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By L. A. Geoffrion, R. H. Perkins, J. C. Biery

Densities of cerium metal and several lour-melting binary cerium alloys were measured over the range 25° to 800°C. A rolumeter, using NaK as working fluid, was used to obtain the data. The cerium, Ce-Co, Ce-Ni, and Ce-Cu alloys all exhibited an increase in density on melting, while a Ce-Mn alloy expanded on melting. FOR the proper design of a nuclear reactor, the change in density of the fuel with temperature must be known. This is especially important in a system utilizing molten fuel, such as LAMPRE (Los Alamos Molten Plutonium Reactor Experiment), since a relatively large change in density usually occurs during the solid-liquid transition. The fuel for LAMPRE is a Pu-2.5 wt pct Fe alloy with a melting temperature of 410°C. However, limitations in reactor design with this fuel have led to consideration of other plutonium-containing alloys for use in future generations of this type of reactor. Several ternary alloys containing plutonium and cerium as two components have satisfactorily low melting points. The system that at the present time appears to be most acceptable is Pu-Ce-Co; it exhibits little change in melting temperature with wide variation in plutonium concentration. Other alloys that have received some consideration contain nickel, copper, and manganese as the third constituent. The proposed fuel alloys are difficult to handle experimentally in the 25" to 800°C temperature range since they oxidize readily, react with many solvents, and contain a poisonous fissionable material. In addition, in this temperature range the alloys pass through the solid-liquid transition. Several techniques are available for measuring the densities and volume coefficients of expansion of solids or liquids. However, the only apparatus that appears suitable for measuring expansion coefficients over this temperature range and through the phase transition is a volumeter. In a volumeter, the indicating medium must be essentially inert to and insoluble in the material being studied. It must also possess a low vapor pressure over the operating temperature range, and its coefficient of expansion must be accurately known. One material that is satisfactory in nearly all of these respects is the alloy Na-78 wt pct K, which melts at -10°C and has a vapor pressure of 860 mm Hg at 800°C. This relatively high vapor pressure at 800°C requires an overpressure of an inert gas to prevent boiling. While a volumeter is capable of determining accurately the volume coefficients of expansion of materials, it cannot be used for absolute density measurements. Therefore, a density determination at a known temperature must be coupled with the volumeter measurements to give all the desired data. The weight-loss technique using immersion in bromobenzene at room temperature proved to be satisfactory. The preliminary work that was done on this experimental program involved developing and calibrating the equipment, and measuring the densities and volume coefficients of expansion of cerium and some low-melting binary cerium alloys. The complications that are caused with the introduction of plutonium into the system were avoided until the equipment was proved to be satisfactory and until experience was gained in its operation. It is this first phase of the experimental work that is described in this report. DESCRIPTION OF EQUIPMENT AND OPERATING PROCEDURE The NaK volumeter is shown schematically in Fig. 1. Basically, the equipment consists of two weld-sealed stainless-steel containers of nearly identical volume. One container holds a tantalum crucible and the specimen being measured; the other contains a tantalum crucible and a tantalum specimen used as a control reference material. To avoid temperature gradients, the bombs are located in a copper block inside the furnace. Stainless-steel capillaries of equal length and volume connect each stainless-steel container to a glass viewing capillary. The stainless-steel containers, stainless-steel capillaries, and a portion of the glass capillaries are filled with NaK (22 wt pct Na-78 wt pct K). The NaK/gas interface in the glass capillary is viewed with a cathetometer which is accurate to *0.5 mm. The cathetometer readings are used to calculate the volume changes of the samples during a run. This volumeter is basically the same as that described by F. Knight in Plutonium 1960. 2 However, changes in equipment design and operating procedure were made to eliminate some major operating difficulties. These changes are summarized below. 1) In filling the manometer with NaK, gas was frequently entrained in the system. Evacuation of the system before filling failed to eliminate the en-

Jan 1, 1965

By S. M. Wu, R. L. Stone, T. D. Tiemann

The dissolution of silica from quartz in sodium hydroxide solutions was investigated by statistical methods. A second-order predicting equation was developed with 28 experiments expressing the dissolution of silica as a function of the variables quartz size, time, temperature and sodium hydroxide concentration. With this equation a comprehensive picture of the dissolution reaction was gained which included the effect on extraction of each variable and their interactions, fractional extractions, reaction rates and activation energies. A previous investigation of the extraction of silica from low grade siliceous iron ore by digestion in sodium hydroxide solutions presented the extraction as a function of time, temperature and sodium hydroxide concentration.' The present paper is an outgrowth of the previous work and develops by a mathematical analysis the functional relationship between the extraction of silica and time, temperature, sodium hydroxide concentration and particle size. Relatively pure quartz was used in this study in order that the basic quartz-sodium hydroxide reaction could be studied without the influence of other constituents that are commonly found in iron ores. The functional relationship between the dissolution

