Search Documents

By C. H. Samans, G. F. Tisinai

HARDENING and embrittlement of the ferritic chromium stainless steels at temperatures near 885 °F have been known for a long time.' However, no satisfactory explanation has been given. Both ordering and precipitation hardening have been suggested. Fisher, Dulis, and Carroll2 discovered a chromium-rich body-centered-cubic precipitate in embrittled alloys. Subsequently, Williams' and Wright4 also have found evidence of this body-centered-cubic constituent. William's hardness, electrical resistance, and magnetic studies led to his proposal of a new constitutional diagram for the Fe-Cr alloys. The new feature of this diagram is the eutec-toidal decomposition, below about 970°F, of the s phase into two stable body-centered-cubic solid solutions, one rich in iron and the other rich in chromium. An observation of Heger5 that the amount of s phase has increased and the amount of chromium-rich body-centered-cubic phase decreased in the interval 5000 to 32,600 hr at 900°F, even though the alloy increased in hardness, casts some doubt on this diagram. If precipitation hardening causes the embrittlement, the precipitate probably is always coherent with the matrix, since no evidence of overaging has been reported. It cannot be stated positively, however, that Fisher's body-centered-cubic constituent is the embrittling phase. According to Preston's data,6 such a chromium-rich phase should have a parameter less than about 0.5 pct larger than that of the iron-rich matrix lattice. Moreover, the constitutional relationships whereby Fisher's constituent forms, and whether it is stable, metastable, or a transition phase, are not yet completely clear. The recent studies of Wright4 and of Lommel,7 as well as the earlier studies of Becket8 and of Hochmann,9 have shown that 885°F hardening occurs in relatively pure Fe-Cr alloys. No evidence of its occurrence or absence in chromium itself has been reported. The rate of hardening in high purity alloys seems appreciably slower than that in alloys containing larger amounts of impurities (chiefly carbon and nitrogen). This may be due merely to the absence of hardening and straining effects from precipitated carbides and/or nitrides. These observations on high purity alloys make it seem unlikely that 885 °F hardening is caused by a constituent containing other than iron and chromium atoms, e.g., carbides and/or nitrides. Wright,4 Lommel,7 and Lena and Hawkes10 emonstrated the accelerating effects of a finely dispersed precipitate of (probably) chromium nitride on the hardening reaction. This appears to be evidence that lattice straining increases the rate of nucleation of the hardening constituent. Some new observations on 885°F hardening are reported here. They show an effect of preheat treatment that should contribute to a better understanding of the 885°F hardening phenomenon. They also clarify a discrepancy which exists in the literature. Some investigators have reported most rapid hardening at 885", whereas others have reported it at 930°F. The present work also shows that 885°F hardening does not occur in electrolytic chromium, and that any long range ordering type of reaction affecting any sizeable part of the volume is unlikely. Materials Studied Table I shows the currlposition of the alloys used in this investigation. In these alloys carbon and nitrogen are present in roughly similar amounts. Presumably both elements precipitate, as carbides and/or nitrides, during the heat treatments given.

Jan 1, 1958

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

Solid-solubility limits at 1500°, l000q and 500°C for carbon, nitrogen, and oxygen in high-purity tantalum were determined by X-ray lattice-parameter methods. For carbon, the solubility was found to be 0.17 at. pct at 1500°C, and less than 0.07 at. pct at 1000°C. A nitrogen solubility of 3.70 at. pct at 1500° C decreases linearly with temperature to 2.75 at. pct at 1000°C, and 1.8 at. pct at 500°C. In the case of oxygen, the solubility was found to be 3.65 at. pct at 1500°C, 2.95 at. pct at 1000°C, and 2.5 at. pct at 500°C. The phases Ta2C, the low-temperature modification of Ta205, and Ta,N of unknown composition but which has a superlattice structure based upon the original bcc tantalum lattice have been identified as the initial precipitates in the respective systems. Metallographic methods were employed to verify the X-ray analyses. The etching behavior of Ta is discussed in terms of lattice i?rzperfections and precipitate phases. The excellent fabricability, high melting point, and nuclear properties of tantalum are responsible for interest in this refractory metal. Data on the solid solubility of the interstitial elements (oxygen, nitrogen, and carbon) in tantalum and on the precipitate phases are somewhat limited. The significant contributions are discussed below. Because the purity of electron-beam melted tantalum (only recently available) is considerably higher than that used in previous studies, the present investigation was initiated. Gebhardt et all-3 have investigated the tantalum-oxygen and tantalum-nitrogen systems with particular reference to the changes in physical properties and to the rates of reaction between these gases and the metal. The solubility of oxygen in tantalum was reported2 to be 3.7 at. pet at 1500°, 2.3 at. pet at 100O°C, and 1.4 at. pct at 750°C. Schonberg4 reported that several oxide phases (Ta40, Ta,O, TaO and Ta,05) exist while X-ray studies by Gebhardtl showed only two oxides, Ta,05 and an unidentified phase which was associated with a platelet-type precipitate. La-gergren and Magneli,' however, questioned the existence of compounds other than the two allotropic modifications of Ta,05 for the tantalum-oxygen system. In the case of nitrogen, the solubility was estab- lished by Gebhardt3 to be of the order of 7 at. pct at 1800°c. The solubility was reported to decrease rapidly with temperature, and, although no limits were established, a precipitate phase was observed by Gebhardt except when the high-nitrogen specimens were cooled very rapidly from the reaction temperature of 1800c. He reported the initial precipitate phase to be a tetragonal distortion of the bcc tantalum lattice while Schonberg6 reported the phase lowest in nitrogen Jo be a cubic super-lattice with a cell size of 10.11 A. Two other nitride phases, Ta,N and TaN, were reported; these appear to be isomor-phous with the carbides of tantalum. The tantalum-carbon system was investigated by Ellinger7 and by Lesser and Braurer. Two compounds, Ta,C and TaC, were reported to exist, each with a range of composition. The solubility of carbon in tantalum was found to be practically nil at all temperatures. Thus, of the interstitial elements which are present in small amounts in high-purity tantalum, carbon might be expected to form precipitates. The present investigation was initiated to obtain additional data on the solid-solubility limits of these interstitials at 1500°, 1000°, and 500' with particular emphasis on the distribution and the identification of the precipitate phases. EXPERIMENTAL WORK AND RESULTS In the present investigations of the solid solubility and of the precipitate phases in the systems tantalum-nitrogen, -oxygen, and -carbon, high-purity tantalum was reacted with high-purity gases, homogenized at 1800°c, and annealed at and quenched from 1500°, 1000,

