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By R. S. Kinasevich, D. D. Crabtree, D. W. Fuerstenau, T. P. Meloy, A. L. Mular

The effect of such variables as feed size, particle shape, cleavage, and hardness on the relative proportion of impact, abrasion, and chipping events in a tumbling mill is demonstrated. The concept of an average event, which is a combination of the three comminution mechanisms, is introduced. It is postulated that the average event in a particular mill determines not only the size distribution but also the energy-size reduction relationship for the comminution process. Fragmentation of particles in tumbling mills appears to result from a combination of impact, abrasion, and chipping grinding.' The relative rates of size reduction attributable to any of the basic grinding mechanisms must depend upon a number of variables, such as feed size, particle shape, hardness, and the number and kind of particles in the mill. The purpose of this paper is to show experimentally how these variables in the properties of materials affect the size distributions obtained by grinding the material's in a laboratory tumbling mill. The resulting size distributions will be intetpreted in terms of a combination of three comminution mechanisms. METHODS AND MATERIALS In this study, minerals of widely differing properties were ground either separately or as mixtures in laboratory mills using rods or balls for grinding media. The materials used include quartz, Tuolomne, limestone (99.8% CaCO3), barite, corundum, galena, pyrite, glass beads, and crushed glass. The mill used was 8 in. in diam. and 9-1/4 in. long. For the ball milling tests, 17.6 kg of steel balls (36: 7/8 in. balls, 178: 1 in. balls, and 44: 1-1/8 to 1-1/4 in. balls) were used. For the rod milling experiments, 17.6 kg of steel rods 9-1/16 in. long (25: 5/8 in., 10: 3/4 in., and 5: 7/8 in. in diam.) were used. In each test, 1 kg of solids were ground wet at 60% solids at 77 rpm. In all cases except where otherwise specified, the feed to the mill was 4 x 8 mesh material. Size distributions of the ground products were determined by a wet-dry sieving procedure with Tyler series sieves. Size distributions of mixed products containing limestone were determined by dissolving the limestone with acid and sizing the residue. EXPERIMENTAL RESULTS AND DISCUSSION If the size distribution of the product from a tumbling mill depends upon the relative proportion of impact and attrition (abrasion and chipping) events, altering the grinding conditions may change these proportions and consequently alter the size distribution of the product. Data to illustrate this point can be taken from Gaudin's classic 1926 paper.2 In one series of experiments, Gaudin ground quartz of different initial sizes for four hours in a laboratory ball mill with 7/8-in. balls. In Fig. 1, his data are reproduced as the cumulative fraction finer than the stated size for the following initial feed sizes: 13.3 x 9.4 mm, 6.7 x 4.7 mm, 2.6 x 1.6 mm, and 0.83 x 0.59 mm. As the feed size was decreased, a dramatic change in the shape of the size distribution curves took place, even though the amount of minus 100-mesh

Jan 1, 1964

By Phillip A. Stoll, Young Ku Yoon

ThE deterioration of the magnetic properties of silicon-steel core materials during service (magnetic aging) is quite undesirable. Although some information about the effects of impurity elements on magnetic properties is available, 1,2 magnetic aging that occurs at low temperatures has not been extensively studied. Moreover, the microscopic techniques used by earlier workers were not suitable for study of fine metastable phases that are precipitated at relatively low temperatures. Recently, several investigators3,4 successfully used transmission electron microscopy in the study of low-temperature precipitation in Fe-C, Fe-N, and Fe-Mn-C alloys. To investigate metallurgical factors that affect magnetic properties after aging, the microstruc-tures of steels having different magnetic-aging

Jan 1, 1964

By N. Arbiter, J. Steininger, C. C. Harris

Power consumption and operating variables in air-liquid systems for a wide range of operating conditions in the turbulent region have been correlated by two dimensionless groups involving the power ratio and the flow number. The form of the correlation was developed by considering flow balances related to the air-liquid composite density in the impeller zone. Data for two phase air-liquid systems, both from literature and from the present investigation, has been correlated with high statistical significance. Two phase solid-liquid and three phase gas-liquid-solid systems have also been correlated. The quantification of power requirements in the agitation of liquids is well established.1 Rushton, Costich and Everett have shown that, for mixers operating in the fully turbulent region with no vortex, the power number

