques centered on microscopy and diffraction. Several nickel- and cobalt-base alloys illustrating cellular precipitation and its interaction with general precipitation were reported previously.1 The group of alloys covered in the present paper demonstrates precipitation-hardening reactions involving two distinct classes of intermetallic compounds where the predominating class appears to depend on base composition. This dependency ties in with a crystal-chemistry regularity first observed some twenty years ago by Laves and Wallbaum but never amplified to our knowledge. Results of electron-microscope and X-ray diffraction studies on systematically aged hot-rolled alloys known commercially as S-816, S-590, Rene-41, Incoloy-901, M-308, and M-647 are reported here. Some of these alloys have previously undergone minor-phase analyses by other investiators. Alloy S-816 was investigated by Rosenbaum, Lane and Grant,3 and Weeton and Signorelli.4 Rosenbaum found only CbC in hot-rolled bars. Lane and Grant found CbC and a small amount of M6C in the cast structure and stated that both carbides form during aging, most of the precipitation being CbC. Weeton and Signorelli found CbC, M23C6 and a weak indication of a phase after a slow step-down cooling cycle from 2250°F. Rosenbaum also investigated hot-rolled samples of S-590 and identified CbC and M6C. Preliminary information on Rene-41, gained partly from the present work, was reported by Morris.5 Long-time precipitation phenomena in Incoloy-901 at 1350°Fwere investigated by Clark and Iwanski.B heir raw data re- semble those of our present heat with 0.1 pct B, while their interpretation of these data resembles our interpretation of data from another heat with only 0.001 pct B; they made no statement as to boron content. No previous minor-phase studies of alloys M-308 or M-647 have been reported. EXPERIMENTAL METHODS Table I gives alloy compositions in both weight and atomic percent. Specimens were solution-treated from 1700º to 2200ºF, aged at logarithmic-time intervals up to 1000 hours between 1200 and 1800 F, and examined in accordance with procedures previously described in detail. &apos; &apos; Phase extractions were carried out in electrolytic cells containing 800 ml of either 7 pct HC1 in denatured ethanol or 20 pct H3PO4 in water. After electrolysis for 48 hr at 0.1 to 0.2 amp per sq inch, residues were separated by filtration or centrifuging. X-ray powder patterns of residues were recorded on a diffractometer for accuracy and on film for sensitivity. Lattice parameters were calculated by least-squares analyses of indexed sin 8 values, and relative abundances were estimated from intensities of strongest lines of each phase. These phase abundances denote relative amounts with respect to each other rather than to the alloy. Mechanically polished specimens were etched in a freshly mixed solution of 92 pct HC1, 5 pct H2SO4, and 3 pct HNO3. Parlodion replicas for the electron microscope were chromium-shadowed in high vacuum at a glancing angle of 20deg. All electron micrographs are reproduced here with the shadowing source above. The correspondence betweenelectronmicrostructures and phases identified by X-rays was established by a high redundancy of correlation between relative amounts at different stages of aging and examination above and below critical transformation or solubility temperatures. EXPERIMENTAL RESULTS S-816 and S-590—The phases found in S-816 and S-590 after various aging and solutioning treatments are listed in Table 11. These data and the observed