Jan 1, 1962

By William G., Pariseau

There are important phenomena in rock and soil mechanics that cannot be explained in terms of theories of homogeneous, isotropic materials. Subsidence of strata about mine openings is an example. In-situ stress measurements in nonisotropic sedimentary, and metamorphic rocks is another. Patterns of joints, faults, fractures, and similar geologic features impart directional mechanical properties to rock masses that are locally isotropic or anisotropic. On the geologic scale, the non-homogeneity of composite rock masses may, in certain instances, be dealt with as homogeneous anisotropy. The mechanics of large rock masses can, therefore, be expected to involve considerations of anisotropy. The source of the anisotropy is not relevant. Once the scale of observation is selected and the material is defined accordingly, the analysis of stress and deformation proceeds without regard to the numerical values of the material constants. There are also important phenomena in rock and soil mechanics that cannot be explained in terms of linear elasticity, theory. For the mechanical description of anisotropic geologic materials capable of de- forming beyond the limit of purely elastic strains, a plasticity theory is required.

Jan 1, 1972

By P. S. Roller

P. S. ROLLER,*College Park, Md.-The author introduces the idea of a grind limit, or lower size limit of the particles formed directly by grinding, and this is stipulated to be 0.70 micron. I wonder where all the particles come from that lie between the resolving power of the microscope and 0.7 micron, which are seen under a microscope in examining a sample of grind? There is also introduced the idea of excess fines; this is all right in itself but the author's quantitative definition seems to be virtually impossible to justify, and, moreover, is obscure. Just why E, the excess fines, should he defined as the distance between an F line and a y line is hard to follow, and just where the distance should be measured does not appear to be stated, as it should be since the F and y lines intersect and the distance between will depend upon where that distance is measured. The basis of the presentation is the relation of log weight against log size that was "discovered" by Schuhmann. While this relation is implied to fit, the only evidence that I can see is a slightly irregular line in Fig. x between 2 per cent and 18 per cent by weight and then a precipitous drop at 18 per cent away from any sort of straight line. Some of the conclusions are rather startling. It is stated that E, the excess fines, remains constant for all the comminution products of any particular material, except that it may decrease for some coarse crusher products. No reason is given for this assertion. One would, on the contrary, expect that excess fines, if such a concept is permissible, would generally vary with different conditions instead of being constant. Again, "as much net energy is required to reduce a ton of quartz to particles of the grind-limit diameter (namely, of course, 0.7 micron) by grinding as is required to melt the quartz." This would require many data to prove, but no proof is given; any consideration would reveal the impossibility of such a result. Still further, ore samples "ground to widely different sizes, and with different circulating loads and different size distributions or product, show the same production of new surface area per revolution of the mill, when this grind limit is used." This statement is confuted by ordinary experience, which teaches that grinding efficiency varies generally with the condition of material. For example, the cushioning effect of fines is widely accepted, while the inefficiency of a ball mill when the feed is too coarse is also well known. R. SCHUHMANN, JR.," Cambridge, Mass. Contrary to Mr. Bond's stand, there is a great deal of miscellaneous experimental evidence that comminution does not stop at around 0.7 micron, nor does it cease consuming energy at that point. Comminution is in fact recognized as an important method of producing colloids., Mechanical comminution methods were used by von Weimarn6 to produce colloidal dispersions of a variety of solids, including the minerals chalcocite, galena, hematite, stibnite. Utzino7 gives average particle sizes ranging from 0.02 to 0.09 micron for colloids produced by mechanical comminution of several crystalline solids. Andreasen and Berg' have ground

