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By Robert F. Mehl

EXTENSION of physical and chemical methods of research in the study of metallic behavior continues rapidly, particularly in the correlation of behavior with crystal structure, and in the analysis of elastic and plastic properties. The growth of the science of metals during 1933 calls for special comment; the need for special reviews and for textbooks and monographs is now acute, as might he supposed from the number of references appended to this article, a list which is much abbreviated.

Jan 1, 1934

By James H. TaVoularis, William J. Wiehagen

This paper discusses the application of commercially available microcomputers for assisting trainers in the delivery and evaluation of new hire, refresher, and occupational training. A brief overview of mine training highlights major issues facing the mine training community. The use of computer-based training has a potential for reducing costs and improving the transfer of conventional training to the job.

Jan 1, 1983

By John Griffen

DURING the past year, purchases of coal-preparation equipment and the discussions and plant-scale tests conducted indicate that much attention is being given to better recoveries of coal by preparation plants and improved quality of the finer sizes to widen their market. In the anthracite regions the new equipment was predominantly for the cleaning of the steam sizes, much of it for treating No. 4 and No. 5 buckwheat. The units installed were largely coal-washing tables, Hydrotators, and Menzies cone separators.

Jan 1, 1944

AT the fall meeting of the Iron and Steel Division, Oct. 4, 1934, in New York, a symposium was held on Slag Control in the Making of Iron and Steel. The chairman was J. H. Nead and the vice chairman, G. B. Waterhouse. The latter presided at both morning and afternoon sessions. The papers and discussions were presented in the order in which they appear on the following pages. To meet space requirements, much of this material has been considerably condensed. CONTENTS [ ]

Jan 1, 1935

By K. Kobayashi, K. Ueda, K. Yamaguchi

Lead concentrates from Kuroko (black ore) mines, which contain 4-7% Cu, 55% Pb, 3-777, Zn, and 0.5-0.9% As, are pretreated by a hydrometallurgical process before electric furnace smelting with other lead resources from Kuroko. The hydrometallurgical pretreatment involves sulfuric acid leaching in the first stage and ferric leaching in the second stage. This paper describes the short history of lead recovery from Kuroko and the performance of laboratory tests and pilot plant and commercial operations.

Jan 1, 1985

[Trans. No. Place Date Vol. Page 1. Wilkes-Barre, Pa.*.. *May: '71.. 1 3 2. Bethlehem, Pa Aug. '71.. 1 10 3. Troy, N. I X Nov. '71.. 1 13 4. Philadelphia, Pa Feb. '72.. 1 17 5. New York, N. Y.*.... May, '72.. 1 20 6. Pittsburgh, Pa Oct., '72.. 1 . 25 7. Boston, Mass Feb., '73 1 28 8. Philadelphia, Pa.*.... May, '73 2 3 9. Easton, Pa Oct., '73 2 7 10. New York, N. Y Feb., '74.. 2 11] [ ]

Jan 1, 1925

[JAMES A. BARR Consulting Engineer Mt. Pleasant, Tennessee Washington) D.C. BEHRE DOLBEAR & COMPANY Consulting Mining Engineers and Geologists 11 Broadway New York 4, N. Y. BLANDFORD C. BURGESS Registered Professional Engineer Mining Consultant Monticello, Georgia GLENVILLE A. COLLINS Mining Engineer Uranium examinations Cable "Coins" 210 La Arcada Bldg. Santa Barbara, Calif. COWIN & CO. Mining Engineers and Contractors Consulting Shaft & Slope Sinking Appraisal Mine Development Reports Mine Plant Construction I- 18th St. S. W. B'ham, Ala., Phone 56-5566]

Jan 1, 1952

By Barry S. Siegal

Spectral reflectance data in the wavelength region of 0.45 to 2.4 µm have been obtained for various rock types and different forms of natural vegetation by means of JPL's portable field reflectance spectrometer. Computer analysis of these data has demonstrated the importance of obtaining remotely sensed spectral data beyond the wave- length region sensed by Landsat. Computer processing techniques have been developed and used for the analysis of these data and their application to a variety of geologic problems.