Jan 1, 1965

By W. C. Winegard, A. Galibois, C. J. Beingessner

The effects of solutes on the distribution of two-dimensional configurations of grains in zone-refined tin have been studied. When solutes with partition coefficients (ko) greater than unity are added, three-sided pains become more prevalent and the growth law changes. It is shown by electron-Probe micro-analysis that a solute buildup occurs ahead of a moving grain boundary when ko > 1. It has been found recently1, 2 that solutes with partition coefficients greater than unity have a larger retarding effect on grain growth than solutes with k, less than unity. ko is defined as the ratio of the concentration of solute in the solid to the concentration of solute in the liquid with which the solid is in equilibrium. Niessen and winegard2 have suggested that this effect is probably due to the complex shape changes which occur during the process of grain growth and that no theory based on single boundary motion3-5 can explain the results. They suggested that the dissociation of the unstable fourfold junction was delayed in alloys where ko was greater than 1 because the boundaries at the junction had to move into a region of high solute concentration. If indeed this mechanism were correct, it was felt that not only would the dissociation of fourfold junctions be affected by the solute buildup ahead of the boundaries, but the collapse of three-sided grains would be impaired. These combined effects would naturally lead to a modification in the distribution of the number of sides per grain seen on a two-dimensional section. The present investigation was undertaken to test these hypotheses by examining the grain-growth process in detail. EXPERIMENTS The Distribution of Grain Configurations in Zone-Refined Tin as Seen on a Two-Dimensional Section. Following the method of Bolling and Winegard,6 zone-refined tin was cast into button-shaped specimens and, subsequently, plastically deformed under a drop hammer at room temperature. The resulting flat coin-shaped samples were annealed at 200°C, some for 50 sec and others for 100 sec. The specimens were then examined to determine the distribution of the number of sides per grain, i.e., the num- ber of crystals adjacent to any particular grain in the section. For simplicity, the grains were classified as three-sided, four-sided, and so forth; this concept is schematically illustrated in Fig. 1. As indicated by smith,' it was necessary to examine every grain within an enclosed area to obtain a proper distribution of the relative frequency of each type. The distributions for the two annealing times are illustrated in Fig. 2. The total number of grains examined is also indicated on the figure. It is evi-

