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By H. L. Teicliman, E. M. Sipprelle

ENACTMENT of Public Law 290 by the 78th Congress authorized the U. S. Department of the Interior, Bureau of Mines, to conduct an experimental program to develop the technology for obtaining oil from oil shale. In adopting and later extending this legislation, the Congress recognized the impending necessity of supplementing ground petroleum reserves with synthetic fuels. Under the provisions of this legislation, the Bureau of Mines, among other things, was charged with the responsibility of developing mining techniques, methods, and equipment for mining the oil shales of the Green River formation of Colorado, Utah, and Wyoming.

Jan 1, 1950

By R. J. Charles

SEARCH for a consistent theory to explain the relationship between energy input and size reduction in a comminution process has accumulated, over the years, an enormous amount of plant and laboratory data. Although some correlation of these data has been possible for purposes of engineering design and for the advancement of research in fracture, there is still great need of a means of predicting behaviour of a solid when it is reduced in size by mechanical forces. The best known hypotheses proposed to describe the energy-size reduction relationships in crushing and grinding stem from a common origin. The present article analyzes problems of comminution in the light of the precepts of this origin. Its object is to reconcile points of difference between these well known hypotheses and to present relationships more widely applicable to comminution studies. Theoretical Considerations: Most existing relationships between energy and size reduction of a brittle solid stem from a single, simple, empirical proposition.&apos; Although this proposition can be demonstrated by observation and experiment, no theoretical derivation is yet possible. Mathematically, the proposition may be stated as follows: dE = -Cdx/xn [1] where dE = infinitesimal energy change, C = a constant, dx = infinitesimal size change, x = object size, and n = a constant. Eq. 1 states that the energy required to make a small change in the size of an object is proportional to the size change and inversely proportional to the object size to some power n. No stipulations are placed on the exponent n in either magnitude or sign. In 1867 Rittinger2 postulated that the energy required for size reduction of a solid would be proportional to the new surface area created during the size reduction. As far as can be determined there is as yet no physical basis for Rittinger&apos;s hypothesis. Rittinger&apos;s hypothesis can be stated mathematically as follows: E, = K(oa-a-0 . [2] Er = energy input per unit volume, K = a constant, <ti = initial specific surface, and o2 = final specific surface. In the size reduction of particles of size x, to particles of another smaller size, x2, Eq. 2 becomes the well known relation: ET = K&apos; {l/x2-l/xx) [3] where K&apos; is a constant. Eq. 3 may be arrived at from the proposition given in Eq. 1 by integrating and by assigning a value of 2 to the exponent n. J dE = J - C dx/x2 E = Kt (1x - 1x) where K&apos; = C. In 1885 Kick3 proposed the theory that equivalent amounts of energy should result in equivalent geometrical changes in the sizes of the pieces of a solid. For example, if one unit of energy reduced a number of equal-sized particles to particles of one half the size, then the same amount of energy applied to the particles resulting from the first test should result again in a size reduction of one half or a final size one quarter the original size. The Kick concept may be expressed as follows: Ek = K" log x1/x2 [41 K" = a constant and E, = energy per unit volume. The expression for Kick&apos;s law may be arrived at by again integrating Eq. 1 and in this case assigning a value of 1 to the exponent n. dE= J - C dx/x Eh = - C In {x/x2) = K" log (x,/x,) where K" = 2.3 C. Application of Kick&apos;s and Rittinger&apos;s laws to comminution has met with varied success. Gross and Zimmerley4 and Piret5 have shown that Rittinger&apos;s equation applies under certain conditions of experimentation. Walker and Shaw6 express the belief that in metal turning and shaping and in grinding of both metals and minerals the production of very fine particles (less than lP) follows Kick&apos;s hypothesis, whereas Rittinger&apos;s concept is valid for the size reduction of coarse particles. For the practical case of crushing and grinding, however, neither of the above hypotheses has received general acceptance. Bond&apos; has lately proposed that since neither Kick&apos;s nor Rittinger&apos;s hypotheses seem correct for plant design work, an energy-size reduction relationship somewhere between the two would be more applicable. The fundamental statement of Bond&apos;s work

