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By W. Vickers

Single-point rotating cantilever fatigue tests have been carried out at 550" to 650°C on beryllium produced by a variety of fabrication routes. All the specimens gave similar plots of stress against number of cycles to failure but failure occurred at a lower stress range in the hot-pressed material than in the extruded material. A discontinuity or "kink" appears to exist in the curves and this is considered. A true endurance limit was not evident up to 10 cycles. When Brush hot-pressed warm-extruded beryllium was tested at 600oC a relationship where Nf = number of cycles to failure, ?ep = plastic strain range, and c = constant, was shown to be applicable for values of ?ep > 6.3 x 10-4. Further for this moterial and temperature and for frequencies between 150 and 4500 cycles per min, the variation of number of cycles to failure with frequency obeyed the expression N = Af0.44 where N =number of cycles to failure, f = frequency, and A = constant. Examination of the fracture surfaces indicated that they were generally intergranular and in all cases the higher the stress the more irregular was the fracture. Microexamination has shown that grain boundary cavities and fine intergranular cracks were associated with the fractures. REVERSING or cyclic stresses set up in fuel elements can lead to failure by fatigue. Fatigue stresses may be developed by instability of the fuel element in the coolant flow leading to rattling against the channel wall or fin vibration. Thermal cycling also sets up reversing stresses due to differential expansion of fuel and can. Fatigue resistance is of some importance therefore in the evaluation of canning materials. At the time the work described in this paper was initiated, beryllium was being considered for the can and endcaps of an advanced gas-cooled reactor fuel element. With this in mind, beryllium obtained from different manufacturing routes was tested on single-point rotating cantilever fatigue machines at temperatures the same as those envisaged in the reactor to obtain appropriate fatigue data. The results obtained indicated a discontinuity in the S-N curves coinciding with the yield stress in the specimens. Although in some cases the data is insufficient to warrant a detailed quantitative analysis, a qualitative analysis of this effect was thought to be justified. 1) EXPERIMENTAL DETAILS The materials used are given in Table I together with the production route and available analyses. The specimen shape is shown in Fig. 1. The fatigue specimens were machined slightly oversize, after which they were given a stress-relieving anneal of 1 hr at '750° C in vacuum. This was followed by an etch in sulfuric-phosphoric-chromic acid mixture down to the finished dimensions given in Fig. 1. Etching served to remove the interference colored oxide film formed on the surface during annealing and very small recrystallized surface grains too. The specimen was mounted in the grips of a cantilever machine and rotated inside a furnace controlled at the testing temperature. The specimen was loaded in increments as the speed was increased until the required load was applied at 5000 cycles per min. A revolution counter was used to record the total number of cycles.