Jan 1, 1962

By T. Toda, R. Maddin

A study has been made of the microstructure and mechanical properties of splat-cooled aluminum-base gold alloys with gold concentration from 0.25 to 5.0 wt pct. These alloys have been quenched from the liquid state by a torsion-catapult technique, which has made it possible to pepare specimens suitable for mechanical property measwements. From the electron micrographs it has been shown that the solid solubility of gold in aluminum can be extended to 2.5 wt pct (0.35 at. pct) by splat-cooling, while the maximum equilibrium solubility is known to be less than 0.3 wt pct (0.04 at. pct). The very fine grain size (several tenths of a micron), the extended solid solubility, and the fine dispersion of a second phase (AuAl2) contribute concurrently to a substantial strengthening effect. In Al-5 wt pct Au splat-cooled specimens of less than 50 thickness, the yield strength is 17 kg per sq mm or 6 times as large as the strength of bulk specimens. For the Al-1.0 to 2.5 wt pct Au solid solution obtained by splat-cooling, the yield strength reaches 7.5 kg per sq mm after an aging treatment (for 10 hr at 200°C), while it is 3.7 kg per sq mm for the corresponding bulk specimens. A great deal of research has been done in recent years on the structure and the properties of metals and alloys rapidly quenched from the liquid state.&apos; The term "splat-cool" has been used with the meaning of a rapid quenching from the liquid state., The splat-cooling techniques have produced large numbers of new structures, which are expressed in terms of metastable phases,3 concentrated solid solutions,4 amorphous phases,5&apos;6 new phases,7 and so forth. Nearly all previous studies have concentrated on the physical properties; i.e., crystallography, structure, electrical resistivity, magnetism, and so forth, of the splat-cooled metals and alloys. The mechanical strength of splat-cooled metals and alloys has hardly been investigated except for some recent work by MOSS&apos; on A1-V alloys. The principle common to all experimental techniques developed to obtain very rapid quenching rates is based on the heat transfer by conduction. Liquid must be in good thermal contact with a substrate of high heat conductivity. Both of the published devices known as the "gun" and the "piston and anvil" techniques suffer from certain shortcomings. For example, the specimen obtained by the gun technique is very small and flaky, and hence inadequate for mechanical properties measurements. On the other hand if the material is forced to yield a continuous speci- men by the piston and anvil technique, it is probable that some plastic deformation occurs during the quench. A novel method for rapid quenching of a liquid metal or alloy, the "torsion-catapult", has been devised by Roberge and Herman9 at the University of Pennsylvania. In the apparatus the melt is thrown out of a curved furnace by a catapult and impinges on a copper substrate. The apparatus has the advantage of producing a continuous foil which is relatively large in size and of a quality suitable for the measurements of mechanical properties. The quenching rate is estimated to be of the order of l05 to l06 ºC per sec, (comparable to rates achieved by the piston and anvil technique). In selecting an alloy to be studied we were made aware of the fact that gold was believed to be "insoluble" in in and consequently age hardening in the A1-Au system appeared to be interesting. Quite recently Heirnendahl13-15 revealed that the solid solubility, as determined by transmission electron microscopy, was 0.3 wt pct Au at 640°C and 0.25 wt pct Au at 600°C, decreasing with decreasing temperature. In an A1-0.2 pct Au alloy after quenching from a solution treating temperature of 600°C the yield stress was 2 kg per sq mm, and it increased up to 6 kg per sq mm after aging for 1 to 10 hr at 200°C. The precipitation occurred in the form of platelike particles mainly on (100) matrix planes. The intermediate phase n&apos;, the equilibrium phase n (AuAl2), and lattice relationships between both precipitates and the matrix were also investigated by electron microscopy. One of the purposes of the present research is to determine whether or not the solid solubility in this system, in which gold has a very small solubility in