Jan 1, 1958

By R. D. Pehlke, P. D. Goodell, R. W. Dunlap

The rate of dissolution of steel bars in molten pig iron has been measured experimentally in the temperature range 2300° to 2650° F. The rate of solution is shown to be a .function of bath composition, temperature, and stirring. A kinetic model based on carbon diffusion in the liquid phase has been derived to fit the experimental results. THE rate of scrap melting has long been an important variable in steelmaking operations. With the advent of the oxygen steelmaking process and the accompanying shorter heat times, the rate of scrap melting has now become one of the rate-limiting factors in steel production. As observed in commercial practice, the solution rate is influenced by the compositions of liquid and solid, the temperature, agitation, and time. However, no definitive work has been done on the Fe-C system, and there is very little information in the literature regarding the relative effects of these variables in steelmaking systems. A number of questions have been raised in regard to scrap utilization in basic oxygen steelmaking operations. Consideration has been given to the optimum size and shape of scrap, and to the use of preheated scrap as a means for decreasing the pig-iron requirement in oxygen blowing. The determination of an optimum scrap practice for a specific installation depends to a large extent upon the economics of the scrap market and also upon the behavior of scrap in the vessel. The present research was undertaken as a preliminary study in evaluating the behavior of steel in a pig-iron bath under various conditions of temperature, composition, and agitation, as might be encountered in oxygen converter operations or in any steelmaking operation where scrap behavior is an important process variable. Related studies have been carried out on non-ferrous systems. The solution rate of solid aluminum in a molten A1-Si alloy has been studied.&apos; Furthermore, the increasing use of liquid metals has created considerable interest in studies related to dissolution of a solid in a liquid, or mass transfer taking place between a solid interface and a liquid metallic phase.2-10 In an effort to clarify the relative importance of factors influencing the dissolution of scrap in Fe-C alloys, this paper presents the results of a study of the rate of dissolution of a low-carbon steel cylinder in a molten Fe-C bath at various bath compositions, temperatures, and conditions of agitation. An attempt has been made to determine the mechanism of solution, and a model has been derived to fit the experimental results. The rate of heat transfer between the molten pig-iron bath and the solid-steel cylinder has also been studied. EXPERIMENTAL PROCEDURE A molten bath of pig iron (nominal composition 4.2 pct C, 0.5 pct Mn, 0.8 pct Si)* was held in a 200- *In view of the fact that the composition of the pig-iron bath was slowly changing with time because of steel dissolution and reaction with the surrounding atmosphere, intermittent samples of the liquid bath were taken throughout each experiment, Table 1. lb induction melting unit. The internal diameter of the furnace was 8-1/2 in. and the bath depth approximately 14 in. Cold-finished 1020 steel cylinders of 1/2-, 3/4-, 1-, 1-1/2-, and 2-in. diameters were cut into 1 -ft lengths for use as test specimens. One end of each bar was machined to fit a hand-driven, mechanical stirring device which rested on top of the furnace. This fixture permitted 7 to 8 in. of the bar to be immersed in the melt. The steel cylinders were cleaned to free the surface of grease and oxide. The rods, at ambient temperature, were immersed into the molten pig-iron bath. The melt temperatures studied in this investigation were 2300°, 2500°, and 2650°F. Different agitation conditions were achieved by operating with a) the power to the furnace, giving induction stirring; b) induction stirring plus mechanical stirring, using hand rotation with a chain and sprocket assembly at approximately 200 rpm; c) mechanical stirring alone with the power off; and d) the power off and no mechanical stirring resulting in minimum agitation, i.e., only that caused by natural convection currents in the bath. The samples were immersed in the melt for prescribed times ranging from 30 sec up to 6 min. Immersion times were measured with a stopwatch and temperature control of the melt was achieved by power adjustment following temperature measurement with an optical pyrometer. The measurements with the calibrated pyrometer were checked out to within less than 10°F with simultaneous thermocouple measurements. Following immersion, the bars were water-quenched and the diameters were measured with a micrometer at several positions on the reduced area, and by volumetric displacement. The dissolution rates calculated from the

Jan 1, 1965

By R. W. Mancantelli, J. R. Woodward

IN 1947 a large low grade deposit of uranium was located in the northwest corner of Saskatchewan, in the Beaverlodge property of Eldorado Mining & Refining Ltd. Most of the values occur as thin seams and as coatings on other minerals, and the ore, which is light and friable, is not amenable to the usual gravity methods of concentration. The acid leaching process developed to retreat the company&apos;s Port Radium tailings was also impractical, as the percentage of carbonates is high and the percentage of sulphides relatively low. Construction of the mill building and installation of equipment, both scheduled for 1952, awaited selection of a satisfactory ore dressing process on or before Oct. 1, 1951. An extensive research program on dressing of ores from the Ace mine therefore was undertaken by the Mines Branch in Ottawa, a research team at the University of British Columbia, and an ore dressing group at the company&apos;s Port Hope refinery. Pilot plant operations were conducted at the Ottawa plant of Sherritt Gordon Mines Ltd. under the general direction of C. S. Parsons, consultant on metallurgy and ore dressing for Eldorado. In mid-September, having compared results of the several research programs, Dr. Parsons recommended a process employing a carbonate or basic leach. He reported that, while the chemistry of the process had been proved, engineering of the flowsheet was incomplete, and he suggested that under normal conditions further pilot plant work at the Ace mine might be profitable. However, since this would involve a delay of 12 to 18 months in bringing the property into operation, he recommended that design of the concentrator proceed immediately. Concentrator capacity was determined by two considerations: 1) the amount of ore then available and 2) the expectation that continued improvements would be made in the ore dressing process as a result of the intensive research being carried out by the Mines Branch of the Department of Mines and Technical Surveys. As these improvements could affect both the chemistry and the en-