Jan 1, 1964

By J. D. Mote, J. E. Dorn

This investigation was undertaken to study the effects of piledup arrays of dislocations on inducing slip, twinning, and fracturing in magnesium bicrystals. A series of variously oriented bicrystals of magnesium having a vertical grain boundary were prepared and tested in tension. It was found that piled-up arrays of dislocations at the grain boundary could, under appropriate conditions, induce slip, twinning- and cracking. The results that were obtained substantiate, at least qualitatively, the general dislocation mechanism for transmission of strain across grain boundaries and the Petch-Stroh concept of fracturing. WHEREAS single crystals of magnesium generally exhibit extensive deformation, coarse-grained poly-crystalline magnesium at subatmospheric temperatures fractures after a few percent elongation.' Although a small amount of ductility is obtained, several features of this fracturing are characteristic of typical brittle behavior. Over a rather broad temperature range the fracture stress is insensitive to the test temperature and the fracture stress increases linearly with the reciprocal of the square root of the mean grain diameter. The course of fracturing is predominantly intergranular, but small fragments of adjacent grains frequently adhere to the fractured surface.2 The brittle behavior of polycrystalline magnesium is attributable to the limited number of facile deformation mechanisms it exhibits at low temperatures. For a general deformation of a randomly oriented polycrystalline aggregate, each grain must exhibit at least five independent mechanisms of deformation to permit accommodation of the imposed deformation from grain to grain.= Although minor amounts of prismatic slip occur in corners of grains where stress concentrations are known to be high, glide in polycrystalline magnesium at low temperatures takes place almost exclusively by basal slip.' The common type of twinning, which takes place on the (1012) pyramidal planes, can under the most favorable orientations, lead to a. strain of only 6.9 pet; the contribution of twinning to the tensile strain would indeed be much less than this in a randomly oriented polycrystalline aggregate of magnesium. Since the three mechanisms of basal slip are coplanar, they are equivalent to only two independent mechanisms, a number insufficient for a general deformation. Consequently, once the permissible twinning has taken place in conjunction with basal slip, no further plastic deformation is possible because of interference to slip at the boundaries of dissimilarly oriented grains. At this stage brittle fracturing takes place due to high stress concentrations at the juncture of slip bands with the grain boundaries; the predominance of intergranular fracturing in magnesium, in preference to transcrystalline fracturing which is prevalent in zinc, has not yet been rationalized. A more atomistic description of the plastic behavior and fracture characteristics of magnesium follows from the analyses made by stroh4 on the stresses induced by piledup arrays of dislocations. Slip first takes place by dislocation motion in the most favorably oriented grains. As the dislocations approach the boundary of a dissimilarly oriented adjacent grain they begin to form an array of dislocations with its attendant stress field. Piledup arrays of screw and edge dislocations introduce high localized shear stresses at the spur of the array; piledup arrays of edge dislocations also induce high tensile stresses localized in the vicinity of the grain boundary. Whereas the shear stresses can induce slip to take place, the tensile stresses, if sufficiently high, can cause fracturing. The localized shear stress will be relieved if sufficient numbers of mechanisms of deformation become operative in the original and the adjacent grain to permit accommodation of the dislocations in the grain boundary. In this event a ductile behavior will be obtained. But if the number of deformation mechanisms is insufficient for complete migration of dislocation arrays into the grain boundary, the tensile stresses due to the edge components of piledup dislocation arrays will continue to increase with increasing applied stress until fracturing takes place. Whereas face-centered-cubic metals have a sufficient number of mechanisms of slip for accommodation of dislocations in their grain boundaries to exhibit ductile behavior, hexagonal-close-packed metals, in general, do not. Consequently, hexagonal-close-packed metals are usually brittle except when conditions such as alloying or temperature permit facile slip by a number of mechanisms. The arguments presented above suggest that the mechanical behavior of magnesium depends on whether or not dislocation arrays in adjacent grains can enter the grain boundary. When such accommodation is possible, ductile behavior is expected; but when such accommodation is impossible, fracturing will ensue. To further test the validity of these arguments it was considered advisable to study the