Jan 1, 1964

By A. P. Pipilen, M. Weintraub, W. F. Hosford, A. A. 230-000-000-006 Orning

In a study of the principal factors affecting the transport of coal-water mixtures through a centrifugal pump and a pipeline, the interrelation between solids concentration, velocity, and pressure drop was established for a minus 2-in. bituminous lump coal in concentrations up to 48% by weight. Optimum concentrations were found to exist for maximum capacity of a given pipeline and for minimum energy requirements per ton of coal. Coal size degradation by particle fracture took place in the pump; abrasion and attrition to form fines took place in both pump and line. A novel system of studying flow of solid-liquid mixtures in pipelines by the determination of relative sound intensities was developed. The hydraulic transport of minerals is in part an established art and in part a relatively new field of industrial technology. The established art developed especially where the mineral was under water, where water was used in hydraulic mining, or where large quantities of water had to be pumped from the mining site to expose the mineral. Power requirements and limited life of pumps and pipelines, under such conditions, were relatively unimportant. Examples may be found in dredging, and in hydraulic mining and transportation of phosphate rock.' In the design of a coal pipeline the most needed information relates to flow characteristics, power requirements, pressure drop, size degradation, and size segregation as a function of solids-water ratio and size distribution of the mineral. A considerable amount of information has become available concerning pressure drop and energy requirements.2'3 These topics were therefore not studied intensively. Coal degradation, however, has not been clearly delineated. Lammers and coworkers4 showed that coal may be severely degraded in size but did not distinguish between degradation produced in the pump and in the line. It is the primary purpose of this paper to outline techniques used to acquire some of the much needed design data. A full report of the investigation is to be published by the Bureau of Mines at a later date. APPARATUS AND PROCEDURE The apparatus for circulation tests (hereafter referred to as Type III tests) consisted essentially of a loop and a centrifugal solids handling pump, with attendant instrumentation, and coal weighing and feeding equipment. It also included an adequate water supply, as shown in Fig. 1. The selection of 6-in., schedule 40, carbon steel pipe was based on the top size of coal to be used. Assuming that the top size of coal should not exceed 1/3 the inside diameter of the pipe, a 6-in. pipe would accommodate 2-in. coal, a realistic size for transport from the mine face. An 872-ft loop was constructed first. Later a few tests were made with a lengthened circuit of 1361 ft by superimposing an additional loop on the original one. All bends used were of 3-ft radius. A noisemeter microphone, taped to the pipe at various points, but generally about 50 ft downstream of the pump, was used to sense segregation of the coal and the length of slugs of coal in water. To measure the stream velocity, radioactive sources were encapsulated in plastic cubes. The specific gravity of the blocks was adjusted to 1.3 and 1.8 to simulate low ash and high ash coal particles. Their passage through the pipeline was detected by a Geiger counter. Because the repeated circuits of the Type III tests did not permit coal degradation in the line to be distinguished from that produced by the pump, the two

Jan 1, 1964

By H. M. Thorne

Oil shale, a potential source of products presently obtained from petroleum, is found in many countries. The most extensive known deposits from the standpoint of potential shale oil in place are those in Brazil and the United States of America. Mining methods used for oil shale range from open-pit operations for shallow deposits to room-and-pillar and longwall techniques for deposits with thick overburdens. Oil shales from different sources vary greatly in the amounts and types of organic and inorganic constituents. By retorting, the organic material is converted to oil, gas, and coke. The largest percentages of oil are obtained from materials having the highest hydrogen content. Over 2,000 retorting systems have been patented, but only a few have been used industrially, and no single process seems best for all types of shales or economic conditions. Shale oils have different characteristics, depending on the source rock and method of retorting. They contain large quantities of olefinic hydrocarbons and more oxygen, nitrogen, and sulfur derivatives of hydrocarbons than most petroleums. Consequently, petroleum refining methods usually must be modified for shale oil. This is particularly true in catalytic processing. Hydrogenation, even under mild conditions, improves shale-oil refinability. Several byproducts may be obtained from both the retorting and refining steps.

Jan 1, 1964

By P. G. Winchell, J. K. Jackson

The strtcture of body-centered Fe-Ni-C alloys (0 to 16.5 wt pct Ni) containing less than 0.015 wt pct C was investigated by measuring the carbon-diffusion peak at low frequencies with a torsion pendulurrr. By determining the Snoek damping in ferrite and in quenched alloys of identical composition, the effects of nickel content and heat treatment were separated, and the existence of a structure in which Snoek damping is greatly reduced was revealed in the quenched ternary alloys. The relative amount of this structure increases with increased nickel content and cooling rate. It is proposed that this structure may be highly imperfect or tetragonal. In Fe-Ni-C alloys containing only ferrite the addition of nickel (0 to 5.1 wt pet) decreases tke area of the carbon-diffusion peak and shifts its position to lower temperatures but broadens the peak only slightljl. The decrease in peak area with increasing nickel implies that short-range interactions with the nickel atoms prevent some of the carbon atoms from participating in the relaxation process. The shift in the peak position indicates a long-range effect of nickel on the movement of carbon atoms so that at 300°K the diffisivity of carbon in -ferrite is increased by about 35 pct by the addition of 5.1 tut pct Ni. The results are presented as distributions of relaxation strength 072 the activation energy under the assumption that the frequency factor is invariant. BODY-CENTERED iron-base solid solutions dissolve carbon interstitially in the octahedral sites. The occupation of an octahedral site produces a tetragonal distortion of the surrounding lattice. These sites fall into three sets according to the orientation of the tegragonal distortion associated with each and may be identified by their lattice coordinates as: type 1/2 0 0, type 0 1/2 0, type 0 0 1/2. At low carbon levels in cubic ferrite the carbon atoms are distributed at random1 among these sites. In high-carbon body-centered iron-base solid solutions, which are unstable with respect to several two-phase mixtures, a tetragonal structure occurs as the product of the diffusionless transformation of austenite. This transformation is commonly accompanied by appreciable microstrain and its product is called martensite. The tetragonality of martensite, a supersaturated solution of carbon in a iron, is maintained prior to decomposition even though local diffusion of carbon occurs as evidenced by carbide precipitation. The tetragonality is taken as evidence that one set of octahedral sites is preferentially occupied by carbon. (This preferential occupation is called ordering below.) Support for this view is presented by the absence of strain-induced carbon-atom diffusion in high-carbon solid solutions (martensite). Such diffusion occurs in ferrite and produces the 40°C internal-friction peak observed at 1 cps frequencies.' Thus, there appears to be qualitative evidence favoring the view that at sufficiently high carbon levels tetragonality arises spontaneously as a result of the ordering of the carbon atoms; however, no experimental evidence exists concerning an equilibrium between cubic and tetragonal body-centered solid solutions. Moreover, attempts to estimate the energy of ordering7-' predict a value too low to maintain the tetragonality observed at medium carbon levels, 0.3 to 0.6 wt pct C. In the present work an attempt using internal-friction measurements is made to establish the presence or absence of tetragonality in low-carbon body-centered solid solutions formed by quenching austenite. Fe-Ni alloys containing about 0.01 wt pct and 0 to 15 wt pct Ni were selected for the study. While the work was in progress Gilbert and Owen10 reported that the transformation which occurs in these alloys during quenching at rates up to 5000°C per sec is not martensitic but is more properly categorized as massive. Thus, the solid solution