Jan 1, 1956

By C. F. Frey, P. J. Ahern, J. F. Wallace

THE high affinity of molten titanium for oxygen and nitrogen has resulted in considerable difficulty in developing a satisfactory melting procedure. It has been found necessary to perform melting operations either in a vacuum or inert atmos-phere, and failure to obtain a satisfactory crucible material has necessitated the use of special melting techniques. These techniques have included cold-mold arc-melting utilizing both consumable and nonconsumable electrodes, skull-melting, drip-melting, and levitation melting.&apos; It has been recognized generally that the melting of both titanium sponge and titanium scrap would be expedited by the use of induction-melting procedures but the lack of a crucible capable of containing molten titanium without objectionable contamination thus far has prevented the use of induction-melting procedures. An extensive investigation: which included the common refractory materials was not successful in developing a satisfactory crucible for induction-melting. Some success in induction-melting has been attained with the use of a graphite crucible material, but in all instances sufficient carbon contamination was encountered to cause an appreciable reduction in the optimum mechanical properties of the titanium or titanium alloys. These investigations"" report an increase in the carbon content from approximately 0.3 to 1.0 pct. A serious reduction in the tensile and forming properties has been observed as a result of this carbon contamination. The development of a satisfactory induction-melting procedure for titanium without undue contamination undoubtedly would have considerable economic significance. Such a process would be particularly useful in melting the large quantities of low-cost scrap now available that can only be reprocessed at considerable expense and difficulty by the more elaborate techniques referred to previously. In addition, the process could provide a satisfactory method of melting and alloying of bri-quetted sponge for forging ingots.

Jan 1, 1959

By ROBERT E. HARDWICKE

THE QUESTION of whether the production of oil should be limited to market demand has been constantly discussed during the last two years. Oil men, legislatures and courts have reached highly conflicting conclusions. Opponents of limitation to market demand assert that it is a scheme of the big purchasing companies to fix prices and to create a monopoly. Proponents, on the other hand, declare that such a limitation is necessary to prevent physical waste and that the effect on prices is merely incidental. A brief review of market demand legislation will disclose the confusion existing. The laws of Oklahoma,&apos; prohibiting waste of oil and gas, specifically&apos; authorize limitation to market demand as a method of preventink such waste. These laws and the proration orders based thereon have been upheld by the Supreme Court of Oklahoma, by several three-judge Federal District Courts, and by the Supreme Court of the United States.&apos; Kansas has a similar law3 but no case has been found which discusses its validity. About a year ago the California Legislature passed a comprehensive conservation act, generally known as the Sharkey Bill giving authority to restrict production to an amount representing current requirements for use, taking into consideration oil and products in storage. This may be considered as equivalent to limitation to market demand. The Act was defeated upon referendum vote after a hard fought campaign in which it was charged that the Act would result in destruction of the independent operators.

Jan 1, 1932

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 C. H. Cheng, C. E. Birchenall