Jan 1, 1965

By R. F. Hehemann, D. J. Cometto, G. L. Houze

The w transformation in the Zr-Nb system was studied using X-ray diffraction, dilatometric, re-sistornetric, hardness, and metallographic techniques. w forms in a diffusionless, completely reaersible manner on quenching and in a diffusion-controlled manner- on aging. The temperature at which w begins to form on quenching was determined as a Junction of composition and was found to decrease with increasing solute content. w formed bv aging establishes a metastable equilibrium with an enriched ß phase. The ß/w + ß transus has been determined for this metastable equilibrium and employed to rationalize retrogression and reversion phenomena observed in these alloys. The decomposition mechanism is discussed in terms of a gradual or continuous transformation from ß to the w state. BETA- stabilizing alloying elements lower the MS temperature of the martensitic bcc (ß) to hcp (a') transformation in zirconium and titanium alloys. In certain titanium alloys, a lower symmetry modification of the martensitic structure, termed (a"), also has been reported.1,2 These martensitic transformations are suppressed when the amount of the ß-stabilizing element exceeds a critical level. However, the high-temperature ß phase cannot be quenched to room temperature without change. At alloy contents just above the critical level, |ß trans-forms to the w phase when cooled rapidly.3-6 The amount of w in quenched alloys is reduced by increasing alloy content, and this phase virtually disappears above a critical composition.5 In addition to the transformation during cooling, w also can be formed by aging ß at temperatures below approximately 500°C, and significant alloy enrichment of retained 13 accompanies the isothermal transformation.1-8 The structure of LC is closely related to that of the ß from which it forms.9-15 The bcc (ß) lattice can be generated using a hexagonal cell with three atoms located at (000) and ±(2/3, 1/3, 1/3). This cell has an axial ratio of 0.612 and is oriented with respect to the cubic cell such that (0001)H (111)C and [1120]H [101]C. Consequently, there are four possible orientations of the hexagonal cell, associated with the four (111) planes of the bee lattice. Formally w can be obtained from 0 by allowing the two atoms at the ±(2/3, 1/3, 1/3) positions to approach the coordinates ±(2/3, 1/3, 1/2) and there are four equally probable orientations of w for each 0 grain. In titanium alloys w retains the cubic axial ratio of 0.612" and hence also can be indexed as triply cubic, but this is not the case for aged Zr-Nb alloys where w is clearly hexagonal with an axial ratio of 0.622." The lattice parameters and atomic positions of w depend on thermal history and alloy content. The atomic positions (000), ±(2/3, 1/3, 1/2) provide reasonable agreement between calculated and observed diffracted intensities for w in the fully aged condition.10,14 In the quenched condition, on the other hand, the atoms appear to be displaced from the central plane12,13,15 and assume positions ±(2/3, 1/3, Z = 0.42-0.48) rather than ±(2/3, 1/3, 1/2). This results in a structure with trigonal rather than hexagonal symmetry. The readily detectable parameter and axial-ratio changes of w in Zr-Nb alloys make this system especially attractive for studying the structural changes that occur in the formation and aging of w. Particular attention in this investigation has been directed to the relationship between the structure of w in the quenched and aged conditions, and to certain aspects of the reaction kinetics. MATERIALS AND PROCEDURE Zr-5, 12, 17.5, and 25 pct Nb alloys were prepared by a double arc-melting practice, encased in stainless-steel cans and hot-rolled to 1/8-in.-thick sheet.* Charged weights have been employed for the niobium contents and interstitial analyses are reported in Table I. Dilatometric, X-ray diffraction (filtered CuK, and MoK, radiation), metallographic, and hardness techniques have been employed to follow the transformations during isothermal and quench-aging heat treatments. In quenched specimens, the electrical resistivity also was studied. Betatizing was conducted for 1 hr at 900°C. With the exception of the isothermal dilatometric studies, samples were

Jan 1, 1965

Coal research and related activities in 1964 by the Bureau of Mines resulted in many advances in the production, preparation, and utilization of this valuable natural resource. Mining research during the year was marked by work on hydraulic mining, coalbed degasification, mine drainage control, mine sealing, strip-mine rehabilitation, and quenching of mine-refuse fires. Bureau research continued to produce information leading to increased safety in underground mining. Such research included roof and rib control via bolting and bonding, pressure monitoring of coal and mine rock during mining operations, and development of safety devices for detecting conditions leading to roof falls. Other safety work was continued on methane detectors, coal-dust suppression, and mine ventilation equipment and techniques. Mine explosion and explosives research, mine equipment and materials, safety rule modernization, and safety education and training of mine workmen were continued. Coal storage and preparation work in 1964 ranged from freezeproofing of lignite for rail shipment, through washability studies of coals and washing equipment, to research on new ways to remove ash and sulfur from coal. Electric power production, which accounts for a major portion of the market for coal, received further study. Unique power generation systems, including coal-burning gas turbine and megnetohydrodynamic generators, were intensively investigated. Conventional power systems were improved through continuation of work on furnace performance, powerplant stack gas purification, and engineering and boiler water service.

Jan 1, 1965

By Wallace W. Key

Mineral raw materials produced in California, other States, and foreign countries were purchased for consumption in quantities valued at over $60 million at 800 of the 1,200 chemical plants operating in California Fn 1960, according to questionnaires completed by company officials. These and other data received from mineral consumers, producers, dealers, and Government agencies formed the basis for this the first of a series of reports designed to present the intricate features and relationships controlling mineral raw material supply and demand in California industries. The results of this study indicated certain changes in use patterns of minerals in chemical manufacturing; a shift in requirements from metals to nonmetals, from inorganics to organics, from natural to synthetic materials, and from distant to local sources of supply.

Jan 1, 1965

The Bureau of Mines has reviewed those portions of the "Tariff Schedules of the United States Annotated 1963" that are of interest to the minerals industry. This study shows to what extent rates of duty were altered (increased or decreased), and provides a bridge where possible from the old Schedule A classification sys tem to the new TSUS system of statistical reporting of import data. In general the new tariff has corrected previous classification defects and inconsistencies, but the rates of duties have not been materially changed.