Jan 1, 1970

By W. A. Backofen, G. Y. Chin, W. F. Hosford

The ductile fracturing process was studied in single-crystal and poly cvystalline aluminum deformed in tension over a temperature range from 295° to 4.2°K. At temperatures as low as 77°K, the fracture of "inclusion-free" material, including zone-refined aluminum, was by rupture (-100 pct RA). At 4.2 OK, fracture was brought on by adia-batic shear. Metallographic examination did not disclose any voids or slip-band microcracks, thus negating for inherently ductile metals any mechanism of void nucleation by vacancy condensation or of cracking due to dislocation pile-ups. In Izigh-purity aluminum not treated to be inclusion-free, fracture at temperatures as low as 45°K was of the double-cup type and a result of void formation. The reduction-of-area decreased as temperature was lowered, corresponding to the earlier appearance of voids. Such behavior was rationalized in terms of a larger increase, with decreasing temperature, in the .flow stress relative to the strength of the inclusion-matrix interface. Evidence for low-temperature adiabatic shear was found in discontinuous flow at 4.2"K, in the transition to a localized shear fracture at low temperatures, and in the suppression of shear fracture with an elastically hard pulling device. A simple analysis for the initiation of adiabatic shew permitted a general correlation of the various contributing factors. It has been pointed out that the duration of shear depends upon effective mass and elastic stiffness of the deformation system. IT has long been recognized that fracture* may Throughout this paper, the term "fracture" is taken to mean any process that results in the separation of a material into two (or more) parts. Thus rupture as it may be encountered in a tension test leading to 100 pct reduction-of-area is included in this category. occur in a ductile mode, and that the process can be of great practical as well as general interest. Much information about ductile fracture has also been accumulated over this period, but only recently has an understanding of mechanism begun to appear. Ludwik,&apos; in 1926, first reported fracture in a tensile specimen starting with a central crack in the necked section. Since then, other studies have disclosed that such cracks may form by the coalescence of voids nucleated in this region where hydrostatic tension is highest.2-4 Rogers and Crussard et al.&apos; have emphasized void formation and reori-entation along localized shear bands as a mode of crack propagation. pines6 has considered the tensile rod as a bundle of fibers joined by weak interfaces, which subsequently separate to allow individual fiber contraction. The notion of cavity growth and coalescence by purely plastic processes was discussed by Cottrell: who added that the tensile reduction-of-area ought not to be sensitive to temperature. On the other hand, it has been observed that the reduction-of-area is greatly increased if tests are carried out at high temperaturesa or under high hydrostatic pressure.&apos; Fracturing anisotropy in wrought products lends support to the idea of void formation from preexisting flaws strongly aligned by earlier processing.&apos;&apos;-l2 There is evidence that many voids result from the fracturing of inclusions or separation at the inclusion-matrix interface Another possibility is that voids grow out of pore volume produced in the initial solidification and never fully removed in later working. In general, a structure 3f particles, pores, and weak interfaces can be expected, at least in materials of engineering interest. Vacancy condensation has been suggested as an alternative mechanism of void formation for materials considered to be inclusion-free.13 Yet experience has shown that tensile reduction-of-area increases with purity, to the extreme of rupture as so often observed in single crystals. Adiabatic shear has an important bearing on ductile fracture. It occurs when the decrease of flow stress, as a result of local temperature rise from heat generated during straining, becomes larger than the increase due to strain and strain-rate hardening. As demonstrated by experiments on punching of plates,14 a large temperature rise may be brought about by rapid straining. Adiabatic flow as a result of the high strain rate reached in an ordinary tensile specimen just prior to separation may account for the cone formation in cup-and-cone fracture;14 evidence of such local heating has been presented.15 For geometrical reasons, however, pure sliding along the conical surfaces is unlikely, and separation under tensile forces is probably an important accompanying feature of the shear.7 In deformation processing operations, a high shear-strain rate may exist at boundaries between plas-

Jan 1, 1964

By N. J. Olson, G. W. Toop

A series of equations previously derived for calculating ternary thermodynamic properties using binary data has been applied to the problem of predicting ternary phase diagrams and quaternary excess free energy. The methods are considered to be rigorous for regular ternary and quaternary systerns and empirical for nonregular systems. The equations have been used to predict ternary phase boundaries in the Pb-Sn-Zn system at 926°K and the Ag-Pd-Cu system at 1000ºK. Calculated quaternary excess free-energy values are presented for the Pb-Sn-Cd-Bi system at 773°K. A method for predicting the location of ternary phase boundaries would be a useful supplement to experimental measurements in ternary systems. This has been recognized with the considerable work that has been done to find models to predict or extend thermodynamic properties and phase diagrams in binary and ternary systems1-18 for which direct experimental measurements are limited. With the access to highspeed digital computers and mechanical plotting devices, it is currently rather easy to compare mathematical models with experimental data. The regular-solution model is consistent with systems which exhibit negative heats of mixing, positive heats of mixing, and miscibility gaps, and therefore it is applicable to simple phase diagrams. The purpose of this paper is to illustrate the use of regular-solution equations to predict, empirically, phase equilibria in some types of nonregular ternary systems. Corresponding equations for regular quaternary systems are given and used to calculate empirical quaternary excess free-energy data. METHOD FOR PREDICTING THE LOCATION OF TERNARY PHASE BOUNDARIES USING BINARY DATA Meijerin1,6 has used the regular-solution model to calculate common tangent points to ternary free energy of mixing surfaces and hence to determine phase boundaries in ternary systems involving miscibility gaps. He used the following equation to calculate ternary excess free energy of mixing values: stants characteristic of the binary solutions, and Ni is the mole fraction of component i. An alternate expression which gives for regular solutions as a function of binary values of along composition paths with constant N1/N2, N2lN3, and N1/N3 may also be derived:15 ternary r xs 1 ?c-*n.Ti*.U*. This expression for is more useful for the empirical calculation of ternary excess free-energy values for nonregular systems because actual binary AFXS data may be used in the expression rather than attempting to find suitable constants for Eq. [I]. The results of this feature of Eq. [2] are illustrated in Table I where calculated excess free-energy values for the Ni-Mn-Fe system at 1232°K are compared with experimental data of Smith, Paxton, and McCabe.19 Although regular-solution equations have been shown to give calculated thermodynamic quantities which agree quite well with experiment for single-phase nonregular ternary systems,14,15 care should be exercised in the use of the equations to predict thermo-dynamic properties of multiphase ternary systems in which strong compound formation is suspected. This precaution is consistent with the simple regular-solution model which for negative values of ai_j will indicate a tendency toward compound formation but even for very large negative values of ai-jwill not give multiphase binary or ternary systems involving a distinct stable compound. Hence, calculated ternary free-energy data using Eq. [2] might be expected to vary between being rigorous and poor, in the following order, for ternary systems which are: a) regular solutions, b) nonregular single-phase liquids in which random mixing is nearly realized, c) nonregular single-phase solids, d) nonregular multiphase systems exhibiting miscibility gaps, e) nonregular multiphase systems with binary compounds but no ternary compounds, f) nonregular multiphase systems with highly stable binary and ternary compounds. The calculated data will be expected to be least accurate for the last two cases. The general method adopted in this paper involves two-dimensional plots of ternary activity curves. The principle used is that tie lines indicating two-phase equilibria join conjugate phases a and B for example, for which a1(a) = a1(B), a2(a) = a2(B), and a3(a) = a3(B). Tie lines may be determined by plotting the ternary activities of two components along an isoactivity line for the third component and the unique points where the above equalities hold may be found graphically.