Jan 1, 1964

By J. B. Newkirk, R. W. Hendricks, R. Baro

STUDIES of the kinetics of precipitation in binary alkali halide systems are of interest from a theoretical point of view, because of the possibility of controlling diffusion rates by additions of aliovalent impurities. This note reports some preliminary results of a study of the kinetics of precipitation of AgCl from supersaturated solid solutions of AgCl in NaCl containing trace amounts of divalent cation impurities. In their study of the system NaC1- AgC1, Stokes and Li1 derived the phase diagram containing a mis-cibility gap with a broad maximum at approximately 170°C. They found that single crystals quenched from above the miscibility gap and aged at various temperatures within the two-phase region gradually turned light blue, then cloudy white, and finally opaque. The rate of transformation depended markedly on the aging temperature. The light-blue color in the early stages of aging was interpreted to be the result of Rayleigh scattering from precipitated particles less than 0.1 µ in diameter. These qualitative observations have been confirmed by us. However, a more precise tool was needed in order to quantitatively follow the growth kinetics of the precipitate particles. Because of the suspected small size of the precipitate particles and for other reasons, small-angle X-ray scattering was thought to be a suitable technique for this study. Small-angle X-ray intensities scattered from powder specimens were recorded on a General Electric XRD-5 diffractometer using the four-slit geometry described by Neynaber, Brammer, and Beeman.2 The slits were 0.08 mm wide by 10.00 mm high. It was found that, with very careful alignment, meaningful data could be obtained to within 3 min from the middle of the direct beam. Chromium radiation (?Ka = 2.29Å) was used in order to spread the scattered intensity to a relatively high angle, as indicated by Eq. [1]. A specimen containing 21.0 at. pet AgCl was prepared by melting analytic reagent-grade AgCl and NaCl under a chlorine atmosphere in a vycor cap-

Jan 1, 1964

By M. J. Marcinkowski, A. Szirmae, R. M. Fisher

Room -temperature hardness measurements obtained from single and polycrystalline samples of a 47.8 at, pet Cr-Fe alloy which were aged for various times al 500°C show a two-fold increase over that of the unaged alloy after annealing for 1000 hr. A detailed examination of the deformation markings in the neighborhood of the hardness imbressions reveals that twinning becomes an increasingly more important mode of deformation as aging proceeds. this observation is shown to be inconsistent with the Proposals that the transformation is eve of order-disorder On the other hand, the results are in agreement with previous observations of Fisher et al. of a coherent chromium-rich precipitate which forms in an iron-rich matrix as a result of a miscibility gap in this alloy system as proposed by Williams . Using the coherent precipitate hypotlzesis as a model, a detailed analysis of the various possible strengthening contributions to both the slip mid twinning stresses is made. In the case of' slip, lattice friction within the chromium-rich phase and the chemical energy associated with the interface between the two phases contribute about 60pet to the total strength. The contributions from coherency strains and modulus differences are thought to contribute the remaining 40 pet of the strength but are difficult to evaluate because of uncertainties regarding the flexibility of the dislocation line. All of the factors have nearly the same or else a smaller effect on the twinning stress in the aged alloy. Twinning is never observed in the unaged alloy because the twinning stress is much higher- than that for slip. With increased aging times, the various contributions to the total stress for both twinning and slip increase, but most of those for slip increase much more rapidly, so that, in the fully aged alloy, it surpasses the stress for twin propagation. When a twin is nucleated by the chance occurrence of an internal stress concentration during a test, the subsequent twin burst results in a low hardness reading. FeRNTIC Fe-Cr alloys from about 15 to 80 at. pet Cr content show considerable change in properties such as hardness, electrical resistivity, saturation magnetization, and so forth, after aging in the vicinity of 500°C.* The most marked change is a large increase in hardness accompanied by a sharp decrease in ductility, so the phenomenon has often been referred to as the 475°C (885°F) em-brittlement problem. Changes in microstructure are rather subtle and most investigators have not been able to observe any X-ray diffraction or metal-lographic changes during aging. There is little doubt that the phenomenon is inherent to the Fe-Cr binary system and is not directly related to the formation of a phase. Two distinct schools of thought have developed during the past decade concerning this problem. Masumoto, Saito, and sugiharal have concluded, from their own specific-heat measurements, that atomic ordering occurs in this temperature range. Pomey and Bastien2 have also attributed the changes in physical properties with aging in the neighborhood of 500°C to atomic ordering. In addition, Takeda and Nagai3 claimed to have found X-ray verification for superlattices corresponding to the compositions FesCr, FeCr, and FeCr3. However, all known attempts to observe superlattices in Fe-Cr alloys using neutron diffraction, which should be much more sensitive, have been unsuccessful. These have been reported by Shull et al.4 for 25 at. pet Cr, williams5 for 75 at. pet Cr, and Tisinai and samans6 for a 28.5 at. pet Cr. steel. The second and more prevalent opinion ascribes the 475°C embrittlement phenomenon to the formation of a coherent precipitate due to the occurrence of a miscibility gap in the Fe-Cr system below about 550°C. This latter concept was first indicated by the results of Fisher, Dulis, and Carroll,7 who were able to extract fine particles about 200Å in diameter from samples of 28.5 at. pet Cr steels aged from 1 to 3 years at 475°C. The extracted material was found to be nonmagnetic, to have a bee structure with a lattice parameter between that of iron and chromium, and to contain about 80 at. pet Cr. Williams and paxton8 and williams5 confirmed these results and first explicitly proposed the existence of a miscibility gap below the a region in the equilibrium diagram. Alloys aged within this gap