Jan 1, 1977

By Tommy Wilson

OIL well drilling fluids have become a vital part of the drilling industry during the past 25 years. From chance usage of drilling mud at the fabulous Splindletop field in 1901, drilling fluid control has become an extremely technical and exacting science. Drilling for oil today involves exploration at depths ranging to 21,000 ft, nearly 4 miles. Geological formations encountered at these depths offer a tremendous challenge to the production, research, and service facilities of any drilling mud company.

Jan 5, 1954

By R. G. Fleck, W. R. Webb

The concentrate produced from the Adirondack magnetites is, of course, too fine for direct use in a blast furnace and must be agglomerated before it can be considered a blast furnace ore. The four operations in the area use sintering -three, including the Jones & Laughlin operation, employing the Dwight Lloyd continuous type machine and one operation using the Greenawalt batch type process. Each operation uses fine anthracite coal, either No. 4 or No. 5 buckwheat size, for the mix fuel.

Jan 6, 1950

By Orvar Nyquist, Klaus W. K. Lange, John Chipman

Liquid Fe-C-Si alloys containing 0 to 12 pet Si and up to 4 pet C were equilibrated with carburizing gases at 1550°C. Two to 5 alloys simultaneously were held in close proximity for 5 to 7 hr to establish uniform carbon activity in the group. Analysis of the data gives the activity coefficient of carbon as a function of the mole fractions of carbon and silicon, Fig. 7. Values of the interaction coefficients at infinite dilution are

Jan 1, 1962

By Joseph D. Weeks

FIFTY-eight years and a day, full of labor, of achievement and of honor had been completed when, at Pittsburgh, on the 5th day of May, 1892, the wheels of a life that had but just before lost its inspiration stood still, and the work here of William Powell Shinn was at an end. Born at Burlington, N. J., May 4,1834, he received such an education (and it was. the only school education he ever had) as the public

Jan 1, 1893

By Roland Kammel

For electrolytic recovery of silver from dilute aqueous solutions improved mass transfer is necessary to achieve favourable current efficiencies and high space-time yields. The many cell designs proposed for this application can be divided into two different groups: cells from which the silver must be redissolved and cells from which the deposit can be reclaimed as a metal. Introduction Electrolytic silver recovery methods have proven advantageous under technical and economic aspects for the treatment of rinse water, still rinses and spent silver solutions in the electroplating and surface finishing industry, of exhausted fixing baths from photographic processing, bleed electrolytes from silver refining processes and leach liquors. Examples of the compositions of typical dilute silver solutions are listed in Table I.