Jan 1, 1970

By H. I. Aaronson, C. Laird

Although the past results of X-ray experiments indicate that the broad faces of 0&apos; plates are coherent with their matrix, dislocations lying in arrays have frequently been observed at these boundaries by transmission electron microscopy. Critical experiments employing the latter technique have been carried out in order to determine the origin of these dislocations. It is concluded that 8&apos; plates are essentially coherent with the matrix at their broad faces throughout the aging temperature/time envelope studied. Virtually all of the dislocation arrays observed are deduced to have been formed by plastic deformation accompanying transformation. The proportion of dislocations arising from convexity of the plates is shown to be negligible by comparison with that from plastic deformation. At the higher aging temperatures, a[001] dislocations appeared in moderate numbers. These dislocations were traced directly, however, to the ledgewise dissolution of 0&apos; occasioned by the formation nearby of 0 crystals. On the other hand, since there is a parametric difference normal to the broad faces of the ?&apos; plates, mismatch dislocations do form at their edges. A previous conclusion that these dislocations have Burgers vectors of type a[001] was confirmed directly. The edges of 0&apos; plates were observed to develop octagonal shapes when growing, but circular shapes during dissolution. 1 HIS paper presents the results of an investigation of the interfacial structures of plates of the transitional phase, 8&apos;, formed in an A1-4 pct Cu alloy. In a companion paper, Part 11, the effects of these structures upon the migration kinetics of a:?f boundaries are reported. This work is pa.rt of a general program designed to establish the basis of precipitate morphology. The present authors in Al-Ag,1 and whitton2 previously in U-C alloys, have used transmission electron microscopy to examine directly the vander Merwe3-6 networks of dislocations anticipated7 to compensate the small amount of lattice misfit normally founda at the broad faces of Widmanstatten plates. Since the broad faces of 0&apos; plates are considered to be perfectly coherent with the corresponding habit planes in the a matrix,&apos; no dislocations should be present at these faces. Many reports have been published, however, giving evidence to the contrary.10-18 The primary objective of this investigation was therefore to ascertain the nature of these dislocation structures. An attempt to do this is described in the first three sections of this paper. Inspection of the matching of the a and 8 &apos; lattices at the orientations of the 0:0&apos; boundary corresponding to the edges of 0&apos; plates raises the possibility that these edges may be made up of rather closely spaced edge- type misfit dislocations oriented so as to be sessile with respect to the lengthening or shortening of the plates. Since this structure should severely inhibit migration of the plate edges (Ref. 7, Part II), a situation not originally anticipated,&apos; an experimental determination of the interfacial structure of the edges of 8&apos; plates was clearly in order, and is reported in Section III. Those aspects of the experimental procedure applicable to both Parts I and I1 are presented in the next section. Specific procedures applicable to individual aspects of each investigation, and also the relevant surveys of the literature, are then individually reported in the appropriate sections. I) GENERAL EXPERIMENTAL PROCEDURE The material used in both parts of these studies was the same as that of a previous investigation:" strips of A1-3.93 pct Cu, 0.009 in. thick, prepared as before, solution-annealed at 548°C for 6 hr, and quenched. Details of subsequent aging, and in some cases deformation treatments, are given in the Experimental Procedure sections of the individual parts of both papers. Specimens of the heat-treated strips were electro-thinned as beforeLg and examined in a Philips EM 200 microscope equipped with a goniometer stage. A commercial hot stage, of the grid-heater type and capable of * 30-deg tilt about one axis in the plane of the specimen, was also used for kinetic studies. The usual precaution of calibrating for the additional heat supplied by the electron beam was taken.19 A 16-mm cine cam-I era mounted outside the viewing window was frequently used to record the transformations. Conventional selected-area diffraction and dark-field viewing techniques were used to identify the precipitates in the foils. Normal bright-field images corresponding to two-beam diffracting conditions or dark-field images were employed to characterize the dislocations observed at the interfaces of the precipitates. The application of these techniques to the study of an interphase boundary, and the interpretation of the images,20&apos;21 has been fully described in a previous paper.&apos;