The fundamental problem in the thermodynamics of solid solutions is the determinatiorl or calculation of the activities of the components as a function of temperature and composition. Since the theory of metals is not suficiently developed to allow a priori calculation of these quantities, they must be obtained from experiment. C. Wagner1 has reviewed the literature of this subject for the period before 1940. Although several important and extensive studies have been made in the meantime, the number of systems to which any sort of quantitative information can be assigned is vanish-ingly small. These data have become of great potential importance in studies of the structure of solid solutions2 and intermetallic compounds, the nature of the diffusion process,3,4 and perhaps even the mechanism of mechanical deformation.5 For these reasons, it. seems very worthwhile to extend the experimental data in this field. Although there is little use in duplicating Wagner&apos;s review, attention should be directed to the most recently reported investigations. A brief enumeration of the methods of measurement previously employed also should be valuable. The most direct method is the determination of the partial pressure of the components in the vapor phase in equilibrium with the solution. Both equilibrium and kinetic methods have been tried in metal systems, but almost exclusively on liquid phases. Only in the ease of carbon in iron alloys and in the copper-zinc system have extensive measure- ments been made which include solid phases. When one of the components is an element, such as nitrogen or carbon, which forms compounds which are very volatile and stable at normal temperatures and pressures (CH4, Co2, CO NH3), it is frequently possible to equilibrate mixtures containing these (such as CH4-H2, CO2-CO, NH3-H2) independently with the elernents (C, X) and with the metal (Fe, Ni, etc.). Such measurernents have been made for carbon in iron, iron-silicon, and iron-manganese alloys by Smith6 and in iron and iron-nickel alloys by Toensing.7 Differences between carbon activity values at the same temperature and carbon content when carboil is introduced from CH4-H2 rnixtures or CO-CO. mixtures indicate that the effects of hydrogen and oxygen in the system are not negligible, and one can only hope that the true value lies somewhere between these sets of results, probably nearer the CH4-H2 data since hydrogen is less soluble in iron than oxygen. This is essentially an equilibrium method, although flowing gas is employed. A kirletic method has been employed which consists of sweeping an inert gas (generally hydrogen) over the alloy at a series of rates, condensing the metal vapor out,, and analyzing it. The metal content can be extrapolated to zero flow rate (equilibrium). Wejnarth&apos;s8 work on Cd-Mg and Zn-Mg is a good example of this frequently used method. A variant of this consists of equilibrating a known volume of inert gas with the alloy, sweeping it out quickly, and analyzing for metal. In common with the above method, it has the disadvantage that the "inert" gas is generally somewhat soluble in the alloy. Moreover, the former continuously displaces the system from equilihrium and may give low values if solid diffusion is involved. The dew point method applied by Hargreaves9 to the alpha and beta brasses and by Schneider and Stolll0 to A1-Zn avoids the introduction of another component to the system, but is useful only in systems in which one component is much more volatile than the other. The alloy sealed in one end of an evacuated silica tube is heated to the desired temperature. The temperature of the other end is lowered until droplets of the volatile component condense. When the temperature is raised slightly, the droplets will evaporate. By careful adjustment of temperature, the range between evaporation and condensation can be narrowed appreciably. An independent determination of the vapor pressure of the . pure volatile component is necessary to give the partial pressure over the alloy. This is the method employed here to determine the vapor pressures of zinc and cadmium over their silver alloys up to 34 pct in cadmium and 76 pct in zinc. The former involves only the a solid solution, but the latter covers the a, ß, y, and e fields. In recent determinations, Herbenar, Siebert, and Duffenbarkl1 used the

Jan 1, 1950

By J. V. Gluck

In the present paper," as in earlier publications, V1&apos;2"1 the authors present experimentally obtained relations for the free energy of solution of oxygen in various metals as a function of temperature. The relations are linear and given in slope-intercept form. The authors give values for the "probable error" of the slope and intercept, citing Birge&apos;s method17 for obtaining these quantities. Birge discussed these methods as early as the period 1929-32.25726 In Ref. 25 the probable error is defined as "the numerical value which the true error is as likely to exceed as not", i.e., 50 pct probability. Ref. 26 is even more detailed and includes a lengthy discussion of the applicability of the Gaussian distribution to experimental data. However, the use of the "probable error" has come under some question. For example, Ezekiel&apos;~ states that "the use of the probable error tends to make the results appear rather more accurate than the standard error". Moroney28 stated (in 1951) that "the term &apos;probable error&apos; was used in former times to denote 0.67450 (50 pct confidence using the normal distribution)....the term, a poor one, is now very much obsolescent. It has been said that &apos;it is neither an error nor probable&apos; ". Bennett and Franklin in 1954" in discussing statistical confidence levels mentioned that "the customary use of the 5 and 1 pct levels is not completely a matter of chance; these levels probably represent a balance between the desire to be correct and the desire to be specific. Also in most people&apos;s minds the borderline between something that could possibly happen and something that is not likely to happen is somewhere in this region. Certainly 5 or 1 pct confidence limits are to be preferred to limits such as the &apos;probable error&apos; which has only a 50/50 chance of including the correct value." It may readily be seen that the 95 pct confidence level, which is given by 1.960 (assuming large sample size), thus corresponds to approximately three times the "probable error". Indeed, limits of one standard deviation correspond only to about 68 pct probability. Even if we triple the tolerances given by the authors in the equations of their Table 111, the deviations do not become excessive and would not detract from their excellent results. It could then be said with a high degree of confidence (95%) that the precision of the slope and intercept values is about *3-5 percent of their absolute levels rather than the 1-2 percent implied in Table 111. This is then compatible with an earlier suggestion of Gokcen~&apos; of a probable accuracy of 5 pct in dissolved oxygen measurements by the technique employed. Alternatively, the authors could have