Jan 1, 1964

By R. A. Wolfe, H. W. Paxton

Self-diffilsion coefficients for cr51 and Fe55 in 12 pct Cr-Fe and 17 pct Cr-Fe for Fe55 in chromium, and for Cr51 in vanadium have been measured. The results are compared with other values for the Fe-Cr system, and with the various theories of diffusion in hcc metals. Some empirical correlations are discussed between Do and Q in hcc systems, or, expressed differently, the constancy of ?G*/T solidus for seveval bcc metals and alloys is noted. It appears very probable that a vacancy mechanism is operative in bcc metals, hut this cannot he stated with certainty. THE great bulk of work on diffusion in metals, both experimental and theoretical, was for many years concentrated on those with close-packed and, in particular, fcc lattices.1,2 There appears to be little doubt that the mechanism of diffusion in these solids is vacancy migration, leading to mass transfer and in substitutional solid solutions to a Kirken-dall effect.3,4 For bcc metals, the picture is much less clear. The Kirkendall effect certainly occurs in several alloys.5-10 However, attempts to understand the factors contributing to the pre-exponential in the usual expression for the diffusion coefficient D =D, exp {-Q/RT) by extension of ideas useful in close-packed lattices have not always been successful. Zener,11 Leclaire,12 and Pound, Paxton, and Bitlerl3 have suggested that various forms of ring diffusion may be important in some bcc metals. For close-packed metals, Do is usually about 1 sq cm per sec and Q - 35Tm kcal per mole (Tm = melting temperature in OK). The theory of Pound et al. suggests for ring diffusion that Do may be about 10-4 and Q, although difficult to calculate with any precision, would be significantly less than 35 T,. The experimental results on self and solute diffusion in ? uranium14,15 and ß zirconium,10 and for solutes in 0 titanium,17 and possibly for self-diffu- sion in chromium below about 0.75 T,," gave some credence to this theory. However, not all bcc materials display low values of DO and Q, and the exceptions were not predicted by any theory. Furthermore, it has recently become apparent that, in bcc materials, log D is not always linear with T-l if a sufficiently wide range of temperature is studied.16,18 This variation may be such that Q may increase18,19 or decrease20 with increasing temperature. The present work was undertaken in an attempt to provide further diffusion data on bcc metals, and to try to understand the factors which contribute to differences in behavior between the various elements. For part of this work, the Fe-Cr system was chosen since it is of considerable technological importance, and data on 12 pct Cr and 17 pct Cr alloys appeared well worthwhile to supplement that existing for the remainder of the stern.18,22 The diffusion of Fe55 in chromium was studied as an example of a more or less "normal" tracer element in a possibly abnormal host lattice. Finally, no data were available for vanadium, the neighbor of chromium in the periodic table, because of lack of a suitable isotope so cr55 was used as a tracer in a few preliminary experiments. For convenience, we shall refer to elements whose Do and Q are low compared to those predicted by Zener's theory as "anomalous". PROCEDURE This investigation determined self-diffusion rates by means of radioactive tracers and the integral-activity method first utilized by Gruzin.23 In this method a thin layer of radioisotope of the diffusing element is plated or coated onto a planar surface of the diffusion sample, which is then given an isothermal-diffusion annealing treatment. The determination of an activity-penetration curve involves measuring the residual activity of the specimen after each successive layer or section has been removed parallel to the original planar surface. The method used here is essentially the same as that used by Gondolf18 and Kunitake.21 Two radioactive tracers, cr51 and Fe55, were used in this investigation. Diffusion coefficients were determined for the diffusion of one or both of these tracers in four different materials, viz., Fe-12 wt pct Cr alloy, Fe-17 wt pct Cr alloy, chromium, and vanadium. The diffusion samples had nominal dimensions of 1.5 cm diameter and 0.5 cm thickness. The grain size was several millimeters for the Fe-Cr alloys and at least 1 mm for the chromium and vanadium samples. Accurately planar surfaces

Jan 1, 1964

Manganese ore has been mined from the Peak Hill Gold- field since 1948 and from the Pi'lbaraòGoldfield since 1954, and it is probable that some deposits- In and, near the Phillips River Goldfield will be mined at a future date', There are also several million tons of mariganiferous ;naterial which is too low in manganese. .co.ntent_ for . present requirements. The manganese deposits¦of Western Australia are mostly superficial. They hav' been formed during the Cainozoic Era by supergene enrichment ò6f Precambbrian: manganiferoius sediments, and by deposition from -solution on, or'in caves in, the Cain- ozoic land surface. The manganese in solution was derived from the weathering of Precambrian manganifer.ous s.edimexsts, None of the deposits are of hydrothermal origin, nor are they related to igneous rocks in any war, other than as ultimate source rocks. There is ho evidence-'t.o.:sugge,st that meta- morphism has been responsible for.the emplacement of any deposit. The tenor of the ore varies'aec'ording'to the quantity of gangue in the orebody and- also to the nature of the part- icular ore minerals. The main ore.mine.rals are the oxides pyrolusite and cryptomelane and the 'o'xide-silicate braunite. The main gangue minerals are hematite, limonite and quartz. The deposits of high grade oreò(-above.45 per cent Mn) range in size from 50 tons to many thousands of tons but most of them are in the 500-5,000-tons r .nge .