Jan 1, 1941

By T. B. Massalski, Horace Pops

Martensitic transformations were observed by optical metallography and electrical-resistivity measurements during cooling at cryogenic temperatures of the bcc pr-phase Au-Zn alloys. The com-position dependence of the MS, MF, AS , and AF temperatures have been determined. It is concluded that the martensitic platelets which grow mainly in the lengthwise direction and which are associated with a very small temperature hysteresis are "thermoelastic" martensite. In some cases the observed structure seems to have no definite crys-tallographic habit or consists of a mixture of- plates and broad transformed areas. THE majority of the bcc /3-phase alloys in systems of copper, silver, and gold with zinc and cadmium are unstable at low temperatures and undergo a transformation upon further cooling into another structure. A large number of such transformations are martensitic. The composition dependence of the Ms temperatures has been determined and reported for CU-~n,' Ag-Cd,' and AU-C~~ alloys. The 50 at. pct ordered Au-Zn p' alloy has been reported by Jan and pearson4 to transform martensitically at 58°K in connection with their study of the de Haas-van Alphen effect The p' phase in the Au-Zn system has the ordered CsC1-type structure. The phase field is shown in Fig. 1: it has the typical V shape which is characteristic of all copper-, silver-, and gold-based binary /3-phase alloys. There appears to be no a priori reason why the transformation should be limited to the equiatomic composition and the availability of a cryogenic stage for optical metallography5 has permitted studies down to the liquid-helium temperature of a series of alloys in this system. EXPERIMENTAL PROCEDURE Predetermined weights of 99.999 pct pure gold and zinc were melted and cast under a partial atmosphere of helium in sealed quartz capsules. Thorough mixing of the molten metals was achieved by vigorous shaking, followed by a rapid quench into a brine solution. All ingots were homogenized at 640°C for 4 days. The loss in weight was usually less than 0.04 wt pct and was assumed to be due to

Jan 1, 1965

By N. P. Pinto

Compacting below the recrystallization temperature was studied. Ideal density was attained at 550° to 600°C using 25 tsi. Compacts have strength and hardness higher than cold worked beryllium. The recrystallization temperature of this highly stressed metal is that of cast, cold worked beryllium and appears independent of pressing temperature. THE process metallurgy of beryllium is beset by many difficulties that hinder the production of sound beryllium shapes of controlled properties. Most of these obstacles are traceable directly to the low density, low ductility, and high affinity for oxygen of the metal. Castings are susceptible to cracking and porosity, and controlled grain size is not easily attained, yet is critical to further working. Any process must carefully avoid oxygen pickup. Conventional metallurgical processes, including melting, casting, forging, rolling, and extruding have been treated previously,'" as have the conventional powder metallurgical methods.' More recently, a method has been advanced for producing powder compacts of high density by hot pressing at 1000" to 1100°C, using pressures of 0.25 to 0.5 tons per sq in. (tsi).3 Here, Seybolt and coworkers attained theoretical density of 1.85 grams per cc using pres-sure-temperature combinations of 500 psi-1100°C, 750 psi-1075"C, and higher. The warm pressing of beryllium is a practical method for producing bars of controlled properties and appears to have certain advantages, particularly when high strength and hardness are required. Other investigators have studied the hot pressing of various pure metals, such as copper,"-" gold," iron,10-11 and aluminum." Their results indicate that ideal densities may be attained by compacting at temperatures less than 50 pct of the absolute melt-

Jan 1, 1955

By William Brewster

DATING back some five years ago, various foundries made inquiries as to the probable total carbon content in a given specification and grade of pig iron. Up to that time we had no data, and except for a few occasional determinations of total carbon, no attempt had ever been made to set up routine determinations of total carbon. In fact, at that time, a cast analysis was considered sufficient, without examining at further length into possible variations of analysis between ladles of the same cast. In view of the various inquiries as to total carbon, we sampled all piles of all grades of pig iron, making complete analyses. Finding some variation in carbon content, we secured more samples and plotted the carbon content with respect to silicon in each grade of iron except for the higher phosphorus foundry iron, where it was necessary to divide the group into twenty-point phosphorus ranges. This is easily understood, owing to the falling off of carbon content with the increase in phosphorus con-tent, silicon in each case being the same. In addition, these curves clearly demonstrate the lowering of the carbon content as the silicon is increased. In order to insure accuracy and reliable determinations the following method of sampling and analysis was employed: Two pigs selected from each end of the car, each car containing iron from one 50-ton ladle, are drilled with a 5/16-in. drill all the way through from top to bottom in the center of one section of the pig. The drillings are collected and transferred to an 80-mesh sieve; the portion passing through and the portion retained are placed in separate envelopes and labeled accordingly. The amount of sample in each envelope is weighed to obtain the proportionate amount of coarse and fine drillings, then a factor weight of sample (1.3636 grams) made up of proportionate