Jan 1, 1984

By F. A. Crossley

The titanium-rich end of the Ti-A1 system has been investigated up to 35 at. pct A1 (23 wt pet). One conzpound Ti3Al was found to occur between primary a and TiAl. It is ordered hcp with DO19 structure, it has virtually no solid-solubility range, and it has a closed maximum at about 875°C. OIL either side of the compound are a +Ti3Al two-phase fields. The limiting a1uminum solubility in primary a at the titanium-rich end is indicated to be 7.5 at. pct A1 (4.4 wt pet) at 550°C and about 6.8 at. pct Al fl wt pct) at 500°C. Quenching alloys from above the a + Ti3Al two-phase field produces the following structures with respect to alloy composition: Up to 13 at. pct A1 (7.8 wt pet), a solid solution; from 15 to 18 at. pct A1 (9 to 11 wt pct), shear transformation product or martensite; from 19 to approximately 30 at. pct (11 to 19 wt pet), submicro-scopic coherent Ti3Al in an a malvix. The twin hcp phase fields reported in the literature are the result of nonequilibrium corzdztions. Ti-A1 alloys, once partitioned by dwelling- in the a + ß phase field during either hot working or heat treatment, are extremely difjicult to homogenize at temperatures below 1000°C. Such partitioned alloys exhibit the characteristics or symptoms of two-phase materials, and may be said to suffer the "twin-phase syndrome". THE earliest investigations of the Ti-A1 system by Ogden et al.1 and Bumps et al.2 reported wide solubility of the primary solid solutions. Aluminum was reported soluble in the low-temperature allomorph to the extent of 37 at. pct (25 wt pct), and the first intermediate phase was reportedly TiA1. Somewhat later Kornilov et al.3 reported a similar diagram with phase boundaries displaced towards lower aluminum contents and higher temperatures. Beginning about this time (1956) reports in the literature made it very clear that one or more intermediate phases occurred at lower aluminum contents than TiAl.4-17 These reports included five major investigations of the titanium-rich end of the Ti-A1 diagram.4,12,14,16,17 Three of these diagrams show two two-phase fields below 37 at. pct Al, while two of them show a single two-phase field. The existence of the phase Ti3A1 is firmly established and is included in each of the diagrams, except one—that of Sato and Huang.12 The new phases are reportedly hcp and differ from primary a only slightly when disordered, and when ordered the "a" parameter is approximately one,4,12,15 two, 6-10,13,14 or four14 times that for primary a. Beyond this, however, the diagrams are remarkable for their lack of agreement. Two tacit assumptions are usually made in phase-diagram determinations of metal systems. These are: 1) equilibrium anneals bring the alloy to equilibrium or to indistinguishable closeness to it, and 2) equilibrium conditions established at elevated temperatures are either "frozen" by rapid quenching for evaluation at room temperature, or quench-transformation products are recognized as such. In the current investigation evidence was obtained that over substantial composition ranges neither of these two conditions was met in any of the more recent major investigations. I) MATERIALS, METHODS, AND TECHNIQUES The alloys of this investigation were prepared by nonc on sum able electrode arc melting. Materials used in the preparation of the alloys are summarized in Table I. The investigative tools employed were: optical and electron microscopy, differential thermal analysis (DTA), disatometry, X-ray diffraction, electron diffraction, and resistometry. Alloys for microscopic and X-ray investigations were prepared as 15-g melts. Alloys containing from 7 through 11 at. pct A1 were hot-rolled out of a furnace at 900°C, from 12 through 15 at. pct out of a furnace at 1000°C, and from 16 through 18 at. pct out of a furnace at 1125°C. Alloys containing more than 18 at. pct A1 could not be hot-rolled. The ingots were covered with Markal coating prior to hot rolling to minimize atmospheric contamination. After hot rolling, alloys containing up to 15 at. pct A1 were ground and pickled to remove 7 mils from each surface; alloys containing 16 and 18 at. pct A1 were skinned to a