Jan 1, 1964

By C. Wert, P. Bunn

Determination of the solid solubility of gases in metals is usually done by one of two methods. The first is an additive method, in which measurement is made at temperature of the maximum amount of gas absorbed by an initially degassed piece of the metal. Gas additions are made until the dissolved gas first comes into equilibrium with a compound. This method is most useful at relatively high temperatures where the amount of gas absorbed is relatively large and where equilibration of the dissolved gas with the gas atmosphere can be achieved in a relatively short time. The second is a precipitation method. A supersaturated solution of the gas in the metal is held at temperature until equilibrium is established between the gas atoms in solution and a compound. The quantity of dissolved gas is then determined by some physical measurement which is sensitive only to the gas in solution. This method is generally useful in low temperatures. This paper describes measurement of solubility of nitrogen in tantalum whereby measurements at low temperatures using internal-friction methods are plotted together with existing measurements at high temperatures. The solubility is thereby known from less than 0.5 at. pet at 350°C to near 13 pet at 2300°C. Several measurements have been reported of the solubility of nitrogen in tantalum. These are collected in Fig. 1. Three single determinations by Ke,1 Andrews,2 and Brauer and zapp3 are plotted along with a series of measurements by Vaughn, Stewart and schwartz4 and Gebhardt, Seghezzi, and Fromm.5 Although not much doubt exists about the solubility being in excess of 10 at. pet above 2000°C, the solubility indicated at low temperatures depends on whose data are selected as being most reliable. The variation is enormous, being at least an order of magnitude at 500°C. Accordingly, a measurement was begun to examine this discrepancy. The method of measurement finally selected was that of internal friction. A solid solution of nitrogen in tantalum was prepared by heating a tantalum wire in a dilute at-

Jan 1, 1964

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,' 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.' 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.' Fracturing anisotropy in wrought products lends support to the idea of void formation from preexisting flaws strongly aligned by earlier processing.''-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 L. D. Jaffe, F. W. Cotter, E. Cordon

The hardenability of titanium-base alloys was studied by metallographic examination and hardness survey of Jominy specimens end-quenched from the B range. Analyses of the data led to the equation log J = -0.57 + 0.25 @ct Fe + pct Mn + pct Mo) + 0.19 @ct Cr) +0.16 @ct V) + 0.03 @ct Zr). Here J is the distance, in sixteenths of an inch, from the quenched end of a Jominy hardenability specimen in the position of peak hardness, for material quenched from the B range. This equation fitted the experimental data with a standard deviation of approximately 0.29. The effects of the elements Al, Sn, W, Cu, Ni, B, C, N, 0, and H, and of pain size, were not statistically significant or not practically significant. A check against hardenability measurements in the literature showed agreement within the stated standard deviation. The equation should be useful in estimating hardenability of new or modified titanium alloys. HARDENABILITY in a titanium-base alloy is the ability of the alloy to retain the B structure on quenching. An alloy with high hardenability will retain the /3 structure even when cooled relatively slowly from a temperature at which B or P plus a is stable. A low hardenability material will retain P only if quenched extremely rapidly from the range of p or 0-plus-a stability, or will not retain it at all, at room temperature. High hardenability is desirable in titanium alloys to be heat-treated to high-strength levels. Its value is by no means limited to large section sizes. With high hardenability, a material can be solution-treated and cooled at a variety of rates, either to give high strength directly or, more generally, to give a soft ductile condition from which high strength can be obtained by subsequent aging. With low hardenability, high strength can be obtained, if at all, only by very rapid quenching, and there will generally be little increase in hardness on subsequent aging; an alloy of this type is limited in its applicability. On the other hand, alloys of very low hardenability have some advantages in weldability; essentially, they are always in the annealed condition, after welding as well as before. For commercial alloys, hardenability data are usually available, in the form either of property data after cooling from the solution temperature at various rates, with or without subsequent aging, or of results of a standard hardenability test, such as that originally developed for steels by Jominy and Boegehold.' When modifications of an available alloy are considered, or preparation of new alloy compositions, it would be Very convenient to be able to estimate the hardenability of the new material without having to make and test it. A method of estimating hardenability of titanium alloys from their composition was suggested by one of the authors some time ago, on a preliminary basis, utilizing scattered data found in the literature.' It seemed worthwhile to carry out a systematic experimental study of the effect of composition upon hardenability. EXPERIMENTAL PROCEDURE Approximately fifty heats of various compositions, weighing 8 to 10 Ib apiece, were melted in a small inert-gas tungsten-arc furnace with water-cooled copper walls. The starting material was 110 Brine11 titanium sponge, with high-purity metals added for alloying. Each heat was bottom-poured under vacuum through a molybdenum burnout strip into a cold graphite mold, to form an ingot approximately 4-1/2 by 3-1/2 by 3 in.* From each ingot were cut *The material was melted and cast by Pitman-Dunn Laboratory, Frankford Arsenal, to whom the authors must express their thanks. two pieces 4-1/2 by 1-1/2 by 1-1/2 in. These were forged, at temperatures adjusted to the composition, into 1-1/4-in. rounds, from which standard 1-in.-diam hardenability specimens3 were machined. A number of small samples were also prepared from forged materials of each heat, annealed, quenched from various temperatures, and examined metallographically. The P-transus temperature was determined by observation of the degree of resolution of primary a in these pieces. samples for chemical analyses were also taken from the forgings. One hardenability specimen of each heat was solution-treated for 1 hr approximately 50°F above the measured transus temperature, and the other for 1 hr approximately 250°F above the transus. (An additional hour was allowed for the specimens to reach furnace temperature.) These are not necessarily the temperatures that would be selected for