Jan 1, 1936

By E. S. Tankins, G. R. Belton

A simple solution model, based upon the formation of molecular species, is developed for strongly electronegative dilute solutes in liquid binary-metallic solvents. Two approximations are considered for the relative concentrations of the species: the random and the quasi-chemical. Equations are presented for the partial molar free energy, enthalpy, and entropy of mixing of the solute. An experimental study has been made of equilibrium in the reaction H2 6) +0 (dissolved) = H2O(g))for the liquid Cu-Co alloys. The standard free energy of solution of oxygen is presented as a function of composition for the alloys at 1550°C and as a function of temperature for five of the alloys. The experimental results for these alloys and also for Cu-Ni alloys are shown to be in reasonable agreernent with the theory in the random approximation. A knowledge of the thermodynamic behavior of dilute solutes in liquid metals and alloys is of importance in understanding and designing refining and alloy-making processes. Accordingly, several attempts have been made to derive suitable solution models to forecast the effect of a third component on the activity coefficient of such a solute in a metal. Alcock and Richardson' reviewed the literature prior to 1958 and also showed that a regular solution model gave a reasonable description in the case of metallic solutes but failed to account for the behavior of the more electronegative solutes sulfur and oxygen. These same authors2 later modified their model by using the quasi-chemical approximation3 to calculate the average composition of the first coordination shell surrounding each solute atom. This modified model was shown to lead to a better qualitative description of the behavior of the electronegative solutes; however, quantitative agreement with experimental data for oxygen in alloys could only be achieved by assuming a very small coordination number. The authors concluded that the major source of error in the model was the assumption that pairwise interaction energies were independent of composition. Substitutional and interstitial random solution models by Wada and saito4 are essentially similar to the first model except that the required interchange energies were derived from the modified solubility parameter equation of Mott, instead of from experimental binary data. Most recently Hoch5 has presented a statistical model for interstitial solutions and has applied the model to the Fe-C-O system. However, as the various interaction energies needed in the model had to be derived from the ternary data, the model does not promise well as a means of forecasting ternary behavior. Each of the above models carries the assumption that the strongly electronegative solutes have the same configurational environment as metallic solutes; i.e., the solute can be treated as a substitutional or interstitial atom in a quasi-crystalline lattice and is surrounded by a normal coordination shell of solvent atoms. There are, however, a number of facts which suggest that this is unlikely. First, the heats of solution are large, being more typical of molecule formation rather than alloying. For example, the heats of solution of monatomic oxygen and sulfur in liquid iron are -90 kea16,8 and -74 kea1,7, 8 respectively. These are to be compared with maximum heats of solution of metallic solutes in liquid iron of about -13 keal (silicon is an exception with -28.5 kea17). The large depression of the surface tension of liquid iron by trace amounts of the electronegative solutes oxygen, sulfur, and selenium9 suggests, by analogy with aqueous systems, the possible existence of polar molecules in the liquid. The effect of these solutes is at least three orders of magnitude greater than normal metal solutes.10 As has been pointed out by Richardson,11 the electron affinities and ionization potentials of oxygen and sulfur are such that it is likely that they exist in metallic solution as negatively charged ions. If this is so, and it is assumed that electrostatic forces play an important role in determining the configuration, it is unlikely that the stable configuration will be that of an isolated ion surrounded by a symmetrical coordination shell of solvent ions. It is more likely that the energy of the system would be lowered by the formation of solute-solvent screened dipoles. The above arguments suggest the formation of "molecular species" between solute and solvent atoms. The idea of the existence of molecular species in such solutions is not new, however', for Marshall and chipman12 have explained in a semi-quantitative manner the C-O equilibrium in liquid iron by postulating the species CO. Chen and Chip-man13 interpreted their measurements on the Cr-O equilibrium in iron in terms of the species CrO. Zapffe and sims14 have also postulated the existence of such species in liquid-iron alloys.

Jan 1, 1965

By James E. York

THE honor so fairly earned and so incompletely and tardily paid to Henry Cort, the inventor of the puddling-furnace and the, rolling-mill, has been fully set forth by Mr. Charles H. Morgan,1 and needs no further emphasis here. In view of the importance of the rolling-mill in the treatment of iron and steel, the paucity of information concerning it is surprising. With the exception of a hook, written about 35 years ago, by Peter Bitter von Tunner, an Honorary Member of this Institute, and of desultory articles on simple sections, which have appeared in technical journals, I know of no pub¬lication attempting to treat this subject, although volumes have been written on the scientific theory and technical manipulations involved in other branches of the iron- and steel-industry. This strange anomaly may be due to the fact that roll-turning cannot be called a scientific business. It does not ordinarily come within the range of an educated engineer; yet it cannot be performed by an ordinary mechanic. It demands some of the qualifications of an engineer, in designing, and those of a mechanic, in execution. The men who have followed this trade have controlled the training of their successors. In many cases the technical knowledge required bas been handed down from father to son, and there has been a motive of private interest to prevent its public dissemination. Moreover, the statement of the various principles involved in the process would require, besides manual experience, a degree of scientific knowledge which roll-turners do not usually possess; and, finally, any book on the subject, in order to possess real, practical value, would have to be so fully illustrated as to make it very costly to publish. Regarding my own experience, I may say that I served a six-