Jan 1, 1961

By A. W. Sommer, H. H. Kellogg

It is shown that SO3-O2 mixtures react with sphalerite at an appreciable rate ill the temperature range of 361° to 527°C to fornz ZnSO4. The rate of reaction follows a parabolle lax. Oxygen, or O2-SO2 mixtures, have a negligible effect on sphalcrite in the same temperatuee range. PRACTICAL roasting of sphalerite is usually performed at 800°C or higher. The calcine is composed of zinc oxide unless the roaster atmosphere contains relatively large amounts of SO2 and the temperature is held to 800oC or lower, in which case zinc sul-fate may also form. Ong, Wadsworth, and assell' have made a careful kinetic study of sphalerite oxidation under these "normal conditions" and have concluded that the rate of the reaction is controlled by the decomposition of an activated complex adsorbed on the sphalerite surface. They found the rate of oxidation to be small at 700°C. Extrapolation of their data to 400°C would indicate an almost negligible rate at this temperature. In our work sphalerite was reacted with air, mixtures of SO2, O2, and N2, and mixtures of SO3, O2, and N2 in the temperature range 361o to 527OC. Negligible rates of oxidation were found, except for the gas mixtures containing SOs. With this latter gas, the oxidation of finely divided sphalerite was fairly rapid and zinc sulfate was the product. Based on the limited evidence available, the rate of sphalerite oxidation by SO3 is postulated to be controlled by gaseous diffusion through pores or cracks in the zinc-sulfate coating. This evidence for the direct reaction of sphalerite and SO, at low temperature may prove of importance to the understanding of zinc-sulfate formation in the dust-collecting equipment usually associated with zinc roasters. The roaster gas carries off fine dust, much of which may be unreacted sphalerite. The temperature in dust-collecting equipment drops from the roaster temperature (about 800°C) through the range of temperature we studied, to ambient temperature. Such dusts are known to contain far larger amounts of zinc sulfate than the primary calcine. It has been assumed in the past that this sulfate is formed by reaction of ZnO dust with SO3 (or SO, plus 0,) in the partly cooled gases. Our work shows that an alternative possibility exists—the direct reaction of SO3 with ZnS dust. EXPERIMENTAL Reaction rates for sphalerite at 350° to 600°C are relatively small so that it was necessary to use finely divided material with a relatively large surface area in order to obtain measureable amounts of reaction. In the preliminary experiments, pure mineral sphalerite, ground to pass a 325-mesh sieve, and chemically precipitated ZnS (in the form of an impalpable powder) were used. In the quantitative rate experiments the ground mineral sphalerite was processed in an Infrasizer to obtain a product with particle size between 9 and 18 µ. The analysis of this material was 66.7 pct Zn, 0.09 pct Fe, and 32.7 pct S (theoretical sphalerite is 67.1 pct Zn, 32.9 pct S). The sized powder was carefully mixed and divided into l-g samples. The apparatus used for the quantitative rate measurements is shown in Fig. 1. For the preliminary experiments the following change was made: The external catalyst furnace (B, C)* was not used. *Letters refer to Fig._______1 .___- Rather, when catalysis of the SO2 + O2 reaction was desired, the glass beads in basket M were replaced by vanadium-oxide pellets. Procedure—A l-g sample of ZnS was placed on a shallow stainless-steel tray, I, and spread evenly to a depth of about 1mm. The tray was placed in the reaction assembly and the assembly inserted in the cold furnace. The furnace tube was flushed with dry argon and then heated to the desired reaction temperature. The temperature was controlled to ±0.5oC. Gas mixtures (O2 + N2 or O2 + SO2) were prepared from tank gases by means of a mixing device identical to that employed by Darken and Gurry.2 The total flow rate of gas was 205 ml per min to point A of Fig. 1. The accuracy of the individual and