Jan 1, 1964

By Norman Brown, Victor V. Damiano

ThE present paper proposes a mechanism of dislocation multiplication at internal inclusions or cavities and presents experimental evidence of such sources in zinc. Using an etching technique recently described by Damiano, Tint, and Herman1 to study the three-dimensional aspects of dislocations in bulk zinc crystals, an investigation was made of helically shaped and closed-loop etch patterns found to be associated with inclusions. Crystals containing 0.1 pet Cd and grown from the melt were deformed slightly by bending and then aged at room temperature to precipitate cadmium at the dislocations. The crystals were cleaved along the (0001) plane and then etched with Gilman's2 etch. Crystals were continuously viewed on the (0001) plane while the etching was in progress and numerous helical and closed-loops etch patterns were continuously recorded as shown in the sequences printed directly from the cine film in Fig. l(a) and (6). These etch patterns are not to be confused with the etch patterns previously reported by Damiano and Herman3 which revealed dissolution spirals on the (0001) plane of high-purity zinc crystals. In the present case, precipitates arranged in the form of closed loops or helicies are progressively uncovered by etching after suitable aging of cadmium doped zinc crystals. Viewed with dark-field illumination as shown in Fig. 2, portions of a helical figure and subboundaries were revealed simultaneously. Continuous viewing while the etching was in progress revealed in Fig. 1(b) that the short line segments observed on single photomicrographs were in fact continuous and described a helix which had its terminus at an inclusion. The observations suggested that a dislocation once nucleated at the interface between the inclusion and matrix may act in such a way as to produce ad-

Jan 1, 1964

By Thomas R. Mager

An in.t!estigation has been made of the equilibrium conditions at 1200°C in the reaction between hydrogen sulfide gas and sulfur dissolved in Fe-Si alloys From this the equilibrium constant, activity coefficient, and activity of sulfur in solution were calculated. A number of studies of the equilibrium of sulfur with iron and iron alloys have given closely agreeing results from which the activity and free energy of the dissolved sulfur may be found. Sherman, El-vander, and chipman1 discussed the significant researches of dilute solutions of sulfur in liquid iron prior to 1950, and the results of this study indicated that the relationship between the ratio of PH2S/PH2 in the environment and the percentage of sulfur in solution is not a linear one. Morris and williams2 studied the equilibrium conditions in the reaction between hydrogen sulfide gas and sulfur dissolved in liquid iron and Fe-Si alloys, and reported that silicon dissolved in iron has a pronounced effect on the equilibrium conditions. They found that the activity of sulfur in iron is increased by the addition of silicon. At a silicon content of 4 pet the activity coefficient of sulfur was about twice that for sulfur dissolved in pure iron. Sherman and chipman3 investigated the chemical behavior of sulfur in liquid iron at 1600°C through the study of the equilibrium: H2 + S = H2S; K = PH2S/PH2 . 1/as [1] From the known equilibrium constant of the reaction between H2, H2S, and S and the experimental data, the activity of sulfur in the melt was determined. They found that the activity coefficient of sulfur defined as fs = as/%s is increased by silicon and decreased by manganese. Morris4 and Turkdogan5 also reported that manganese decreases the activity coefficient of sulfur in liquid iron and iron-base alloys. A recent technique of sulfur analysis developed by Kriege and wolfe6 of the Westinghouse Research Laboratories permits an accurate sulfur analysis of 0.5 * 0.2 ppm in the range of 0.1 to 3 ppm, whereas in the range of 3 to 50 ppm the accuracy is ±1 ppm. This technique of sulfur analysis was utilized in this experiment. Previous unpublished data reported that sulfur analysis by the combustion technique was not accurate below 20 ppm. EXPERIMENTAL PROCEDURE Five 5-lb ingots of high-purity Fe-Si were prepared. Three of these ingots were prepared without the addition of manganese but with a variation of silicon contents from 2 to 4 pet. The remaining two ingots contained 3 pet Si with the addition of manganese. Ingots were made at each of three silicon levels: 2, 3, and 4 pet. No alloys were made with less than 2 pet Si since below approximately 1.8 pet Si the binary alloy exhibits a to ? transformation. The two additional ingots of 3 pet Si-Fe were made at each of two manganese levels: 0.20 and 0.50 pet. To minimize the effects, if any, of impurities on the activity of sulfur on Si-Fe, the best metals available were used for melting. All ingots were vacuum-melted in magnesium oxide crucibles. After obtaining samples for chemical analyses, the ingots were processed. This consisted of hot rolling and subsequently cold rolling the alloys. Each ingot was hot-rolled at 1000°C, reheating between every pass to minimize grain growth. All heating was done in a protective argon atmosphere. The slabs were hot-rolled to strips 50 mils thick. After hot rolling, all the material was pickled to remove the scale formed on the surface of the strip during hot rolling. The material was then cold-rolled to 12-mil strips. Single strips of the material used in this experiment were hydrogen-annealed at 1200°C for 16 hr in an alumina tube. Chemical analyses of strips M-1, M-3, M-4, M-7, and M-8 are given in Table I. Sulfur, silicon, and manganese analyses were made from the millings from the cold-rolled 12-mil strips. The oxygen analyses were made from slugs of the as-cast material. The hydrogen sulfide used in these experiments was supplied from cylinders containing a mixture of argon and 1 pet hydrogen sulfide. The parts per million of hydrogen sulfide were determined from the analysis of the exit gas of the annealing furnace during each anneal. The flow rate of hydrogen was approximately 1 liter per min in all anneals. The