May 1, 1906

By H. H. Kellogg

Available high-fernperatzwe equilibrium measurements and other thermochernical data have been critically reciewed for sulfation reactions of the type: Recommended values for log K and ?Fo as junctions of temperature are given for thirty-six suck reactions involving twenty-six different metals. Methods of calculation and choice between conflict-ing data are discussed. SELECTIVE sulfation now enjoys a considerable renaissance as a metallurgical unit process due, in large part, to the available of the fluid-bed re- actor—a device capable of the close control of temperature and gas composition necessary for a successful sulfation process. An additional need, however, if sulfation chemistry is to be approached in a scientific manner, is a reliable body of data on the equilibrium and kinetics of sulfation reactions in simple and complex systems. This paper offers a critical review and compilation of equilibrium data on pure sulfates (simple systems). The last such review, by K. K. Kelley in 1935:30 has proven itself most useful, but the existence of many new data makes necessary a re-evaluation of the available information. METHODS OF CALCULATION For a simple sulfation reaction such as MS04(c) = MO(c) + SO3 [1] there are two approaches one may take toward establishing the value of ?Fo or K as a function of

Jan 1, 1964

By R. S. Handy

The No. 2 unit of the West Mill of the Bunker Hill & Sullivan Mining & Concentrating Co., which went into commission Apr. 17, 1912, is structurally a twin of the No. 1 unit, which was started Nov. 9, 1909. Up to the point where the ore enters the concentrating-de-partment, it follows precisely the process described by G. Cae-tani in his article entitled, Milling of Lead-Silver Ores,' under the heading, Preparation of the Mill-Ore. The process from this point forward, in the No. 2 section, is outlined on the accompanying flow-sheet. In describing it I shall attempt to analyze the products of each separate process. The constancy of the tonnage and the uniformity of the quality of the feed render this practicable. No. 1.—550 tons of feed, all having passed 30 mm., is washed into two 15-mm. trommels, 4 ft, in diameter, 60 in. long, 17 rev. per min., 1 in. slope, 3/8-in. gauge steel.

Jan 1, 1913

By Robert E. Green, Kenneth Reifsnider

A microscopic X-ray diffraction technique was employed for the simultaneous study of the behavior of several families of lattice planes, whose local orientatiotz changes are manufestations of internal distortions resulting from specimen deformation. Photographs taken using aluminum were single crystals 1/64 in. In diam are presented which illustrate the appearance of various types of deformation- or growth- induced structural variations. Slip and lattice bending were detected in tensile tests for strains as small as 0.1 pct. Evidence of deformation bands, lineage structure, and void formation wns also shown. AmONG the most important methods of studying internal stresses in metals is the utilization of various X-ray techniques. The general subject of X-ray metallography has been treated in a most excellent manner by Taylor,1 and the use of X-rays for the direct observation of imperfections in crystals has recently been reviewed in an article by Newkirk2 and in the book edited by Newkirk and Wernick.3 Since the inception of metallographic X-ray analysis, there have been numerous technological developments and refinements, each with its particular advantages and disadvantages and, acrording to these, its particular applications. X-ray diffraction techniques can be divided into two general categories, that of X-ray diffraction microscopy and that of X-ray diffraction macroscopy. In the former are included such methods as those of Berg-Barrett, Lang, and Schultz2,3 which are concerned with microscopic imperfections such as dislocations. The second category includes all work concerned with the study of the condition of a crystal lattice structure as indicated by the marroscopic detail in its diffraction patterns. An example of this is the study of the diffraction manifestations of inhomogeneous plastic deformation as manifested by formation of deformation bands and inhomogeneous lattice rotations. The method used in the present investigation was an X-ray diffraction macroscopy technique. The geometry and analytical aspects of the method were similar to those of Julien and Cullity.4,5 The source was collimated with a single slit in a manner simi- lar to the "parallel beam'' method of Barth and Hosemann6 except that a continuous spectrum of radiation was employed. The apparatus produced large-beam transmission Laue patterns of thin cylindrical aluminum-wire crystals, which were deformed either in tension or torsion. Although the conventional X-ray target and interposed slit were not capable of the high resolution obtainable with a fine-focus X-ray source as employed in a microfocus apparatus, resolution was a secondary consideration in our technique, and was sacrificed to obtain sufficient intensity along a sizable length of the specimen. By using a grid indexing technique similar to that of Barth,7 we were able to study several diffraction lines from various planes simultaneously. The results of these tests give additional information with regard to the inhomogeneous deformation of single crystals, and the indexing procedure used provides a correlation between portions of the test specimen and portions of a diffracted beam. EXPERIMENTAL TECHNIQUE The experimental arrangement used is shown schematically in Fig. 1. A source of continuous X radiation from a vertically mounted Machlett X-ray tube possessing a copper target and operated at 20 kv and 10 ma was passed down a horizontal lead tube 80 cm long which terminated in an adjustable vertical brass slit. The slit opening was adjusted to correspond with the diameter of the test specimen. In front of the brass slit it was possible to place a screen wire mesh, one horizontal strand of which was a lead wire which served as a fiduciary mark, the screen itself serving as an indexing system as will be described later. Behind the screen was the test specimen which consisted of an aluminum single crystal wire 1/64 in. in diameter and 3 in. long. These 3-in.-long crystals were cut from