Jan 1, 1965

By Sabri Ergun

NEW theoretical data are presented for the intensity of X-rays diffracted from randomly oriented aromatic and alicyclic molecules and diamondlike structures such as are found in coals, cokes, and carbonaceous materials. Data have been computed using the Debye interference function. Computations for the smaller molecules have been made with the Univac 1204 computer: those for large structures, with either the IBM 704 or Bendix G-20 computer. A brief theoretical introduction of the Dobye interference function is given, and an outline is made of the treatment of experimental data so that the experimental interference function can be obtained.

Jan 1, 1965

By James R. Kerr

This study reviews the sulfur and suliuric acid industries in Eastern United States with emphasis on patterns of consumption and marketing. Output of sulfur in the East is relatively small, and most of the area's sulfur requirements are met by gulf coast Frasch sulfur. Over the long ten recovered elemental sulfur from sour natural gas and petroleum may become the East's major source of sulfur. In 1958 sulfuric acid manufacture consumed over 80 percent of the area's sulfur requirements. The leading uses for sulfuric acid were the manufacture of superphosphates and chemicals. Over the years, unit requirements for sulfur and acid in many major markets have been reduced through improved technology, but new markets always have been developed to keep the industry vital and growing.

Jan 1, 1965

By Robert E. Green

Experiments were performed in order to investigate the influence of magnitude of driving force, recouery, and previous heat treatment on grain boundary migration in deformed aluminum crystals. The frequency of occurrence of strain-free grains possessing Preferred crystallographic orientations was studied both as a function of heat treatment and as a function of amount of deformation of the matrix crystal. Aluminum of such composition as to exhibit precipitation-hardening behavior was used. CONSIDERABLE work has been devoted to the factors influencing grain boundary migration in metals.1'52 Aust and Rutterl-9 have studied grain boundary migration into matrix crystals containing a striation substructure, which provided a thermally stable driving force during the course of the migration experiments. These authors state that, while variations in the striation pattern were sometimes observed, it was possible to obtain reasonably uniform and reproducible striation structure by careful control of the solidification conditions. Admittedly, this source of driving force is a unique one and has served well in numerous experiments. However, although the striation substructure provides a thermally stable driving force, the subject of its reproducibility from crystal to crystal is questionable. In fact, Aust and Rutter3 attribute the scatter shown in some of their experimental points and several anomalies in boundary migration rates to variations in the substructure driving force along a single specimen. A further limitation on striation-induced driving force is that the driving force cannot be varied over wide ranges in a controlled manner. More often used as a source of driving force is the strain energy stored in a crystal during plastic deformation. This type of driving force has the disadvantage that it is not thermally stable due to recovery taking place simultaneously with the grain boundary mobility measurements. On the other hand, this strain-induced driving force is very reproducible from crystal to crystal since it is very easy to grow single crystals possessing the same purity and crystallographic orientation and then to strain them identically. In order to measure grain boundary migration rates two different methods are primarily used. Most often the technique employed is the heat-cool-etch method1' which involves thermal cycling, while the other technique, developed by Graham and Cahn11 using an X-ray diffractometer and goniometer furnace, involves continuous heating only. Thus the influence of thermal cycling vs continuous heating is a factor to be considered in grain boundary migration rate measurements, particularly in cases where the source of driving force is the strain energy stored in the deformed matrix, and recovery is likely to occur. Numerous recent investigations have shown that extremely small impurity additions to zone-refined metals exert a marked effect on grain boundary migration rates1-5, 9, 12-27 and a few have considered the effect of the distribution of impurities.28-35 The concentration of impurities and their distribution as influenced by heat treatment must also be taken into account in migration-rate studies. In the present article consideration is given to the influence of the magnitude of driving force, recovery, and previous heat treatment on grain boundary migration rates. In order to vary the driving force over a large range it was necessary to use as a source of driving force the energy stored in the matrix crystal during plastic deformation. A majority of the investigations were performed on aluminum specimens which were of such compositions as to exhibit precipitation-hardening behavior.