Jan 1, 1964

By D. E. Hartman, J. M. Roberts

A detailed study of the temperature dependence of the critical stress, TB . necessary to cause a damping loss of 1.41 x 10-6 g mm per mm3 in pre-strained magnesium single crystals has been carried out in the temperature range 82" to 320°K. Tb is found to be linearly related to the reciprocal of the ahsol~cte temperature in this temperature range. The temperature dependence of the anelastic limit, TA, defined as the stress necessary to form open unidirectional stress-cycle damping loops has been measured between 82" to 320°K. ta is found to be independent of temperature in this range. It is suggested that TA is determined by the stress necessary to activate Frank-Read dislocation NUMEROUS studies1-9 have been reported concerning the details of yielding and microstrain near and below the generally discussed macroscopic flow stress. The work of Kramer and coworkers10-13 is helpful in determining certain qualitative facts. concerning preyield phenomena. The absence of a stress-dependent delay time in annealed copper and aluminum single crystals between 83" and 298 suggests that the preyield mechanism is temperature-independent in this range. This is not sources. The temperature and stress dependence of the effective activation volume (Veff) has been measured in the damping-loop region in prestrained magnesium single crystals. The data suggests that Veff/kT is approximately constant, equal to 2 4.5 sq mm per g in the temperature range 130°to 298°K, and that Veff is almost independent of stress at stress levels greater than 10 g per sq mm. A restricted model is developed to predict the stress (rb) necessary to cause a small fixed damping loss as a function of temperature, effective activation volume, and dislocation density. Various possible dislocation mechanisms controlling TB are discussed. true for zinc, p brass, and iron crystals in the same temperature range, however, since the existence of a stress-dependent delay time suggests a thermally activated preyield mechanism in these materials.10-13 The work by Vreeland et a1.14 confirms the work by Liu et al.ll on delayed yielding in zinc single crystals. A stress-dependent delay time between 82" and 298°K was found12 in prestrained aluminum and copper crystals. These results suggest that the preyield phenomena may be different between prestrained and unstrained or annealed crystals. The temperature dependence of the yield point at 2 x 10-8 plastic strain found by Rosenfield and Averbach3 in annealed copper and aluminum is not in agreement with the delay-time data, unless possibly the delayed yielding experiment only de-

Jan 1, 1964

By Gary A. Kingston

This examination of Pacific Northwest (Idaho, Montana, Ore on, and Washington) ferrous scrap-industry opera ions, principally those in Oregon and Washington, points out factors influencing the supply and consumption of scrap materials, such as the complete dependence of steel ingot producers in these States on scrap as a metal raw material and the sizable quantity of scrap exported from Seattle and Portland to Japan. The pattern of the industry is presented as a movement of materials from their diverse sources to the consuming market. The geographic locations of the consuming industries in relation to the area generating scrap materials and the movement pattern of the supply from source to destination strongly influences the cost of the commodity. The best measure of the scrap supply available in an area is experience in terms of how much scrap was withdrawn at a given price. Scrap availability is not finite, because the return of materials as scrap is secular and influenced by constantly varying market conditions. Steel ingot producers use 75 percent of the approximate 500,000 tons of scrap consumed in Oregon and Washington; steel foundries take 15 percent of the total; and iron foundries, ferroalloy plants, and other miscellaneous consumers utilize the remainder. Also, from 1955 to 1960 an average of about 200,000 tons has been exported annually from Oregon and Washington. The foreign exports are supplemented by lesser .shipments to other steel producing States, principally in the western United States. From 1955 to 1960 the preferred and higher value heavy melting scrap grades accounted for about 60 percent of total withdrawals which varied between 600,000 and 950,000 tons annually. Total scrap withdrawals from Oregon and Washington are projected to 1.8 million tons by 1985, 60 percent (1.1 million tons) of which will be heavy melting grades. No. 1 heavy melting scrap is most attractive to scrap consumers at $35 per ton or less. Price-supply relationships compared with projected scrap requirements indicate future prices possibly over $35 per ton. High prices over a long period could motivate the Pacific Northwest scrap consumers to produce steel from iron ore. However, technologic changes taking place at integrated steel plants could reduce scrap withdrawals from the Pacific Northwest, which might keep the scrap price sufficiently attractive to obviate production of competitive iron products by the Pacific Northwest scrap consumers.

Jan 1, 1964

By D. E. Etter, J. E. Selle

HIGH-PURITY cerium metals, supplied as 99.9 pct pure, by various suppliers, vary widely in melting points and in the shapes of the differential thermal-analysis curves obtained as the samples are heated. A definite correlation is noted between the melting point, amount of premelting, and the number of inclusions present in the material. Briefly, the DTA apparatus, previously de-