Jan 1, 1965

By P. A. Tucker, C. R. Hudgens, D. E. Etter, D. L. Roesch, D. B. Martin

The equilibrium phase diagram of the Pu-Cd system is presented based on data obtained by differential thermal analysis, metallography, and electron-microprobe X-ray analysis. Liquidus temperatures range from 320° to 934°C. The system contains one congruently melting compound, PuCd, (945°C), and three incongruently melting compounds, PuCd, (800°C), PuCd, (730°C), and PuCd11 (410°C). A liquid-miscibility gap extends from 2 to 60 at. pet Cd with the monotectic reaction isotherm at 910°C. INTEREST in the potential use of plutonium alloys as reactor-fuel materials has prompted investigation of the phase equilibria in plutonium binary systems. A cursory investigation of the phase equilibria in the Pu-Cd binary system was conducted by differential thermal analysis (DTA), metallography, and electron-microprobe X-ray analysis (EMX). Extensive solid solubility of cadmium in both e and 6 plutonium was predicted1 based on atomic radii and electronegativities. Liquid immiscibility between these two elements was also predicted based on Mott's extension of Hildebrand's method. In the only previous investigation of the Pu-Cd system,2 two intermetallic compounds, PuCd11 (incon-gruent melting point 406°C) and PuCd8, were identified. EXPERIMENTAL The plutonium metal used in this work had a total impurity content of 500 ppm; the major impurities were: carbon (215 pprn), silicon (75 ppm), iron (60 ppm), nickel (40 ppm), and aluminum (25 ppm). The cadmium was reagent grade with a purity of 99.99 pet. The DTA technique for the study of plutonium alloys was previously described in detail.3 The alloys to be studied were prepared in tantalum DTA specimen capsules which were sealed by inert-gas welding. The alloys were homogenized in the liquid state in these sealed capsules which prevented the loss of cadmium by vaporization. Only the thermal arrests in the DTA heating curves were used to define the transformation temperatures of the system since supercooling affected many of the results during cooling. After the alloys were analyzed by DTA, the same alloys were used for the metallographic studies. Metallographic examinations were conducted in the manner described for plutonium alloys., No reaction was detected between the alloys and the tantalum capsules. Alloys for EMX analysis were placed in metallographic mounts together with specimens of unalloyed plutonium and cadmium which served as standards. The samples were highly polished but unetched. No protective coatings were applied to the surfaces of these radioactive specimens. Such coatings are detrimental to the excitation conditions and have been found to be unnecessary for the control of radioactive contamination. RESULTS The results of the DTA studies are presented in Table I. The phase diagram, constructed from these data plus the metallographic and EMX results, is presented in Fig. 1. The congruently melting compound, PuCd2, was identified by the occurrence of a maximum melting point (945°C) at 33.3 at. pet Pu-66.7 at. pet Cd and by the presence of a single phase in this composition.

Jan 1, 1965

By F. E. Bachman

Although it has been apparent to me for a long time that too great weight was currently given to the silicon-contents of foundry-iron, and that the theory of the control by silicon of the carbon-contents of cast-iron is unsound, or that, at best, the influence of silicon is too small to be of much practical value as a guide in foundry-work, it never seemed to me desirable to enter the lists against either the " silicon-fad " or the theory, for the reason that I had neither the time nor the facilities to prove my position, nor any better theory to offer. But since Mr. Summers has taken the step, it seems but right that I should give such facts as are at hand in support of his contention. At the same time I do not think these are enough to prove the case if the contrary proposition were not itself, as it seems to me, based on insufficient evidence. Both Keep's and Turner's conclusions seem to be drawn from irons carrying less than the normal amount of carbon; Turner's " base " being, moreover, a steel rather than a pig-iron, and both the white base and the ferro-silicon of Keep being so low in carbon that compounds of them would not give a material approaching the carbon-contents of a normal casting, and having, therefore, little value as showing the effects of silicon on foundry-irons, even if his samples were treated under the same conditions as those to which pig-metal is subjected in making castings.