Jan 1, 1967

By R. L. Fleischer, W. F. Hosford

Tensile data for coarse grained aluminum Polycrystals suggest that the "grain size" effect is not due to dislocations piled up at grain boundaries but rather is primarily a relative size effect due to surface crystals being weaker and less confined. STUDIES directed at interpreting hardening of poly-crystalline metals normally identify their strain hardening properties with those in some particular type of single crystal.1"4 The recent recognition in face centered-cubic metals of a nearly linear stage with rapid hardening occuring at comparable rates for both polycrystals and single crystals, suggested that the same process or processes determine both cases and hence that there exists some justification for the use of single crystals to understand polycrystals. Further evidence for the above view may be found by an approach initiated by Chalmers:5 By using bicrystals of controlled orientation it is possible to begin to assemble a polycrystal and also to study grain boundary effects in detail. In this way it has been found that a single grain boundary affects easy glide but not the subsequent stage II hardening.6 This result suggests that a sensitive way to observe grain boundary effects in polycrystals would be to vary grain size and measure easy glide. As will be seen, easy glide is only possible for coarse-grained samples, and hence the results will serve to fill in the gap in measurements between single crystals and bicrystals on one hand and fine-grained polycrystals on the other. One problem inherent in comparing single crystals with polycrystals is the uncertainty as to what slip systems are acting in a polycrystal. To compare the two types of samples, rates of shear hardeninn---L. on the acting -planes are needed. and these may be computed only if it is known what particular systems are active. The acting systems were examined for a coarse-grained polycrystal and it will be shown that the systems supplying the preponderance of slip can be determined with little ambiguity. EXPERIMENTAL PROCEDURE Twelve samples of aluminum were prepared by chill casting into a heated graphite mold, followed by annealing at 635° ± 5°C for 24 hr with an 8-hr fur- nace cool, and finally either etching7 or electropol-ishing.' The samples, with a 7 to 10 cm length between grips and 4.4 by 6.6 mm in cross section, were deformed at a strain rate of about 3 10 -3 . per min in a tensile device which has been described elsewhere.5 The composition was reported by Alcoa as 99.992 pct Al, 0.004 pct Zn, 0.002 pct Cu, 0.001 pct Fe, and 0.001 pct Si; nine samples were deformed while immersed in liquid helium and three in air at room temperature. The stress-strain curve for one of the samples (P-1) deformed at 4.2 "K has been reported previ~usl~.~ This sample was selected for determination of active slip systems. Eighteen of the crystals were examined by optical microscopy to determine the angles of slip line traces and by X-ray back reflection to determine orientation. By this means the slip planes were determined and the resolved shear stress factors for possible slip systems could be computed. Finally each sample was sectioned so that after etching, the number of crystals could be counted for each of ten newly exposed surfaces. The average of these ten values will be termed n, the number of crystals per cross section. Values of 11, varied from 1.9 (nearly bamboo structure) to 12.7. Sketches of typical cross sections appear in Fig. 1. RESULTS AND DISCUSSION: SLIP SYSTEMS 1) Determination of Acting Slip Planes—The stress axis orientation and operative slip planes in eighteen crystals of sample P-1, as determined by slip line traces and crystal orientation, are summarized in Fig. 2. For one of the crystals two planes had a common trace. so that the traces alone did not distinguish which plane or planes were slipping. However it was found that the stress resolving factor for the primary system was 0.386, .while that for the most stressed system in the other plane (indicated bv the dotted arrow) is 0.138. It will be assumed tgerefore that only the primary plane acted. Since the orientations were determined after extending the samples 4 pct, the stress axes may be rotated from their original value by as much as 2 deg in some cases. It is interesting to note that in five crystals only one slip plane acted, in eight two acted, and in five three planes were observed—an average of two slip

Jan 1, 1962

By T. G. Digges, C. L. Vold, M. R. Achter

A study was made of the effect of the growth conditions on the perfection of single crystals of niobium (columbium). Dislocation densities, determined by means of double-crystal diffractometer measurements , were not greatly affected by the method of crystal preparation but could be reduced by annealing treatments. However, the size, sharpness, and tilt angles of the substructures, observed with X-ray reflection macrograph, were sensitive to variations in growth procedures as well as to subsequent thermal treatments. Although the dislocation density was the same in both types, there were more low-angle bound-aries in crystals grown by zone melting than in those prepared by strain anneal. Mechanisms to account for these observations are discussed in terms of dislocation movements. A planned study of the structure-sensitive properties of refractory metals required the use of single crystals of a high degree of structural perfection and, for ease of handling, of large cross section. It appeared that the strain-anneal technique could satisfy both of these requirements. First, crystals grown in the solid state have been reported to be more perfect than those obtained from the melt.' Second, the diameters of rods which may be produced by zone melting should have a theoretical limit determined by specific gravity, thermal conductivity, and surface tension, while the diameter of strain-annealed rods is limited only by practical considerations. Previously it was shown that niobium (columbium) single crystals of 1 in. diam2 may be grown by strain anneal, compared to the 0.5 in. maximum diameter achieved by zone melting, as reported for molybdenum by Belk.3 The current research was undertaken to investigate and optimize the effect of various process variables on the perfection of 1/4 and 1/2-in.-diam niobium single crystals grown by strain annealing and to compare their perfection to those grown by zone melting. Characterization of these crystals was more conveniently accomplished by means of X-ray than by metallo-graphic techniques. EXPERIMENTAL PROCEDURE Specimen Preparation. Zone-melted crystals of 1/4 in. diam were produced by the standard electron-beam zone-melting technique. The swaged and cleaned rods were outgassed, in the solid state at a temperature near its melting point, at a rate of 12 in. per hr, and single crystals were grown by making two molten passes at 2 in. per hr. By maintaining a zone length of 4 to % in., very uniform single crystals several inches long were obtained. For the strain-annealed crystals, an induction heater was used, in preference to other types of heating, to take advantage of the good penetration of large sections. A five-turn coil, 1 in. long, operating at 10 kc and powered by a motor generator, was contained in a vacuum chamber. The rod, suspended from the upper end, was raised through the coil for both recrystallization and crystal growth. In preliminary work single crystals of the same material were also grown with single and multiturn coils powered by a 450-kc generator. A vacuum of 2 X 10-6 Torr was maintained at temperatures up to 2400°C. Starting with electron-beam-melted ingots of 21/2 in. diam, the analysis for which is given in Table I, the material was cold-swaged to the desired cross section of 1/4 and 1/2 in. diam and then recrystallized. The rods were then strained in a tensile machine and converted to single crystals by passing through the induction coil. As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and smallman,4 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point in the poly crystalline portion. Finally, it is returned to the chamber and growth is continued "around the corner". This procedure has certain limitations. If the bending operation exceeds the critical strain, recrystallization may take place. Also, the amount of bending which can be imparted to the rod is limited by coil geometry, and up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. In preparation for X-ray examination, single crystals were sectioned and planed by means of the spark-erosion technique. To obtain the maximum reflected intensity, the (110) plane was exposed for examination. They were then etched 3 to 5 min in a mixture of con-