Jan 1, 1964

By M. H. Pilkuhn, H. Rupprecht

The junction luminescence of GaAsxP1-x diodes containing up to 47 pct Gap was studied. Diodes were prepared by diffusing zinc into n-type material which was eithw boat- or vapor-gvown. Observations concerning the energy and the line shape of the spontaneous emission are presented and discussed; in particular the influence of inhomogeneous phosphorus distribution is considered. The role of reabsorption of the junction radiation is pointed out. With increasing current, the peak emission shifts to higher enwgy. This is alm true in cases where slow line narrowing occurs simultaneously. The length dependence of the threshold current density for lasing at 77 °K was examined for lasers made from the same material. It was found that longer lasers have lower threshold curvent densities, Estimates of the characteristic laser losses are given. Data concwning the range of Gap concentration in which stimulated emission was observed are presented. FORWARD-BIASED p-n junctions in mixed alloys of GaAsxPl-, emit light whose wave length depenfs on the composition of the alloy ranging from 8400A (x = 1) to 5350A (x = 0) at 77°K. Laser action in vapor-grown material was first reported by Holonyak and evacqua,' and in boat-grown material by Ainslie, Pilkuhn, and Rupprecht.' In both cases this was observed for low Gap concentration where GaAs,Pl-, is still a "direct" semiconductor with the lowest conductance-band minimum at k = 0 and a subsidiary minimum in the [loo] direction. As the Gap concentration is increased, the subsidiary [loo] minimum in the conduction band is lowered and finally becomes the lowest minimum for Gap concentrations above 50 pt,3 making the alloy an ''indirect" semiconductor. It is of interest to determine up to which Gap concentration stimulated emission can be observed. EXPERIMENTAL Boat-grown material was prepared by N. Ainslie of IBM by horizontal Bridgman technique. The material was n type and silicon-doped up to a concentration of 10'' cm-'. Vapor-grown material was made by E. Hull of IBM or received from Merck & Co. Diodes were fabricated in a similar manner as in the case of GaAs by zinc diffusion. Details about the diffusion can be found in a later paper.4 All diodes were of Fabry-Perot structure with two parallel sides cleaved and the other two sides sawed. Their width ranged from 50 to 150 p and their length from 50 to 700 p. RESULTS AND DISCUSSION Spectral Distributions. A typical display of the junction luminescence of a GaAsxPl-, diode is shown in Fig. 1. The liquid-nitrogen and room-temperature curves which were taken at a very low current (25 ma dc) show a relatively sharp high-energy emission which is band-edge radiation. They also show a broad low-energy emission which is due to transitions to deep impurity levels. This latter emission line may have different shapes and positions depending on the nature of the material. It can sometimes be quite near the band gap giving rise to "bumps" in the high-energy line. The results presented in this paper will be concerned only with the high-energy emission which becomes more intense relative to the low-energy emission when the current is increased and the temperature is lowered.

Jan 1, 1964

By A. U. Seybolt, D. H. Haman

The rate of oxidation of the lowest nitride of chromium, Cr2N, was measured to be equal to the rate of oxidation of chromium metal. It was found that, while the presence of Cr2N in chromium does not affect the oxidation mechanism, a long exposure at high temperature affects the morphology of Cr2N in chromium, causing a massive internal nitriding along chromium pain boundaries. Marker expen' -ments showed that the rate of oxidation of Cr2N layers on chromium is determined by the rate of chromium diffusion through Cr,03. The rate of formation of Cr2N is determined by diffusion rate of nitrogen through Cr2N. This rate at 1000°C is around thirty times faster than the rate of oxiahtion. Evidence is presented which suggests that nitrogen from the air reaches the chromium through the Cr2O9 by migration through pores or cracks rather than by a diffusive process. IT has long been recognized that, when chromium or alloys containing substantial amounts of chromium are oxidized in air, some chromium nitride (Cr2N) is formed under the oxide scale. Although the presence of this nitride layer has often been described, there appears to have been no systematic study of the role played by the nitride during the oxidation process. Indeed, there have been conflicting re-ports'92 on the kinetics of oxidation of chromium and chromium alloys in air and in oxygen. However, it is now well-established'-5 that the rate-controlling process during the parabolic oxidation of chromium to Cr2O3 is chromium-ion diffusion through Cr2O3. Because of the importance of chromium-containing alloys as oxidation-resistant materials, it seemed desirable to investigate the behavior of chromium during oxidation with and without the presence of chromium nitride. Since a semicontinuous Cr2N layer forms relatively early during the oxidation of chromium in the air, chromium atoms must either pass out of or through the Cr2N layer to become incorporated in the growing Cr2O3 scale. Therefore, it seemed desirable to examine the oxidation behavior of the pure nitride. MATERIALS AND EXPERIMENTAL PROCEDURE The chromium used in this investigation consisted of slices of an ingot made from "five-nine" iodide chromium which had been argon-atmosphere melted in a Y2O 3-stabilized ZrO2 crucible in an induction furnace. The only impurity of any significance was 625 ppm of 0, which was usually reduced to a microscopically invisible amount by hydrogen annealing at 1400°C. However, one sample of chromium was used with the as-cast oxygen level as explained below. The samples were used after abrading through 600 Sic paper and then washing in toluene and alcohol. Both nitriding and oxidation experiments were performed in a vertical tube furnace connected to a glass vacuum system. 'This system was equipped with pressure measuring instruments for the range of 10 p to 1 atm, and a cartesian-diver pressure-control device was used in conjunction with a needle valve to allow control of pressure in the range of about 10 to 760 mm. The nitrogen or hydrogen gas was purified by passing through hot copper chips at 600°C, anhydrous calcium sulfate (Drierite), and liquid nitrogen. Oxygen gas was dried through the Drierite column and a dry-ice trap (-78°C). Changes in specimen weight were followed by a Pyrex helix used in conjunction with a cathetometer which could reproducibly be read to +0.001 cm, yielding an accuracy of about +0.2 mg. The spring was maintained in the cool upper part of the furnace tube where the temperature did not rise above about 35°C. The nitride in equilibrium with metallic chro-

Jan 1, 1964