Jan 1, 1899

By H. W. Rogers

THE first steam shovels used in this country were built by the Otis Company, of Boston, about 50 years ago, but as they were of very crude construction and rather unsuccessful only a few were built. For possibly 10 years prior to 1884 successful steam shovels were made and used on certain classes of work, but it was not until that time that they were manufactured in quantities and began to play an important part in all classes of excavation. From that time up to the present day there have been gradual but continuous improvements on the original shovel, not only in the mechanical construction, but also in the design of boilers and engines which are best adapted to this class of service. In proposing a change from steam to electric operation we have to deal with a steam equipment which has not only proved its worth but has probably reached its highest stage of development and efficiency. That the electric shovel is a possibility cannot be denied, as at present from 12 to 18 shovels are in operation in this country. These shovels may be divided into three classes: the friction electric, which is operated by a single constant-speed motor with friction clutches; the three or four motor direct-current equipment, and the three or four motor alternating-current equipment. It is the second and third classes that I wish to deal with, as the first class does not compare favorably with the steam shovel so far as speed is concerned, although it may be operated as cheaply. There is probably no other class of machinery that presents a duty cycle as severe as that of the shovel, which is very short, varying from 7 to 12 sec. on the hoist, from 7 to 12 sec. on the thrust, and from 10 to 18 sec. on the swing, making a complete cycle in from 17 to 30 sec., and the motor to meet these requirements must have a sufficiently low armature inertia to permit of rapid acceleration and quick reversals under small power. It should also be a motor of rugged design, as it must be subjected to severe overloads and shocks and frequent reversals. This is especially true of the hoist motors and, to a lesser degree, of the swing motor; the thrust motor being practically stalled during the digging operation, although it may revolve or overhaul, according to conditions, and is operated at full speed only after the hoisting operation is completed.

Jan 2, 1914

By S. A. Spachner

An analysis of the powder patterns of the omega transition phase in three binary titanium alloys containing 8 pct Cr, 13 pet Mo, and 15 pet V, respectively, showed that all could be indexed on an orthorhombic unit cell. The unit-cell dimensions were all quite similar. There is evidence for the occurrence of more than one transition phase in Ti-Cr and Ti-V alloys. FOLLOWING the discovery of a new brittle phase in certain titanium-chromium alloys by Frost, Parris, Hirsch, Doig, and Schwartz,' named ? by these investigators, much interest has developed concerning the identification of alloy systems in which this phase exists, kinetics of the transformation in such systems, and the crystal structure of the ? phases appearing. Omega has been found in alloys of titanium-manganese, titanium-molybdenum, titanium-iron,' and titanium-vanadium.' In the present work, a study was made of the powder patterns of the ? phase occurring in alloys of Ti-8Cr, Ti-13Mo and Ti-15V in an effort to obtain a basis of comparison for ? phases appearing in these different alloys. Comparison of Alloys for ?-Phases Two hundred mesh powders of Ti-8Cr, Ti-13Mo and Ti-15V were prepared. A portion of powder sufficient for three x-ray powder specimens was placed in a Vycor tube, evacuated to less than 0.1 µ pressure, filled with argon, and sealed. The tubes were then heated to 900°C, held at this temperature for 30 min, and water-quenched. Following this transformation to the ß phase, the specimens were quenched in lead or solder pots, held at the desired temperature for varying lengths of time and water-quenched. The heat-treatments used and the phases identified are listed in Table I. The intermediate water quench was used in lieu of direct downquenching from 900°C to the bath temperature desired to circumvent the possibility of transformation of the powder specimen from ß to (ß + a) while it was being moved from the homog-enization furnace to the lead bath. To check the possibility that upquenching to the bath temperature might bring into play a different mechanism than downquenching to this temperature, resistivity measurements were compared on Ti-8Cr rod specimens which were transformed isothermally at 400°C by downquenching from the solution-treatment temperature and those which were transformed at 400" C by upquenching ß specimens from room temperature. The results are shown in Fig. 1. No difference in transformation mechanism was noted. It soon became apparent that sufficiently detailed Debye-Scherrer photograms of the ? phase in the alloys which were to be used could not be obtained by the use of copper radiation. Although satisfactory photograms of ß and ß + a phases were obtained with this radiation, the ? phase appeared to exhibit mild fluorescence, making interplanar spacing computation virtually impossible. Molybdenum radiation appeared to offer promise in cutting down this fluorescent effect, the mass absorption of titanium for molybdenum radiation being 23.7 in contrast to 204 for copper radiation. The reduction in the accuracy in determining the location of the photo-gram lines caused by the shorter wave length of molybdenum characteristic radiation did not appear to be a significant factor. Utilizing a camera of 57.3 mm radius, best results were obtained for exposure times ranging between 30 and 40 hr. Tube potential

Jan 1, 1959

By J. Walter Snavely

PRESENT-DAY processing in many industries, calcining, sintering, briquetting, beneficiation and nodulizing, increasingly calls for the handling of large volumes of hot bulk materials. Various types of conveyors have been employed. This discussion will cover the factors governing their selection. For temperature ranges up to 400°F, or approximately 200°C, a wide range of conveyors is available. Special constructions of rubber conveyor belts. steel conveyor belts, vibrating and shaker conveyors, apron conveyors, and drag chain conveyors, all are used successfully. As temperatures go well above 400°F, however, choice of conveyors is narrowly limited. This paper will consider the problem of handling bulk materials only where the temperatures exceed 400°F.