Jan 1, 1967

By J. W. Freeman, J. P. Rowe, R. F. Decker

HEAT-to-heat variations in properties of an alloy of constant nominal chemical composition have been a perplexing problem to the metallurgist. These heat-to-heat differences have been especially baffling in high-temperature metallurgy. In order to establish fundamental reasons for these heat-to-heat variations, the National Advisory Committee for Aeronautics has sponsored and financially assisted an extended research program on heat-resistant alloys at the University of Michigan. As part of the program to find the contribution of processing variables, Frey, Freeman, and white&apos; studied effects of heat treating on nickel-base alloys and Ewing and reeman&apos; investigated effects of hot-working practice on N155 alloy. To extend the program to the study of effects of melting practice on high-temperature properties, a 55 Ni-20 Cr-15 Co-4 Mo-3 Ti-3 pct A1 composition was selected for experimentation. The objective of this program was to establish the melting-practice variables which influenced the hot-working characteristics and creep-rupture properties and, at the same time, establish the metallurgical mechanisms for the effects. During the course of the investigation of practices using vacuum melting, it became increasingly evident through chemical analyses supplied by industrial concerns that a major variable was melt reaction with the crucible. This paper is devoted to the results of this phase of the melting-practice study. EXPERIMENTAL PROCEDURES Experimental 10-lb heats were induction melted in the University of Michigan vacuum-melting unit with the melting practices outlined in Table I. Aim analysis for the basic alloy, in wt pct, for all heats was as follows: Cr Co Mo Ti Al 20.0 15.0 4.0 3.1 3.1 Mn Si C Ni 0.12 0.12 0.08-0.15 Bal. Small amounts of boron and zirconium were added to certain heats as listed in Table I. These additions

Jan 1, 1959

By H. F. Bishop, F. A. Brandt, W. S. Pellini

The solidification mechanism of experimental steel ingots (7x7x20 in.) was studied by thermal analysis. It was determined that solidification proceeds in wave-like fashion at rates which are determined by the carbon level, superheat, and mold thickness. The thermal cycles of the mold walls were related to the course of solidification. ESPITE marked advances in the field of solid state transformation, metallurgical research has contributed comparatively little exact quantitative data on the mechanism of solidification of metals. There is, therefore, a great need for such data in the various metallurgical industries. The mechanics of solidification of ingots have been investigated in the past primarily by studies of the rate of skin formation as indicated by bleeding or "pour out" tests. The "pour out" method, however, is a tool which gives only approximate information. In the case of alloys with wide solidification ranges, such as irons and certain nonferrous alloys, the method will not work at all; in the case of alloys of intermediate solidification ranges, such as commercial steels, the information may be misleading. Thus, the general adoption of this method has resulted in divergent conclusions regarding the solidification process. Chipman and Fondersmith1 by means of bleeding tests have shown that the linear growth of a solidifying ingot wall follows a parabola of the general form, D = K C, with the start of solidification delayed until superheat is exhausted, as indicated by the constant C. These tests were carried only to a wall thickness of about 5 in. using an ingot of approximately 17x39 in. in cross-section; hence the latter stages of solidification were not studied. Matuschka2-3 indicated that linear solidification of ingots is rapid at first, then slow, but toward the end of solidification the rate becomes extremely rapid again. Spretnak&apos;s4 bleeding studies indicated that, wall growth is expressed more rigorously by two parabolas, and that their point of intersection corresponds to a change of solidification mode from columnar to equiaxed. Spretnak also showed that the K values of the first parabola are always the same regardless of superheat. Nelson bled ingots of square cross-section and found that linear wall growth is initially rapid but decreases continually until the end of solidification. He also concluded that rate of solidification in ingots of square cross-section increases 2.15 pct for every 10 pct increase in cross-sectional area of the mold. The mold ratios considered (ratio of cross-sectional area of the mold to cross-sectional area of the ingot) were all less than 2 to 1. The subject of solidification has also been treated mathematically in many cases, but because of the lack of accurate thermal constants and the simplifying assumptions required, as their authors generally acknowledge, they represent only approaches to the actual conditions of ingot solidification. A third method of studying solidification is the electrical analogue method promulgated by Pasch-kis6-7 and by Jackson and coworkers.8 This method treats solidification as a heat transfer problem with the solidification cycle synthesized on an electrical circuit. Paschkis in his treatment of solidification considered the fact, which was generally ignored, that solidification of steel is not simply the growth of a plane solid wall but a more complex process occurring over a temperature range as indicated by the constitution diagram. Undoubtedly, the anomalous results obtained by bleeding tests arise from the inability to measure quantitatively this mushy condition. The shape of Paschkis&apos; solidification curves are more nearly in accord with those of Matuschka, in that they indicate rapid linear solidification at the beginning and end of solidification with intermediate solidification occurring at a slower rate. Paschkis indicates a definite lengthening of solidification time with increasing superheat. Thermal analysis is a direct method providing exact information for all types of metals regardless of solidification range and was thus adopted in the present program to follow the entire course of solidification from the surface to the centerline of the ingots. The method has the added advantage of being adaptable to following the thermal cycle of the ingot mold during the course of solidification. Test Methods The ingots studied were of square cross-section, 20 in. long, tapered from 71/4 in. at the top to 63/4 in. at the bottom, and fed with a hot top 7 in. in diam and 12 in. high. The molds were uniform in wall