Jan 1, 1960

By E. O. Wagner, V. F. Parry, J. B. Goodman

The low-rank coals containing 10 to 50 pct natural bed moisture represent over half of the tonnage reserve of the available solid fuels of the United States, but only about 2 pct of United States coal production is derived from these fuels. Increased utilization of these large reserves will result if the bed moisture can be removed at the mine in high-speed low-cost processes. This paper presents a theoretical and experimental study of the factors affecting high-speed drying of coal dusts. The time required to heat particles of coal is proportional to the square of their diameter, and it is calculated that the probable time in minutes is equal to 6D2. In other words, a 1/16 in. coal particle should be heated to drying temperature in 1.5 to 2.0 sec. Likewise, 1/8 in. particles should be heated in about 6 sec. The net heat required to dry subbituminous coal and lignite varies from 240 to 375 Btu per pound, depending upon the moisture removed, and this heat can be obtained from 42 to 61 cu ft of hot gases at 600°F. The necessary heat also can be obtained from 7.5 to 11 cu ft of gas at 2000°F. A description of the design and operation of a pilot plant for flash drying coal dusts is presented. This plant dries 1/16 in. by 0 coal dust in suspension in 1.5 to 2 sec with 600°F gas at a rate of 1300 lb per hour per square foot of column area and operates continuously at an efficiency of about 85 pct. The design and operation of another pilot plant for drying 1/8 in. by 0 coal dusts Is also described. This unit dries coal in the fluidized state using the sensible heat of gases introduced at 2000°F and processes coal at a rate of about 1500 Ib per hour per square foot of grate area at 85 to 90 pct efficiency. Over 90 pct of the bed moisture of low-rank coal dusts can be removed by the methods described. The heating value of lignite can be increased 45 pet and that if subbituminous coal 25 pct in a few seconds. The physical and chemical properties of coal dusts before and after drying are presented in the report, and it is shown that the bulk density of the dried coal is equal to that of the raw coal. This phenomenon makes it possible to ship 25 to 45 pct more heat in a railroad car with consequent savings in freight costs. Introduction For several years the Subbituminous Coal and Lignite Section of the Coal Branch of the Bureau of Mines at Golden, Colo., has been concerned with upgrading low-rank coals by removal of natural bed moisture. These fuels contain 10 to 50 pct total moisture, which reduces their industrial value considerably. In 1938, investigations were initiated in cooperation with the University of North Dakota to study drying of lignite by the Fleissner process with heat derived from high-pressure saturated steam. Two pilot plants were built, and two reports were published giving the results of this work.l,2 It was demonstrated that lump lignite and subbituminous coal

Jan 1, 1950

By Neils Hansen

The microstructure of dispersion-strengthened aluminum aluminum-oxide products containing from 0.2 to 4.7 wt pct of aluminum oxide has been examined by optical and transmission electron microscopy, and the flow stress has been determined at room temperature and at 400C by tensile testing. Products were examined as recrystallized and as high-temperature extruded, and the microstructures consisted of a fine dispersion of oxide particles in a matrix divided by respectively recrystallized grain boundaries and subgrain boundaries. The flow stress (0.2 pct offset) at room temperature of recrystallized dispersion strengthened aluminum aluminum-oxide products is the superposition of dispersion strengthening and grain boundary strengthening. This superposition has been found to be linear. The flow stress (a) can be related to the grain size (t) by the Petch equation: ing content of oxide and k is a constant independent of the oxide content. For extruded products a similar relation has been found by replacing the grain size by the subgrain size. The k-value is of the same order for the two types of structure, which shows that the subgrain boundaries are as effective slip barriers as grain boundaries. Tensile testing at 400C of re-crystallized and extruded products shows that oxide dispersion strengthening is very effective, whereas the strengthening effect of grain boundaries and subgrain boundaries is small. THE microstructure of dispersion-strengthened products consists of hard particles finely distributed in a metal matrix. The strengthening effect of the dispersed phase has been fairly well established,1 and it has been found that the size and volume fractions of the dispersed particles are important structural parameters. However, in many dispersion-strengthened products which have been worked and heat-treated during manufacture the matrix is divided into well-defined grains or sub-grains, which may also have a strengthening effect. A model of the matrix strengthening in dispersed products worked during manufacture has been proposed,2 introducing the energy of the structure as a strengthening factor, especially at low temperatures. A difficulty in this model is, however, to relate this (stored) energy to the structural parameters directly observable as for instance grain size. The strengthening effect of the matrix grain size after recrystallization has been in- vestigated for nickel-thoria (TD-Nickel) products3 and for copper aluminum-oxide products. Conclusive results were, however, not obtained as the grain size of TD-nickel was constant. 5 to II , after recrystallization at temperatures from 700 to 1200°C and as the copper products containing 5 to 1 wt pct of aluminum oxide could not be recrystallized even after severe cold reduction and heat treatment at 1050C. For aluminum aluminum-oxide products containing from 1 to 5 wt pct of aluminum oxide it has been shown that the tensile strength at room temperature decreases when an extruded product is cold-worked and recrystallized. The matrix in the extruded products is divided into well-defined subgrains of micron size, and as the grain size of the recrystallized products is about two orders of magnitude higher, it is obvious that grain boundary strengthening occurs. Preliminary results8 have indicated that the flow stress containing no grain boundaries, A is a constant and t is the subgrain size. At elevated temperatures the effect of boundaries is more complex; it has been shown11 that recrystallized products having an oxide content of about 3 wt pct are more creep resistant than extruded material in the temperature range 400° to 600°C, whereas on application of a higher strain rate the tensile flow stress (0.2 pct offset) is higher in extruded than in recrystallized aluminum—5 wt pct aluminum oxide products at temperatures from room temperature to 427°C (800), Finally it has been shown12 that the Brinell hardness at 350°C of extruded products having about the same content of aluminum oxide increases with decreasing grain size, determined by X-ray line-width measurements. The present study was undertaken to obtain a quantitative relationship between the tensile strength and the grain size of aluminum aluminum-oxide products in the recrystallized as well as in the extruded state. The tensile testing was performed at room temperature and at 400uC. The grain size of the recrystallized products was varied by changing the degree of cold-work preceding the recrystallization heat treatment. In extruded products grain (or subgrain) size variations were obtained by high-temperature heat treatment after extrusion. EXPERIMENTAL a) Materials. Aluminum aluminum-oxide products have been manufactured by consolidation of aluminum powder covered with a layer of aluminum oxide formed during powder manufacturing. The products examined were manufactured from atomized powder containing