Jan 1, 1967

By D. Mills, G. B. Craig

ZIRCONIUM has been float-zone-refined in an electron-beam furnace and the redistribution of oxygen, iron, and tungsten has been measured. The iodide zirconium used in the present experiments initially contained both oxygen and iron in the range 100 to 200 ppm by weight, and tungsten in amounts less than 10 ppm. Float-zone refining of zirconium, using induction heating, has previously been attempted by Kneip and Betterton1 and Langeron.2 Kneip and Betterton were primarily interested in the removal of iron and nickel. They achieved some purification, with respect to both these elements, in material given up to six passes at 150 mm per hr under an argon atmosphere. Langeron reported purification for a large number of elements after four completed passes in a static vacuum system operating at pressures less than 10-6 mm of Hg and with rates of zone travel between 30 and 40 mm per hr. He did not report oxygen concentrations, but stated that there was inverse segregation of this element. westlake5 has also used a minimum of four zone passes to remove iron from zirconium. No rates or conditions were given. Belk6 has shown that tungsten contamination can occur during electron-beam melting. He reported an increase from 0.01 to 0.05 pct by weight tungsten in molybdenum after four complete zone passes. The vacuum system for the electron-beam unit used in the present investigation consisted of a single-stage rotary pump backing a liquid-air-trapped oil-diffusion pump. A pressure of less than 10-8 mm of Hg was obtained with Dow-Corning 705 fluid in the diffusion pump. In order to avoid contamination of the zirconium by evaporation from the tungsten filament, a special focusing cage4 was employed. Three rates of zone travel, 114, 38, and 4 mm per hr, were investigated, with the liquid zone moving from the bottom to the top of the bar. The bars used were 3 mm diam and the total melted length was 130 mm. Oxygen was analyzed by neutron-activation analysis using a neutron flux of 10' neutrons per sq cm per sec to form the isotope N16 by the 016 (n,p) N16 reaction. The standard deviation is quoted for each oxygen determination. The iron and tungsten analyses were performed spectrographically, and the precision is estimated to be ±6 pct. Analyses for tungsten were all below the detectable limit of 10 ppm, confirming the protection given by the focusing cage. No significant redistribution of oxygen was found at the two higher rates of zone travel. The redistribution of oxygen and iron obtained after five passes at a rate of zone travel of 4 mm per hr (1.1 x 10-4 cm per sec) is recorded in Tables I and 11. Burris, Stockman, and Dillon3 have estimated the distribution of solutes during multipass zone refining. Using their curves for an effective distribution coefficient of Keff = 1.5 and 2 for oxygen and Keff = 0.3 for iron, the expected concentrations were estimated for the present material. These are shown in Tables I and 11, along with the experimentally measured values. The calculated concentrations are based on a molten-zone length of 10 pct of the total melted length, whereas in the present experiments the molten zone was approximately 5 pct of the total melted length. The effect of zone length on solute redistribution is most pronounced after a large number of zone passes. Comparison with Pfann's published data8 for solute redistribution for various Keff's and zone lengths indicates only small differences at low numbers of completed zone passes. It is evident that the expected distribution has not been realized in the case of iron. Scrapings of material deposited on the inner surfaces of the electron-focusing cage were found to be magnetic. It is, therefore, concluded that redistribution of iron is masked by evaporation. Deposition of iron inside the focusing cage was observed at all rates of zone travel. The results of the investigation may be summarized as follows: 1) Segregation of oxygen is typical for a solute with a distribution coefficient, Keff > 1. 2) No redistribution of oxygen takes place at high rates of zone travel. 3) The distribution coefficient for oxygen lies between 1.5 and 2.0. 4) Purification with respect to iron occurs mainly by evaporation. 5) The focusing cage is effective in preventing tungsten contamination.