Jan 1, 1953

By A. U. Seybolt

The pressure-temperature relations required to maintain the existence of Si3N4 in silicon-iron of 0.44-11.7 pet Si have been partially explored. The critical data obtained have allowed the calculation of some thermodynamic quantities, and have shown evidence of an order-disorder two-phase field extending at 800°C from about l pet to 5.5 pet Si. THE presence of silicon nitride in electrical sheet, nominally about 3 1/4 pet silicon, balance iron, has been described by several authors&apos;" but there has been some discrepancy among them regarding the identity of the nitride. Also, little has been reported on the quantitative thermodynamic prop- erties. In the work to be reported here, the nitride has been found to be more stable than described by Corney and Turkdogan." Several silicon nitrides have been described in the past, including SiN, Si3N4 and Si2N4 (see, for example, Abegg6 and Pascal7). However, the literature on nitrides other than Si,N, is all very old. No recent investigators using the more powerful tools available today have reported the presence of any nitride other than S3,N4. W. B. Hicke and L. R. Brantley8 in 1930 determined the dissociation pressure of Si3N4 which they made by reacting nitrogen

Jan 1, 1959

By J. Chipman, N. J. Grant, H. L. Bishop

Lime and dicalcium-silicate crucibles were equilibrated with molten iron and liquid slags containing iron oxide and small amounts of sulfur. The oxygen content of metal, iron oxide activities, and desulfurization values of the slags were determined in the temperature range 1530 to 1700°C. The influence of magnesia in the slag and the temperature dependence of the solubility of lime in liquid iron oxide and the ferric oxide content were established. The temperature contour of the liquidus surface of iron-silicate slags saturated with lime and dicalcium silicate was also established at 1600°C. THE importance of the role that slag composition plays in the refining of steel has been known for many years. Numerous studies have been made using actual plant data in order to establish the relationship between the composition of the slag and metal during the refining of a heat of liquid steel. These results rarely represent equilibrium conditions since completion of the various chemical reactions involved in steelmaking is seldom realized. In order to establish quantitatively the equilibrium conditions existing between the slag and metal, several laboratory studies have been conducted in the past 20 years to determine the reactions important in slag control. These investigations have included studies of simple liquid basic and acid slags as well as more complex slag systems which approach those commonly found during the refining of a heat of steel. Since most of the previous studies of simple basic iron-oxide slags equilibriated with molten iron were made in magnesia crucibles, it was not possible to establish the distribution of sulfur and oxygen between molten iron and slags consisting only of the three essential components, lime, silica, and iron oxide. This investigation was undertaken to establish the equilibrium conditions for simple lime-iron oxide and lime-silica-iron oxide slags. Accordingly, it was expedient to prepare crucibles both of lime and dicalcium silicate to establish the equilibrium conditions between molten iron and iron-oxide slags saturated with the refractory materials and free from other components. The only other studies of the equilibrium between molten iron and lime-saturated slags are those of Fischer and vom Ende, 1, 2 in which the solubility of oxygen was determined in an air atmosphere. The

Jan 1, 1959

By Ralph C. Flow

In Cleveland County, North Carolina, 1 ½ miles south of Kings Mountain, Foote Mineral Co. operates an open pit for the production of spodumene, feldspar, mica and commercial stone. Spodumene concentrate is sent to Foote Mineral&apos;s Sunbright, Va., plant and to other customers. Exton, Pa. and New Johnsonville, Tenn., plants produce lithium com- pounds sold to the oil industry for multipurpose lithium-base greases, to the metal industry as welding flux, to the air conditioning market and to the glass industry. Ceramic-grade spodumene, feldspar, and mica concentrates go to other processing companies from the Kings Mountain plant. Waste amphibolite is delivered to a neighboring quarry operation. Geology and exploration of the deposit have been described by T. L. Kesler, Chief Geologist of Foote Mineral Co., in the September 1961 MINING ENGINEERING. Measured ore reserves as published at that time were 20.7 million tons. The ore deposit consists of a series of lithium-bearing pegmatites enclosed in amphibolite and mica schist wall rocks. The general strike of the pegmatites is northerly, and in the southern part of the pit, they dip slightly towards the west. The largest body being mined has a fairly uniform thickness of about 200 ft. Other pegmatites in the pit area range from 20 to 100 ft in thickness. Minerals in the pegmatites are 20% spodumene, 32% quartz, 6% muscovite, 41 % feldspar and 1 % trace minerals.