Jan 1, 1969

By R. M. Hudson

The removal of nitrogen from a nitrogenized low-carbon sheet steel that contained 0.011 wt pct N was determined during heat treatment in Hz-N, mixtures. TIze process followed a first-order rate law; that is, plots of the logarithm of nitrogen content in steel were linear with the time of treatment at a given temperature. The rate of removal increased with an increase in temperature from 900" to 1300°F. By 1400°F the rate in dry hydrogen had decreased to a value intermediate between the rates at 1200" and at 1300°F; in wet (2.47 vol pct water vapor) hydrogen the rate at 1400°F was less than the rate at 1300°F and nearly the same as the rate at 1200OF. The rate at a given temperature increased as the 3/2 power of hydrogen concentration in the atmosphere. While wet atmosplzeres were generally more effective than the corresponding dry atmosplzeres, the effect of water vapor was much less pronounced than the influence of hydrogen content. NITROGEN is the principal agent in the strain aging of ferrite, the effect of carbon being secondary.&apos; To eliminate the return of the yield point after straining and aging, it is claimed2 that the amount of nitrogen in solution in steel must be reduced to 0.0002 wt pct. Strong nitride-forming elements (titanium, vanadium, zirconium, and aluminum) can act to eliminate strain aging by combining with nitrogen. It is extremely difficult to decrease the nitrogen content in commercial steels to the low level required by conventional coil annealing because of the poor contact between the strip surface and the reactive atmosphere. However, a variety of gas-metal reactions can be effected by use of the open-coil annealing method,3 in which the metal surface is fully exposed to the atmosphere. With this possibility in mind, the Applied Research Laboratory has studied the influence of time, temperature, and atmosphere composition on the removal of nitrogen from low-carbon sheet steel. MATERIALS AND EXPERIMENTAL WORK Samples from a commercial nitrogenized low-carbon steel (0.010 in. thick) in the cold-reduced condition were used. The chemical composition of this steel is given in Table I. The gas mixtures used are listed in Table 11. The moisture content in the "wet" annealing atmospheres was controlled at a +70°F dew point (2.47 vol pct water vapor) by passing the gas mixture through a glass tube packed with a solid mixture of 10 pct anhydrous oxalic acid and 90 pct oxalic acid dihydrate held at 127°F; this technique has been described previously.4 For "dry" atmospheres, the gas mixtures were passed through a cold trap immersed in liquid nitrogen. A hinged-top Hevi-Duty electric furnace was used with a Vycor-glass furnace tube. When the furnace was at the desired temperature, the gas mixture was passed through the furnace at a flow rate between 1.1 and 1.2 cfh; coupons (size 3 by 3/4 in.) of the steel were pulled into the center of the Vycor-glass