Jan 5, 1953

By T. E. Leontis

ONLY a limited amount of information has been published on the effect of thorium as an alloying ingredient in magnesium. McDonald13'2 showed that the addition of thorium in amounts up to 3 pct increases significantly both the ductility and the strength of rolled magnesium sheet. A recent publication by Sauerwald" indicates that thorium contributes strength and creep resistance at elevated temperatures to magnesium in both the cast and wrought states. The observations of Sauerwald are confirmed in this paper, which presents the results of a systematic study of the effects of compositional variation on the tensile properties, creep resistance, conductivity, density, and metallography of Mg-Th alloys containing up to 50 pct Th both in the sand-cast and in the extruded states. The effect of the addition of cerium to Mg-Th alloys is also reported. Experimental Methods The alloys studied in this investigation were pre.pared in small laboratory melts according to the melting practice described by Nelson4 as the crucible method. Electrolytic magnesium was used as the starting material to which the thorium* was introduced in metallic form. It was observed that the behavior of thorium in molten magnesium with respect to reaction with protective fluxes is similar to that of rare-earth metals. In order to obtain the highest possible alloying efficiency, it is necessary to use non-MgC1, fluxes and to apply all the precautions described by Marande6 for melting, alloying, and casting magnesium-rare-earth alloys. .Under these conditions it is possible to obtain an alloying efficiency in the range of 85 to 95 pct. The Mg-Th-Ce alloys were made with cerium of the highest purity available, not with the commercial product "misch-metal" which contains approximately 50 pct Ce. The total rare-earth content of this material was 97.1 pct, of which 0.3 pct was rare-earth metals other than cerium; the major impurities comprising the balance were iron and magnesium. The thorium and cerium contents of each alloy were determined chemically. Test bars 6% in. long with a 2% in. long reduced section of % in. diam were cast in sand molds using a four-baf pattern. In most cases, a 3 in. diam extrusion billet 10 in. long was cast in a steel mold from the same melt used for making the sand-cast test bars. For the higher thorium alloys, it was necessary to remelt the foundry scrap from the test bars in order to make the extrusion billets. The billets were scalped to a diameter of 2 15/16 in. and the ends faced to a length of 9% in. as limited by the size of the extrusion container. The alloys were extruded into % in. diam rod on a 500-ton direct-extrusion press. The details of the extrusion process are as follows: Billet preheat 925°F (2 to 16 hr) Container temperature 900 °F Die temperature 900°F Extrusion speed 10 ft per min Reduction ratio 36:1 Percent reduction 97.3 Alloys containing up to 10.2 pct Th were preheated at 925°F for 2 hr; all alloys with higher thorium contents were preheated for 16 hr. In order to establish the effect of extrusion temperature, billets of

Jan 1, 1953

By James C. M. Li

The thermodynamics of the set of functions including the activation enthalpy. the activation free energy, and the activation entropy for the motion of dislocations at low temperatures is formulated without a specific model or a mechanism. The behniiior near absolute zero of all these functions and of other relevant quantities related to dislocation mobility Is examined in the light of the third law of thermodynamics. The velocity measurements of Stein and Low for edge dislocations in Si-Fe are used .for illustrotion. In the plastic deformation of crystalline materials, a fundamental assumption, which is supported by direct measurements using etch-pit techniques,'-4 is that the average velocity of a certain mobile dislocation is a single-valued function of temperature and the effective shear stress exerted on the mobile dislocation: Sometimes under certain assumptions, even without direct dislocation-velocity measurements, an activation volume can be obtained from a change in strain rate in a simple tension test. Similarly an ac tivation enthalpy can be obtained by changing the temperature in a creep test. However, the assumptions involved should be studied carefully before using the results of these tests. Consider, for example, a tensile specimen at some stage of deformation with a distribution of mobile dislocations. Let the total length of dislocations of type i be pi per unit volume. The Burgers vector of these dislocations is hi which makes an angle ?i with the tensile axis. With respect to the same tensile axis, let the normal of the slip plane of these dislocations

Jan 1, 1965

By David Kramer, Cecil G. Rhodes

Critical transport currents were measured as a function of perpendicular external magnetic field in Ti-22 at. pct Nb wire samples. These samples were heat-treated to yield w Phase precipitates at denslties ranging from 10 to 10 17cm-3. The Precipitates are ellipsoids of revolution with major axes of 50 to 1300A. Flux-Pinning by w precipitates is responsible for the high critical transport currents that were ob- ThE ability of a type II superconductor to sustain a zero-resistance transport current (Jc) in an external magnetic field (H) is due to the presence of micro-structural features which can impede the motion of magnetic flux penetrating the superconductor under the influence of a Lorentz force. Such features are referred to as pinning sites. The pinning strength is tained. A sample cooled from 800°C and annealed 1 hr at 450°C carried a critical tramport current of 10 amp per sq cm at 30 kG. Variations in the current-carrying ability of this alloy are due to changes in its pinning strength which is a function of precipitate density and composition and of the composition of the matrix. the reaction of the bulk superconductor to the Lorentz force and depends on the efficiency of the individual pinning sites and on their volume density. The super -current density increases with pinning strength, other things being equal. The above concepts are discussed in detail in a comprehensive review by Livingston and Schadler.' In Ti-Nb alloys, as in other binary titanium alloys, the metastable hexagonal w phase usually forms below the p/a + p phase boundary near the titanium side of the phase diagram. Stiegler et a1.' have summarized much of what is known about w phase in titanium and zirconium binary alloys. The present work deals with

Jan 1, 1968