Jan 10, 1962

By B. W. Howlett, M. B. Bever, Somnath Misra

The heats of Formation of the compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 and the heats of solution of tellurium and selenium in liquid bismuth have been measured in a liquid metal solution calorimeter. The heat capacities near the melting point, the heats of fusion, and the melting points of the two tellurides have been measured in a constant temperature gradient calorimeter. The thermo-dynamic quantities are interpreted in relation to the stability of the compounds and the nature of the solid-liquid transition. THE selenides and tellurides of several elements of Group VB of the periodic system are of interest because of their electronic properties. The compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 are semi- conductors; they also have gained prominence in the fields of thermoelectricity and photoconductivity. However, little is known about their thermody-namic properties. As part of a research program on the thermo-dynamic properties of intermetallic compounds, the heats of formation of the compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 were measured in a liquid metal solution calorimeter. The heat capacities near the melting point, the heats of fusion, and the melting points of the two tellurides were measured in a constant temperature gradient calorimeter. The results, in addition to their intrinsic interest as thermodynamic quantities, contribute to an understanding of the stability of the compounds and the nature of the solid-liquid transition. 1) EXPERIMENTAL 1.1) Materials. Samples of the compounds SbzSe3 and Bi2Se3 were prepared by melting the elements in stoichiometric proportions in evacuated Vycor capsules followed by quenchinn in water. They- were then annealed in vacuum for 12 hr at 550°C. A sample of Sb2Te3, consisting mainly of one large grain, supplied by the Lincoln Laboratory,

Jan 1, 1964

By R. M. Brick, Arthur Phillips

The Institute of Metals Division Lecture in 1936, given by R. F. Mehl, on diffusion in solid metals1, was introduced with the statement that "the phenomena of diffusion are intimately related to many basic problems of the metallic state, but in addition to this the process of diffusion is of first importance practically." In view of the scope of that lecture, it does not seem necessary to review the importance, history or present status of diffusion problems. One aspect of the subject of diffusion that has received little attention became of some immediate importance in the course of a study on segregation. When a solid solution alloy freezes, the familiar mechanism of solidification requires that the first nuclei formed be low in solute concentration, with a resultant normal segregation or coring effect during freezing. Theoretically, musion of solute atoms during solidification should result in a homogeneous solid solution. Actually, of course, it is impossible in most binary alloys to obtain a cooling rate that will permit diffusion to eliminate coring in the freezing dendrites. For a given alloy, the extent of diffusion attained up to the point of final solidification will determine the degree of enrichment in solute atoms of the final liquid phase. The flow of this liquid into dendritic contraction channels and the solute concentration of the liquid seem to be the determining factors as to whether the final gross segregation is normal, inverse or absent. The purpose of the present study of diffusion was to determine to some extent the separate diffusion rates of copper and magnesium into pure aluminum with a view to clarifying previous results on segregation in these alloys; i.e., the fact that under similar freezing conditions aluminum-copper alloys segregate inversely and aluminum-magnesium alloys segregate normally. Of concomitant interest were the questions of the homogenization times required for segregated ingots or partially melted, i.e., "burnt," structures, and the solution heat-treatment times required for cast, hardenable aluminum-copper and aluminum-magnesium alloys, for worked and annealed structures, and so forth.

Jan 1, 1937

By Fun-Den, Wang

An open pit rock structure usually contains geological planes of weakness. They are formed by joints, faults, bedding planes, fractures, and cleavages. Rock slope failures often occur in the form of sliding of rock blocks along a plane or several planes. Such a rock block has three- dimensional geometry, and consequently a vector method of analysis has been found useful in evaluating its stability. Rock blocks of a tetrahedral shape with one free surface have been analyzed by Londe. Rock blocks formed by sets of parallel joints have been analyzed by Wittke. The present chapter presents the analysis of rock blocks formed by planes of weakness of arbitrary orientation, and of three-dimensional geometry.

Jan 1, 1972

By A. H. Willis

In this paper the results of an exploratory study conducted by personnel of the Knolls Atomic Power Laboratory on 18.6, 22, and 40 wt pct uranium-zirconium alloy will be presented. LARGE power output and long life or endurance from small, compact nuclear reactors require the use of enriched uranium for a fuel material. However, the ability to remove heat from the element, the tolerable fission product concentration, or some physical limitation of the system can limit the allowable fuel enrichment, or the volume of the fuel. In such an event, the fuel-element designer must find a suitable diluent for the uranium. Zirconium is an attractive material for such a purpose as it has good nuclear properties and a low absorption cross section. Because it has a good corrosion resistance in water, zirconium is a suitable cladding and the uranium-zirconium alloy makes a good core material. The alloy has a high thermal conductivity, a low elastic modulus, and a low thermal-expansion coefficient, all of which tend to minimize the thermal stresses in the core. Furthermore, the unirradiated material is reasonably ductile and has adequate strength. DESCRIPTION OF SAMPLES Two types of cylindrical samples were used in this study 1) short, 1/2-to 1-in.-long samples to test the irradiation stability of the alloy and 2) 2-ft-long samples to investigate the resistance of an element to longitudinal deformation. Composite samples having 0.060-to 0.140-in. core diameters and clad with a 0.010-in. thick zirconium jacket were fabricated by coextrusion and by hydrostatic pressure bonding of the cladding to the preformed core material. Both fabrication processes produced the uniform metallurgical core-to-cladding bond which was felt necessary to minimize the uncertainty of the central core temperature. Both consumable-arc and induction-melting techniques were used to melt the uranium-sponge zirconium core alloy. Since a graphite crucible was used in induction-melting this alloy contained more carbon impurity, which resulted in a finer grain size than the arc-melted alloy. The core to cladding interface was uniform in elements coextruded from the fine-grain, induction-melted core material, while those elements fabricated using arc-melted core material had very irregular interfaces because of the coarser grain size. Both cold-worked and heat-treated fuel materials were irradiation tested. Cold-worked alloys were swaged to about a 5 pct final reduction in area without subsequent annealing. The heat-treated alloys were heated to 800°C, held at temperature for 15 min and furnace-cooled to about room temperature. This