Jan 1, 1965

By Edna A. Dancy, Ronald L. Pastorek, Gerhard J. Derge

In an earlier study1 in this laboratory, it was found that there is a minimum in the specific conductance of Ni-S melts in the region of the stoichiometric composition, Ni3S2. This and similar observations on other sulfide1 and telluride2 systems suggest that short-range order exists in the molten phase for several hundred degrees above the melting point, and a qualitative energy-band model has been proposed, with intrinsic semiconduction at the stoichiometric composition and degenerate electron and hole conduction at metal- and tellurium-rich compositions. This suggestion has been substantiated for the telluride systems by Seebeck coefficient measurements which showed a change in sign from negative on the metal-rich side to positive on the tellurium-rich side. In the present investigation, in order to substantiate still further the proposed model, Seebeck coefficient determinations have been extended to the Ni-S system over a composition range in the vicinity of Ni3S2. The experimental method was essentially the same as that used for the telluride systems, with minor modifications on cells for high sulfur melts to permit the use of tungsten wires and W— W-Re th~rmocouples instead of the chrome1 or alumel wires and chromel-alumel thermocouples originally used. Chrome1 and alumel both deteriorate very rapidly in atmospheres containing sulfur. The Ni-S alloys were prepared as described in the conductivity paper. Initially, a portion of the solidified melt was analyzed at the end of a run, but after this was found to be inaccurate because of segregation during cooling, the whole sample was analyzed. The nickel content, only, was determined, the sulfur content being obtained by difference. The results are summarized graphically in Fig. 1, and clearly show a change in the sign of the Seebeck coefficient in the region of the stoichiometric composition. This change of sign near Ni3S2, coupled with the minimum in the conductivity, is suggestive of an intrinsic semiconductor at the stoichiometric composition, with degenerate electron and hole conduction on either side of this composition, in keeping with the proposed model. The negative temperature coefficient of conductivity, normally indicative of metallic conduction, is not inconsistent with this model. In the completely degenerate region it would be expected, while in the vicinity of Ni3S2 the suggestion originally made by Argyriades, Derge, and pound3 for the Fe-S system can probably be applied. They proposed that the forbidden gap between the valence band and the conduction band is small, and that the increase in the number of the conducting species with increase in temperature is not large enough to compensate for the loss of mobility through thermal scattering. The research was sponsored by the Office of Naval Research under Contract NONR-760(22) Project NR 039-081. 'E. A. Dancy and G. J. Derge: Trans. Met. Soc. Aime, 1963, vol. 227, pp. 1034-38. 'E. A. Dancy: Trans. Vet. soc. AIME. 1964, vol. 233, pp. 270-77. 'D. Argyriades, G. Derge, and G. M. Pound: Trans. Met. Soc. . 1959, vol. 215, pp. 909-12.

Jan 1, 1965

By James R. Kerr

This study reviews the sulfur and suliuric acid industries in Eastern United States with emphasis on patterns of consumption and marketing. Output of sulfur in the East is relatively small, and most of the area's sulfur requirements are met by gulf coast Frasch sulfur. Over the long ten recovered elemental sulfur from sour natural gas and petroleum may become the East's major source of sulfur. In 1958 sulfuric acid manufacture consumed over 80 percent of the area's sulfur requirements. The leading uses for sulfuric acid were the manufacture of superphosphates and chemicals. Over the years, unit requirements for sulfur and acid in many major markets have been reduced through improved technology, but new markets always have been developed to keep the industry vital and growing.