Jan 1, 1970

By V. A. Phillips

Transmission-electron micrographs of electro-thinned samples of bulk-aged Cu-3.1 pet Co alloy show an aging sequence, supersaturated solid solution — coherent particles — quasi -coherent particles — noncoherent particles. Hardening is due to precipitation of coherent spherical fee coball-rich particles showing coherency strain fields, which are resolved at between 15 and 30A diameter. Loss of- full coherency did not occur until well into the overaged region, even with the assistance of deformation after aging. Different average particle diameters of 123, 92, and 149 ± 10Å were observed in samples aged to peak yield strength at 600°, 650°, and 700°C, respectively, indicating that there is no critical size for peak hardening. Noncoherent particles tended to develop (111) faces and became octahedral in shape. Dislocations tended to nucleate spherical coherent particles which eventually grew together forming large elongated particles. The surface energy of a noncoherent (low-angle) inter-phase boundary is estimated to he about 50 ergs per sq cm. A number of particle lining-up phenomena were observed. Overaging is principally attributed to increase in particle spacing, progressive loss of coherency, and increase in amount of discontinzdous precipitation. COPPER dissolves about 5.6 at. pet (5.2 wt pet) of cobalt at 1110oC1 and the solubility decreases to 0.75 at. petl (0.54 at. pet)2 at 650°C and to 0.1 at. pet or less at lower temperature.' It has been known for many years3-5 that Cu-Co alloys are capable of age hardening. Since cobalt is fee above 417°C and its atom size is only about 2 pet smaller than that of copper, precipitation of coherent particles would be expected. The equilibrium phase precipitated at 700°C and below contains about 10 pet Cu in solution which tends to stabilize the fee structure, lowering the transformation temperature to 340oc.l The alloy is known to undergo discontinuous precipitation in addition to general precipitation; while the former can be seen with an optical microscope, the latter precipitates are not visible except in the grosly overaged condition.5, 6 Extensive use has therefore been made of the ferromagnetic properties of the precipitate in order to follow the course of aging, and it has proved possible to measure the average particle size, spacing, approximate shape, and volume fraction and to determine that the particles are coherent without ever seeing a particle (see for example Refs. 2, 7, and 8). The magnetic measurements of particle size are limited to diameters below about 120Å.7 The present study was undertaken using the techniques of transmission-electron microscopy in order to check the above conclusions, to extend the previous magnetic work to larger particle sizes, and to attempt a more detailed correlation of properties and structure. A portion of this work has already been published.9-11 The present paper is concerned with the metallographic features of precipitation in relation to aging curves. Bonar and Kelly12'13 have published preliminary results of a similar study on single crystals of Cu-2 at. pet Co. EXPERIMENTAL Preparation of Alloy. A Cu-Co alloy, containing 3.12 wt pet (3.36 at. pet) Co by analysis, was prepared from 99.999 pet purity oxygen-free copper and electrolytic-grade cobalt. The alloy was melted and cast in vacuo in a high-frequency furnace using a graphite crucible and mold: Analysis showed chat 0.004 pet C was picked up during melting. The 1-1/2-lb ingot was homogenized in hydrogen for 24 hr at 1000°C. Slices were cold-rolled to 0.005 or 0.003 in. thickness, with an intermediate 650°C anneal in hydrogen at 0.080 in. thickness. Batches of six to ten strips were solution-treated in sealed-off quartz tubes in high vacuum in a vertical furnace and quenched by dropping into iced brine containing a device which snapped off the nose of the tube. Solution treatment consisted of 1 hr at 990°C or 2 hr at 965°C. The latter was employed for all mechanical-property studies, since a tendency was noted for the higher temperature to give porous material. Strips were usually aged individually in a horizontal vacuum furnace, inserting into the hot zone and withdrawing into a cold zone without breaking the vacuum. This method gave a rapid heating rate, permitting the use of short aging times. In some cases, particularly for the longer aging times at the higher temperatures, samples were sealed individually in quartz tubes in high