Jan 1, 1967

By H. S. Chiang, D. F. Lu, S. S. Peng

INTRODUCTION The most important element in a successful lingual mining is a good roof control. The modern longwall mining employs hydraulic powered supports for roof control at the face area. The application of hydrau¬lic powered support requires the knowledge of over¬burden strata behavior for proper selection of sup¬port type and capacity. Failure to do so could lead so serious loss. There are several methods available for determining the required support capacity (1-3). While these methods are simple for application, they do not include the complicated roof behavior observed in longwall mining. As research progresses and operational experience accumulates (4,5), the concept about the designing and selection of powered support improves. The design of a longwall powered support consists of three major phases: 1. structural integrity and stability of the powered support, 2. external loadings induced by the movements of the overburden strata, and 3. interaction between the support, roof and floor. Phase 1 involves structural analysis (5) and full-sized testing (6) of the supports. Its validity is limited by the accuracy of the assumed external loading because of the uncertainty about the actual loading underground. The third phase includes the reaction of the support and the floor to the movements of the overburden strata and vice versa. Among the three phases, the second phase concer¬ning the external loading seems to be the least known because of the complicated behavior of the roof strata. There are many unresolved problems. For example, does the main roof break periodically and cause periodic roof weighting in the face area? If so, are there any rules governing its behavior? How does the roof load on the support canopy! Finally, how can one determine the required support capacity and select a proper type of support to meet a certain roof behavior? In order to answer those questions, underground instrumentation and observations were performed at 4 longwall panels in 3 separate mines for the past two years. This paper summarizes the current findings. PANEL LAYOUTS AND EQUIPMENT EMPLOYED The three mines selected are all located in West Virginia; two in northern and one in southern West Virginia. As shown in Table 1, seam conditions (i.e. seam, depth and thickness) and panel layouts are different among the three mines. The most significant difference in equipment is the face powered supports. Three mines used three different types of shield; 2-leg caliper, 2-leg lemniscate, and 4-leg lemniscate chock-shield. (Fig. 1) UNDERGROUND INSTRUMENTATION AND OBSERVATION PROGRAM Two events were instrumented in each observed longwall face: one was the hydraulic pressure (resistance) of the powered supports and the other was the canopy load distributions. In addition, the gob caving conditions were visually observed and recorded. Leg and Support Resistances One or two automatic Weksler Pressure Recorders were installed at the designated shield support,. In most cases, the daily charts were used to record the pressure variations in both the front or the rear legs (for the 4-leg shield), or in both the leg and the fore-pole ram (for the 2-leg shield). The recorded pressure w a s then converted to load or resistance by multiplying it by the cross-sectional area of the hydraulic leg or canopy ram piston. Fig. 2 shows the typical pressure-recorded charts for the 4-leg and 2-leg shields in a 23-24 hour period. The support resistance is the summation of the resistance in each of all the legs for that support. Generally, the resistance of the fore-pole ram will not be considered in determining the capacity of the support because of its rather small vertical compo¬nent force at the tip of the fore-pole. Canopy Load Distribution External load distribution on the canopy as exer¬ted by the roof was monitored. The measurements employed 12-14 pieces of pressure cells (6-inch square) that were uniformly arranged in two rows on the canopy. After support setting, the pressure changes in the cells were monitored at various stages of the mining (supporting) cycle while the support leg pressures were recorded continuously by the pressure recorders. Based on the calibration chara¬cteristics of each pressure cell as performed in the laboratory before and after each underground test, the cell pressures were converted to actual loadings. From these load measurements the canopy load distri¬butions and the relations between measured canopy loadings and support leg resistances were determined. Accordingly, the supporting efficiency of the shield support can be determined.