Jan 1, 1965

By E. Miller, J. M. Eldridge, K. L. Komarek

The liquidus curve of the Mg-Pb system was accurately redetermined. The compound Mg2Pb decomposes peritectically at 538.2° ± 0.3°C to liquid and to a compound p' which melts congruently at 35.0 at. pct Pb and 549.0° ± 0.3°C. The solidus curve of ß' was determined. X-ray diffraction studies indicate that 4' has an orthorhombic structure. Activity values of magnesium calculated from the phase diagram agree with those published in the literature. EXPERIMENTAL thermodynamic properties of binary metallic systems have to be consistent with values calculated from the phase diagram. In systems forming intermetallic compounds the shape of the liquidus curve near a compound is determined by the thermodynamic properties of the coexisting solid and liquid phases. Hauffe and Wagner' neglected the temperature dependence of the chemical potentials and obtained the potential differences of the components of the liquid alloys, relative to stoichiometric liquid. Their calculations were based on the liquidus curve and on the heat of fusion of the compound, and were only valid near the congruent melting point. Steiner, Miller, and Komarek2 developed equations which account for the temperature dependence and obtained the chemical potentials of liquid Mg-Sn alloys over the entire phase diagram from the liquidus and solidus curves and from enthalpy values with the pure components as the standard states. The Mg-Pb phase diagram has been studied by several investigators whose results have been compiled and critically evaluated by Hansen.3 Although the liquidus curve was poorly defined, the general features of the diagram, i.e., one congruent melting compound, Mg2Pb, of essentially stoichiometric composition, two eutectics, and limited terminal solid solubilities, seemed to be suitable for a similar thermodynamic analysis. A careful redeter-mination of the liquidus by thermal analysis revealed, however, the existence of another compound. The liquidus curve between the two eutectics was precisely delineated and the structure and solidus curve of the new compound were investigated. The revised phase diagram was thermodynamic ally analyzed to evaluate the activity of magnesium in the liquid alloys. EXPERIMENTAL PROCEDURE The magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) had a purity of 99.99+ pct; lead (American Smelting and Refining Co.) contained 99.999 pct Pb. Most experiments were carried out in graphite crucibles. Several experiments were made in high-purity alumina (Triangle R.R., Mor-ganite, Inc.) and in Armco iron crucibles to test the inertness of the graphite crucibles. Chemical analysis of magnesium and detailed description of the procedure for thermal analysis have been given previously. For the determination of the solidus curve of the compounds, specimens of initial composition Mg2Pb were equilibrated in a closed isothermal system with magnesium vapor. The source of the magnesium vapor was an alloy which had a gross composition lying in the 0' + L field at the temperature of equilibration. As equilibrium was approached, the specimens lost magnesium to the two-phase reservoir thereby lowering the activity of magnesium in the specimens until activity and composition equaled that of the ß'/ß' + L boundary. Crucibles (1.9 cm ID by 2.2 cm OD by 4.1 cm high) and tightly fitting lids were machined from a molybdenum rod; small, shallow trays were fashioned from thin (0.005 in.) molybdenum sheet, and all the molybdenum components were degreased in hot carbon tetrachloride and then dried. The pieces were then degassed in vacuum at 950°C for about 6 hr. The two-phase alloy was placed at the bottom of the crucible and small specimens of the Mg2Pb compound, weighed on an analytical balance, were placed in two molybdenum trays above the two-phase alloy. The crucible was closed by forcing its lid on and then inserted in a titanium crucible. This crucible was evacuated, flushed twice with argon, and welded under argon. The specimens were equilibrated for about 1 week in a resistance furnace regulated by a Celectray controller, and the runs were terminated by water quenching. The specimens were again weighed and the equilibrium compositions were calculated on the basis that the weight losses were solely due to a loss of magnesium to the two-phase alloy. The structure of the B' phase was investigated by the Debye-Scherrer X-ray diffraction technique. Selected ingots from thermal-analysis experiments containing about 35 at. pct Pb were re-melted, slowly cooled, and crushed in an argon-filled glovebox until the entire ingot passed through a 50-mesh sieve. The powder was thoroughly

Jan 1, 1965

By Michael G. Zabetakis

THIS is a summary of the available limit of flammability, autoignition, and burning-rate data for more than 200 combustible gases and vapors in air and other oxidants, as well as of empirical rules and graphs that can be used to predict similar data for thousands of other combustibles under a variety of environmental conditions. Specific data are presented on the paraffinic, unsaturated, aromatic, and alicyclic hydrocarbons, alcohols, ethers, aldehydes, ketones, and sulfur compounds, and an assortment of fuels, fuel blends, hydraulic fluids, engine oils, and miscellaneous combustible gases and vapors.