Jan 1, 1964

By J. E. Campbell, G. D. Calkins, N. M. Ewbank, M. Pobereskin, A. Wesner

GRINDING for size reduction affects the economics of many processes and products. It is essential as the first step in many industrial processes and is also a finishing step for materials with properties depending on particle size, such as talc, cement, and silica sand. Intermediate and fine grinding are vital operations in the U. S. cement industry, which is producing more than 250 million bbl of cement per year.&apos; Wear of the grinding media is a large part of the grinding operation cost. Problems encountered in grinding cement are so complex that evaluation of efficiency and economy of grinding media is difficult.2 It has been especially difficult to evaluate the relative effectiveness of different types of balls because there are no good testing techniques. Many other industrial operations can be evaluated on a laboratory scale with reasonable accuracy. This does not hold true for evaluation of grinding balls. The consistent results obtained in a laboratory test under a given set of conditions are not always borne out in field application. Rough evaluations of the effectiveness of various compositions and types of grinding balls have been made in the field by using a full charge of one type in a mill and comparing the production record with another run using another type of ball. This method is time-consuming and not very precise, as the second run may not have been carried out under identical conditions. Laboratory-scale tests, on the other hand, have yielded inconclusive results, and many investigators have turned their attention to the development of a field testing technique. Field testing small sample lots of grinding balls has been impractical because it is difficult to identify and recover the test specimens from the grinding mill, and individual groups of balls that have undergone different heat treatments can not be separated.".4 To overcome these difficulties, previous investigators have identified the balls by distinctive marks, notches, and drilled holes, but this procedure has three serious drawbacks: 1) Grinding characteristics and quality of the steel balls may be affected. 2) Physical markings may be worn away in the grinding process, especially during a prolonged run. 3) Recovery from the bulk of the charge will be extremely difficult because the markings are hard to see and may be masked by a coating of the product. To circumvent these difficulties, a radioactive-tracer technique was proposed for recovery and separation of steel grinding balls and subsequent evaluation of the various compositions of the balls. The proposed technique involved five basic operations: 1) Thermal-neutron irradiation activation5 of each group of test grinding balls to a different level of specific radioactivity. 2) Addition of groups of radioactive steel-ball specimens into a ball tube mill. 3) Recovery of radioactive steel-ball specimens from the bulk of the mill charge. 4) Separation of the various groups by their specific radioactivity. 5) Evaluation of actual grinding ball wear. Before any physical tests were performed, required neutron irradiation intensity and time were calculated. Probable composition of the steels to be used was ascertained. An examination was made of the radioactive nuclides8 to be formed which would contribute measurably to the radiation level immediately after irradiation and during the test operation. The radioisotopes formed, their types of radiation, and their half lives are listed in Table I. Of these radioisotopes only iron-59 and chromium-51 were significant for the actual wear test. The intensity of radiation that could be detected by a Geiger counter when the test was completed was the basis for the minimum activation level established. The intensity of radiaton that could be safely handled at the beginning of the test was the basis for the maximum activation level, although this was not considered a major problem. Ten groups of grinding balls of various composition and/or surface or heat treatment were to be tested. One group was designated for the minimum irradiation time. The remaining groups were designated for irradiation periods that increased by increments of 33 pct from that of each preceding group. This difference was considered enough for separation and identification of the groups by comparison of specific activity. Potential Hazards: Possible radiation hazards that might be encountered during this experiment were evaluated for the three important phases: 1) the radiation hazard of placing balls and removing them from the mill, 2) contamination of the product cement by radioactive material worn from the balls, and 3) contamination of the steel by the radioactive balls left in the mill. The radiation intensity expected from the whole group of radioactive balls was calculated to be 250 milliroentgen per hr at 1 ft. This meant the balls would require special shielded packaging and warning labels on the shipping containers. In a radiation field of 250 mr per hr a man can work for 1 hr without exceeding maximum permissible weekly exposure. Since the balls could be dumped into the mill in a matter of seconds, relatively little radiation exposure was anticipated at this stage of the operation. If the weight loss in the balls was 7.7 pct per month and the cement feed through the mill was