Jan 1, 1982

By K. G. Davis

Dilute alloys of silver and of thallium in tin have been solidijzed unidirectionally under controlled conditions, to study the segregation associated with a cellular interface under conditions where both thermal and solute convection are present. Autoradiography and radioactive tracer counting techniques were combined with electron-probe microanalysis to study both macro- and microsegregation. It was found that, for concentrations giving only small amounts of constitutional supercooling, cell formation had little effect on the macroscopic distribution of solute along the specimen. At higher concentrations the effective distribution coefficient was higher than that expected for a smooth interface. Node spacing was independent of initial solute content at lower concentrations, becoming greater as keff increased. Silver content at the segregation nodes of silver in tin alloys was independent of initial concentration and considerably in excess of the eutectic composition. SINCE the investigation of cell formation at advancing solid-liquid interfaces by Rutter and Chalmers,' a large volume of work has been dedicated to the determination of solidification conditions under which a planar interface will break down into cellular form. Early experiments were explained satisfactorily by the concept of constitutional supercooling,2 but, due to poor measurement of temperature gradients in the liquid, lack of accurate data on liquid diffusion and equilibrium distribution coefficients, and uncertainty about the effects of thermal and solute convection, these experiments cannot be used as proof for the theory. More recent work, however, has shown that under conditions where convection is eliminated or can be ignored good correlation is observed.3,4 Investigations into segregation at cell caps5 and at cell nodes6-'' have been made, but no measurements appear to have been done on the overall, macroscopic segregation down a unidirectionally solidified rod of material which has solidified with a cellular substructure. This has practical importance in casting, where regions of material with cellular substructure are often encountered, and also in zone refining where the thermal conditions necessary for a planar interface are unattainable. Further, as will be shown, the macroscopic segregation can give information on the following question. Granted that a cellular solid-liquid interface develops from a planar one when the conditions for constitutional supercooling are exceeded, how much supercooling is present after the cells have formed? EXPERIMENTAL PROCEDURE AND RESULTS Specimen Preparation. Specimens 25 cm long with a square cross section 0.6 by 0.6 cm were grown in graphite boats by solidification from one end. Alloy compositions are given in Table I. Two specimens of each composition were grown. The tin was 5-9 grade and the silver and thallium both 4-9 grade. Ag110 and Tl204 were used as tracers. Each composition had the same quantity of tracer so that auto radiographs of specimens containing different concentrations of the same element could be easily compared. Thermocouples inserted through the lid of the boat into a dummy specimen showed that, over the first 10 cm of growth, thermal conditions were quite steady, with a rate of interface advance of 5.8 cm per hr and a temperature gradient in the melt ahead of the interface of 3.0°C per cm. The specimens were seeded from tin crystals of a common orientation to eliminate orientation effects. Dilution of the specimen by seed material was minimized by the provision of a narrow neck between specimen and seed crystal. Macrosegregation. After growth, the specimens were sectioned with a spark cutter. The rods of silver alloy were cut into 1-cm lengths and analyzed for Ag110 using a y -ray counter with fixed geometry. The specimens containing thallium were cut into 2-cm lengths and analyzed for T1 204 by taking 13 counts from each end of the cut lengths through an aperture in lead sheet approximately 0.4 cm square. The results are summarized in Figs. 1 and 2. To find the effective distribution coefficient for the silver in tin alloys under smooth interface conditions, the region of substructure at the bottom surface of one of the 10 ppm specimens, see Fig. 3, was removed by spark machining before counting. Autoradiography. For both alloy systems the samples were polished on sections taken alternately parallel and perpendicular to the growth direction, and autoradiographed by placing the polished surfaces in contact with Kodak "Process Ortho" film. Figs. 3 and 4 show the structures revealed. The alloy containing 10 ppm Ag showed substructure only after a few centimeters of growth, and then substructure was limited to a narrow layer at the base. The "speckled" substructure reported previously in this system4 is here clearly seen to be an intermediate stage between planar and cellular interface conditions. The other samples show a remarkable similarity considering