Jan 1, 1965

By P. G. Sprang, S. Rosen

The Y-Al- C ternary phase diagram for the com -position range from 55 to 100 at. pct Y and for a temperature of 950°C has been constructed from metallographic and X-ray diffraction data. The significant features of the isothermal section which is presented are the small solubility of aluminum in the binary Y3C phase and the presence of a ternary carbide phase with a small homogeneity range around the composition Y3AlC. The similarity in structure and composition between these two carbide phases is discussed in the light of the misci-bility gap which exists between room temperature and 1300°C, which was the temperature range studied. THE occurrence and stability criteria of ternary T3BC, carbide phases having the L'12 structure and the general formula T3BCx have been discussed in detail by stadelmaier1 and more recently by the present authors., Stadelmaier found many representatives of these phases formed between the T metals Mn, Fe, Co, and Ni and the B metals Mg, Al, Zn, Ca, Ge, Cd, In, Sn, Hg, T1, and Pb. The present authors reported on a new series of iso-structural carbide phases formed between the T metals of the Sc group and the B metal, aluminum. These new phases are unique in that many of the Sc group elements form stable binary carbide phases which occur about the composition T3C and which crystallize with a structure similar to that of the T9BCx ternary carbide phases. Furthermore, these binary and ternary phases are found to coexist in equilibrium with each other. The similarity in structure and composition between, for example, Y3C and Y3AlC in the light of the mis-cibility gap which had been found to exist between these two phases indicated a need for a more thorough knowledge of the phase relations which occur in alloys based upon these compositions. Consequently, an investigation of the phase equilibria in the yttrium-rich portion of the Y-A1-C phase diagram was undertaken. The limiting Y-A1 binary diagram determined by Lundin and Klodt3 and the results of Spedding et al.4 governing the Y3C phase were used as guides in , constructing the diagram. EXPERIMENTAL Alloys weighing about 10 g were prepared by arc-melting powder compacts made from the various components on a water-cooled copper hearth using a tungsten electrode in a gettered argon atmosphere. Good homogeneity was obtained by melting the alloys three times. The purity of the yttrium used was 99.9 pct (0.07 pct rare earths). The purity of the aluminum and the carbon was 99.99 pct. The results of chemical analysis on five representative alloys showed that losses during the alloying process were predominantly carbon losses and that in no instance did the measured concentration of this component differ by more than 3 at. pct from the intended composition. For this reason the alloy compositions which are reported are those of the charges prepared for melting. Three alloys which were analyzed for copper, tungsten, nitrogen, and oxygen compositions showed that no contamination had occurred either during casting or during the subsequent annealing treatments. For the major part annealing treatments were carried out on specimens which were placed in

Jan 1, 1965

By H. Fechtig, R. H. Buck, A. G. Guy

MULTIPHASE diffusion has been studied for many years in two-component systems1,2 and many of the experimental aspects are now fairly well understood.314 Although by no means all of the problems connected with the two-component case have been solved,' attention has recently been directed to the more complex situation involving three components. The pioneer work of Clark and Rhines6 yielded a qualitative picture of the types of behavior that can occur, and Clark7 has suggested conventions for describing the various phenomena. Kirkaldy and co-workers8,9 have made quantitative studies in several ternary systems and have offered explanations of the occurrence of isolated and nonisolated precipitates. At present, however, there is no comprehensive theory for the variety of phenomena observed in ternary, multiphase diffusion. By analogy with several studies that have been made of multiphase diffusion in the binary Cu-Zn system,2'10'11 a similar exploratory study was made of Cu-Zn-Ni alloys lying along the line in the ternary diagram from the point 80 Cu-20 Ni to the zinc corner of the diagram, Fig. 1. A principal question to be answered was whether initially plane interfaces would remain plane during the course of one-dimensional diffusion. The diffusion specimens studied are described in Table I. The five separate alloys from which they were made were melted in evacuated Vycor capsules from 99.9 pct purity copper, zinc, and nickel. Since some of the alloys were too brittle to be swaged, all of the alloys were used in the cast condition. To facilitate later homogenization, the molten alloys were solidified by plunging the capsule in water. Homogenization heat treatment was done at 720°C for 20 hr. The five nominal compositions in weight percent zinc and nickel, respectively, were: 37.5, 12.5; 44.0, 11.2; 50.0, 10.0; 55.0, 9.0; 65.0, 7.0. Ln Table I the alloys are identified only by their zinc content. Sandwich-type diffusion specimens were prepared by pressure welding disk specimens, each about 3 mm high by 10 mm in diameter. Welding was done in a special threaded vise which was heated at 500°C for about an hour in an atmosphere of flowing hydrogen. A measurement of the separation of the phase interfaces was made on a polished flat on the welded specimen, and then the specimen was sealed in an evacuated capsule and given the diffusion treatment shown in Table I. The diffused specimen was sectioned longitudinally

Jan 1, 1965

By G. J. Hawkes

"We all know that every man who works for us should have a thorough knowledge and understanding of his responsibilities. But how about ourselves? Du we have a thorough knowledge and understanding of our own responsibilities as Mill Superintendents?I once had an occasion to say to a Manager that I did not know something was my responsibility and he replied with suitable emphasis ""Everything inside those four walls is your responsibility"". That makes the extent of our responsibilities clear but does not give us a check list to keep an eye on as we do our job from day to day.What are our responsibilities? I suggest they are the following:1. Developing and maintaining efficient operating and maintenance crews.2. Milling the required tonnage.3. Recovering the economical maximum amount of gold.4. Keeping costs at the economical minimum.5. Seeing that the figures are reasonably accurate for tonnages, assays, production, losses, and costs.6. Preventing accidents.7. Preventing fires.8. Maintaining the equipment and building and keeping them clean and tidy.9. Enforcing company rules and regulations."