Jan 1, 1958

The October General Meeting of the Institute was held in Kelvin House, Johannesburg, on 15th October, 1969, at 4.30 p.m. Mr J. K. E. Douglas (President) was in the Chair. There were also present 17 Members, Messrs: M. Barcza, R. C. J. Goode, J. A. Nixon and V. C. Robinson (Council Members), M. L. Fitzgerald, D. F. H. Graves, C. G. Hinds, S. D. Hill, J. S. Hall, D. F. Malan, T. Meyer, W. pyne-Mercier, K. S. Rae, S. G. Taussig, L. W. P. van den Bosch, Dr A. Whillier, C. H. Wyndham. Four Associate Members: Messrs O. Davel, M. J. Martinson, M. P. J. Sandys, T. G. Harington. One Student: R. P. W. Henrard. Three Visitors: Messrs A. V. Pike, B. Schmitz, A. P. Raats. Secretaries: D. C. Visser and S. de. Gersigny. Total present: Twenty-eight. OBITUARY The President: "It is my said duty to announce the death of Pieter Ulrich Fischer, Member, who joined the Institute in 1961 and passed away on 24th June, 1969. As a mark of respect to the memory of the deceased and in sympathy with the bereaved I would ask you all to rise and observe a few moments&apos; silence." MINUTES The President: "The minutes of the last meeting will only appear in next month&apos;s Journal and I would request that the confirmation of these minutes be held over." MEMBERSHIP The President: "I have much pleasure in announcing that the names of the undermentioned candidates, having been published in accordance with By-Law 5.2.2, Council has elected them to membership of the Institute in the following grades:" Members: Alexander Edward O&apos;Meara, Anton Leopold Melvill, WilIiam Harold Wise, Eric John Dunstan, Frank Nel, Lubertus Hendrikus Jakob Poortier. Associate Members: Michael Irvine Britten, Selwyn Wilson Lange. James McCormack, Christiaan Lodewyk de Jongh, WilIiam Andrew Hustrulid, Reinhold Johannes Ortlepp, Felix Henry Lancaster. Graduates: Willem Adriaan Gericke, Hamish David Sneddon Miller, David lan Ossin, Robert Antony Layboume, Ewart John Shillaber, Colin Hewitt Wiggett. Affiliates: Bernard Andre Thomas, Waiter Arthur Wood, Andrew John George Paschalides, David John Perry, Alex Richardson, Gert Blekker Kotze. Student: Matthys Jacobus de Beer. MEMBERS TRANSFERRED TO A HIGHER GRADE From Associate Member to Member: David Alphonso Viljoen. From Student to Associate Member: Michael Charles Carruthers. "I welcome the newly elected members to the Institute and congratulate the members who have been transferred to a higher grade." PAPERS FOR PRESENTATION The President: "Professor Wyndham, may I call on you to deliver the paper entitled &apos;Factors affecting the mechanical efficiency of men shovelling rock in stopes&apos;, written jointly with J. F. Morrison, J. H. Viljoen, N. B. Strydom and A. Heyns." After the presentation of the paper the President said: "Gentlemen, I would like to thank Dr Wyndham and his colleagues for once again reporting through the medium of this Institute the results of the very important work they are carrying out at the Human Science Laboratories. It is most appropriate that this work which is leading to a better understanding of the capabilities and efficiency of the human body under the arduous conditions encountered underground should be reported to this forum. In this way our members, who are actively engaged in the job of mining, can firstly learn something of this research and secondly, can, with their practical knowledge of conditions underground, contribute to what has been learnt and possibly pose new problems for our scientists in the laboratories. The scientist should always have the opportunity of subjecting his research to the scrutiny of people engaged in practical operations. By the very nature of our gold mines we are unfortunately heavily dependent on a large labour force and while mechanization has been introduced wherever feasible, we are likely to continue to be heavily dependent on this labour. In accepting this fact we can be proud in this country of what has been achieved, not only in obtaining the best efficiency from labour but in ensuring that their working conditions are reasonable and that their health and well-being are adequately cared for. When one visits our gold mines, one cannot help being impressed with what is being done to ensure that we have a satisfied, happy and healthy labour force. The Human Sciences Laboratory with its scientific approach has assisted greatly in promoting a better understanding of the problems associated with labour under the conditions experienced on our mines. Thank you." Mr M. Martinson then contributed to the discussion. (This contribution will appear in a later issue of the Journal.) "Professor Wyndham, may I call on you to deliver the paper entitled &apos;Acclimatizing men to heat in climatic rooms on mines,&apos; written jointly with Prof Strydom." After Dr Wyndham had presented the paper the President said: "Thank you Dr Wyndham for so ably describing the work associated with the acclimatization procedures on our gold mines. It has certainly been an eye-opener to those of us not familiar with this work and I believe it is very important that everyone and not only people in the gold mines should know about it. It is fortunate that all industries do not have the same arduous heat conditions experienced on our mines but other industries such as our chemical and metallurgical industries do have other problems relating to the adjustment of labour to the work situation. The scientific approach employed by the gold mines in tackling this problem is an example to these industries of what can be achieved by logical

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