Jan 1, 1960

By Guy N. Bjorge

HOMESTAKE&apos;S mining methods today are of necessity controlled to a considerable extent by that which has been done in the past. This may be shown by the fact that our two main operating shafts now, the B. & M. and Ellison, were begun in 1878 and 1896 respectively, so that-the loca-tions of shafts, locations of all the drifts on the upper levels, and a great deal of sloping was done before any of us now connected with the mine had anything to do- with it. Anything that I may say is not to be construed as criticism of those who have gone before for it would be a sad commentary indeed on us if we had not learned something from their experience. The levels down to the 1100 in the Homestake mine are spaced at 100-ft. intervals, and below that at 150-ft. intervals. The general plan of develop-

Jan 1, 1934

By A. M. Turkalo

IT is a well-known fact that martensitic steels show a greater resistance to brittle fracture than do pearlitic and bainitic steels. It was, therefore, thought worthwhile to investigate the mode of brittle fracture with respect to structure by studying the effect of various austenite decomposition products on the propagation of brittle fracture in steel by means of electron microscopy. Newly developed replication techniques together with the advantages of the electron microscope such as great depth of field, available high magnification and easy adaptation to stereophotography make electron microscopy very suitable for fracture studies. EXPERIMENTAL PROCEDURE An essentially plain carbon steel containing 0.56 pct C, 1.30 pct Mn, 0.02 pct P, 0.03 pct S and 0.22 pct Si was used in this investigation. The following table gives the heat treatments used to obtain the various austenite decomposition products: The resulting austenite grain size from the 870°C austenitization treatment was about an ASTM No. 7 grain size. The specimens which were 2 in. long, 1/4-in. diam bars were austenitized in a tube furnace through which argon gas was blown. The tube was not, however, air-free and the specimens were not completely oxide-free. Isothermal treatments were done in a lead bath. With the exception of the fully hardened specimen and the one as-isothermally transformed at 300°C the heat treated specimens were notched in the following fashion with a jeweler&apos;s saw. A cut about 0.08 in. deep was made perpendicular to the length of the bar. The specimen then was rotated about 45 deg and another cut about 0.08 in. deep was made. In the case of the hard martensitic and bainitic specimens, only one cut was made and the depth was not controlled. The design of the two-cut notch caused fracture to initiate at the point of intersection of the two saw cuts. The specimens were broken at -196°C in a Charpy impact testing machine. In order to hold the specimens securely in the impact machine two square pieces of mild steel were made about 5/8 in. long having the same cross section as that of a standard Charpy specimen but containing a hole 1/4 in. diam through the center of the cross-section. These adapters were slipped over the ends of the test specimen which was then secured tightly by means of set screws in the adapters. The specimen with the adapters was cooled to -196°C in liquid N,, then placed in the impact machine and broken within 3 sec. One half of the broken specimen was used for the electron microscope study of the actual fracture surface. The other half was nickel-plated and a cross section through the notch and fracture was polished for electron microscope examination. Carbon replicas of the fracture specimens for the electron microscope study were made essentially according to Bradley&apos;s evaporation technique.&apos; Both direct carbon and two-stage carbon replication techniques were used. In the case of the direct carbon technique, a thin layer of carbon was evaporated first at an angle of about 45 deg to the mean fracture surface and then another film of carbon was evaporated normally to the fracture surface. The carbon replica was freed electrolytically.2 The specimen was made an anode in a 10 pct Nital polishing solution. It was etched intermittently by shutting off the power now and then. The freed replica was washed in 40 to 50 pct water solution of nitric acid for 10 min or so, then washed in water and picked up on a screen for examination. The two-stage carbon replication technique involved first making a primary replica of cellulose * acetate from which a carbon replica was then made. One side of a strip of cellulose acetate wet with acetone was pressed lightly against the surface of the specimen, allowed to dry and then stripped. Prior to the deposition of carbon, which was done at 90 deg to the cellulose acetate replica surface, chromium was evaporated at 45 deg. After the carbon evaporation the cellulose acetate was dissolved in acetone according to the Jaffe method3 leaving the carbon replica preshadowed with chromium for examination.

Jan 1, 1961