Jan 1, 1965

By Stewart W. Daniel

Competitive pressures involving product duality, uniformity and economics are increasing the interest in and accelerating' the adoption of automation by the cement industry. The demands of this industry on instrumentation and control manufacturers for more effective and reliable control of process variables is also increasing. The trend to replacing small grinding mills with a fewer number of larger mills is lowering the investment requirement per unit of capacity both for the mills and for their automation. Cement process control systems of today are more sophisticated than the equipment installed two or three years ago, not because the process itself is more complex but because todays demands require a higher degree of control action and accuracy. Because of increasing labor costs, an important objective of an automation program is a reduction in the process labor content. This can be realized by allowing the operator free time for other duties, by increasing the number of grinding circuits one operator can supervise and by removing to. a large extent the need for the operator to make process' adjustment decisions.

Jan 1, 1965

By Mark J. Klein

An internal-friction profile induced by nitrogen in Cr-35 at. pet Re was studied as a function of nitrogen concentration and heat treatment. From these studies, the solubility of nitrogen in this alloy was deduced. The equilibrium solubility of nitrogen in chromium does not appear to be substantially changed by the addition of 35 at. pet Re to chromium. However the precipitation kinetics of nitrogen from solution are significantly decreased. IT has been found that rhenium has a beneficial effect on the low-temperature ductility of Group VI-A metals. As part of a study to investigate the mechanism of this increased ductility, it was of interest to compare the concentration of interstitials retained in solution in one of these ductile bee alloys with the concentration retained in solution in its base metal. In this regard, a study of the solubility of nitrogen in ductile Cr-35 at. pet Re was selected for this phase of the investigation because the solubility of nitrogen in the base metal, chromium, has been determined over a fairly large temperature span.1-3 In addition, nitrogen is known to have an embrittling effect on chromium,4 but does not appear to have a comparable embrittling effect on Cr-35 at. pet Re.5 The experimental method selected for this study was the measurement of internal friction. This technique allows interstitial-concentration measurements to be made in bee metals that are sensitive to small changes in the concentration of a particular interstitial, even when other interstitials are present. When subjected to a cyclic stress, interstitial atoms in solid solution give rise to an internal-friction peak whose origin is the stress-induced ordering of interstitials into preferred lat- tice sites. These internal-friction peaks signify a dissipation of elastic energy which is greatest when the period of oscillation is comparable with the relaxation time for the attainment of an equilibrium interstitial distribution. For dilute interstitial binary alloys, the height of the internal-friction peak is proportional to the concentration of interstitial atoms in solid solutions. snoek8 has shown that the internal friction, Q-1, may be expressed by the equation where A is the relaxation strength, ? is the angular frequency, and 7 is the relaxation time. The relaxation strength, A, is proportional to the concentration of interstitials taking part in the relaxation if no interaction occurs between solute atoms. Thus values of peak height, which can be determined as a function of temperature, give a measure of the relative concentration of interstitial atoms in solution at various temperatures. If equilibrium has been attained, the peak heights will be proportional to the interstitial solubilities. The constant that relates A to the interstitial concentration can be determined experimentally from peak-height measurements as a function of concentration for specimens of constant crystallographic orientation. When this has been done, Q-1 measurements can be used to determine solubilities according to the equation C - KQ-1 where C is the soluble interstitial concentration and K is a constant that can be experimentally determined. It is possible, however, that lattice imperfections may bind interstitials to certain lattice sites. Internal friction does not measure these interstitial~, but does measure interstitials which are free to move in the normal lattice sites when subjected to an applied oscillating stress. On alloying the pure metal with a substitutional

Jan 1, 1965

By Dr. O. M Solandt

CANADA is not an old country we are just now planning to celebrate our lOOth Anniversary. Nonetheless, we have already developed some well-established traditions. One of the minor traditions is the standard speech on the need for more research and development in Canadian industry. I am sure that you have all listened to it many times -I certainly have given it more than once. Much as I am tempted to honour this tradition by repetition, I shall only give you a thumbnail sketch of the ancient address for the benefit of any unfortunate visitors who have not heard it before, and also to provide a base for some further ideas that I want to leave with you. Briefly, the traditional story is that, for a variety of historical and environmental reasons that I shall not attempt to describe in detail, research and development in Canada has grown up in a pattern that is ill adapted to foster the expansion of our manufacturing industries. The story continues by saying that research in the universities is of excellent quality but that we are very short of money to meet the expanding needs

Jan 1, 1965