Jan 1, 1969

By Jean Howard

RECENT attempts to produce secondary recrystalli-zation in high-purity iron have given conflicting results. Coulomb and Lacombe1'2 did not find it but Dunn and Walter3,4 did. The latter workers have stated that (100) [001] and/or (110) [001] orientations develop depending on the oxygen content of the annealing atmosphere. This Technical Note records results which are in agreement with Dunn and Walter in so far as it shows that secondary recrystallization can be produced in high-purity iron, but does not confirm that both types of orientation are obtainable. Similar observations have been made on chromium-iron and molybdenum-iron, although when this technique is used on 3 1/4 pct Si-Fe, both types are obtained as in the work of Dunn and alter.' Pure iron strip was cold-rolled from sintered compacts prepared from Carbonyl Iron Powder-Grade MCP of the International Nickel Co. (Mond) Ltd. The powder contains about 0.5 pct 0, 0.01 pct C, 0.004 pct N, (0.002 pct S, $0.005 pct Mg and Si, and 0.4 pct Ni—that is, it is substantially free from metallic impurities other than nickel, which is thought to be unimportant in the present work. The iron powder was (a) pressed at 25 tons per sq in. into blocks measuring 3 by 1 by 0.3 in., (b) deoxidized in hydrogen (dewpoint -60°C) by heating first at 350°C and then at 600° C until the dewpoint returned to -60°C at each temperature and (c) sintered in hydrogen (dewpoint -40°C) at 1350°C for 24 hr. (when dewpoint is referred to in this Note, it is the value as measured on the exit side of the furnace). The sintered compacts were cold-rolled to 1/8 in., annealed in hydrogen (dewpoint -60°C) at 1050°C for 12 hr and cold-rolled to 0.004, 0.002, and 0.001 in. with inter-anneals at 900°C for 5 hr and a final reduction of 50 pct. Final annealing of strip between alumina or silica plates at 875" to 900°C in hydrogen with dewpoints of -20°, -55" and -80°C produced secondary grains with the (100) in the rolling plane; the extent of secondary recrystallization was greatest when the dewpoint was -55°C. Annealing in a vacuum of 2 x 10"5 mm Hg at the same temperature produced no secondary recrystallization at all. With strip thicker than 0.002 in. very few secondary crystals developed whatever the conditions of annealing. Using a processing schedule somewhat similar to that described above, secondary recrystallization was produced in two bcc alloys of iron, viz. 80 pct Fe + 20 pct Cr and 96 pct Fe + 4 pct Mo. The former was reduced to final thicknesses of 0.001 to 0.004 in. and the latter to final thicknesses of 0.001 to 0.016 in. With the chromium-iron, a final anneal at 1250°C (found to be the most effective temperature for developing secondary crystals in the 0.004-in material) with a dewpoint of -25°C produced a greater degree of secondary recrystallization than with dewpoints of -50°C or -20°C. Secondary crystals developed in strips of all thicknesses from 0.001 to 0.004 in. Final annealing in vacuum produced no secondary crystals at all. For the molybdenum-iron a temperature of 1200°C was most effective. It was found that a dewpoint of -50°C during the final anneal gave better results than a dewpoint of -25 "C on the 0.008 in. material. Final annealing in vacuum gave slightly worse results than annealing in hydrogen with a dew-point of -50°C. Secondary crystals were developed in strips of all thicknesses up to 0.008 in. The experiments show that the extent of secondary recrystallization is a maximum for certain critical values of oxygen content of furnace atmosphere and annealing temperature, and that these values are different for different alloys. The thinner the material, the less critical these values are. The general conclusions are that secondary recrystallization can be obtained in high-purity iron, chromium-iron, and molybdenum-iron, using a processing schedule similar to that which will cause the phenomenon to take place in high purity 3 1/4 pct Si-Fe. Unlike the silicon-iron, however, only the (100) (0011-- orientation has been produced in these alloys, irrespective of the temperature of final annealing and the oxygen content of the furnace atmosphere. The information used in this Note is published by permission of the Engineer-in-Chief of the British Post Office.

Jan 1, 1962