Jan 1, 1964

By W. R. Hudspeth

AS an outgrowth of its spodumene recovery operation at Kings Mountain, N. C., Foote Mineral Co. has been recovering a heavy mineral by-product. Foote leased this idle plant in 1951, reactivated it, using a new spodumene recovery process, and purchased plant and properties in October 1951. While the operation at Kings Mountain is primarily concerned with the production of spodumene concentrate, pilot plant work determined that the pegmatites also contained heavy minerals including cassiterite. Plans were made to recover the heavy minerals as a by-product and the flowsheet incorporated these facilities when the mill was modified for the new spodumene recovery process. The orebodies consist of spodumene, feldspar, quartz and mica. Apatite, tourmaline, and beryl are present in small quantities. The wall rock is pre- dominantly hornblende shist. The heavy minerals, including cassiterite, columbite, pyrrhotite, monazite, pyrite, and rutile represent about 0.2 pct of the ore. The fine-grained heavy minerals are disseminated throughout the dikes, apparently unassociated with the spodumene. The pegmatites are quarried and secondary breakage is by mud-capping and block-holing. Power shovels load into trucks transporting the ore to a coarse ore bin. A Telesmith 10x36-in. apron feeder delivers the ore to an 18x36 in. Traylor Jaw crusher adjusted to discharge -3 in. product to a primary conveyor. The conveyor delivers to a 4x5-ft Tyrock single deck vibrating screen using 3/4 in. cloth. The screen undersize is elevated to the crushed ore bin. Screen oversize goes to an Allis-Chalmers Hydrocone Crusher fitted with 4 in. concave and set to deliver approximately 66 pct minus 3/4 in. The crusher discharge returns to the primary conveyor. The crushing and screening installation has a capacity of about 60 tons per hour. Spirals The crushed ore is delivered at a rate of 350 tons per day to two 6x8-ft Hardinge Pebble Mills, equipped with 20 mesh Ton-Cap trommel screens. The screen oversize is pumped to a 12-in. hydroclone for primary desliming. The hydroclone underfl spirals. There is no heavy mineral loss in the hydro-clone overflow. The spirals bank consists of eight 5-turn Model 24-A Humphreys Spirals. The top port and the last four ports of each spiral are blanked, the remaining nine port splitters are adjusted to remove about 5 pct feed weight. The heavy mineral rougher concentrates are upgraded on a Deister Overstrom table. The spiral concentrates contain approximately 4 pct heavy mineral, and the spiral reject, which goes to another section of the plant for spodumene recovery, contains about 0.03 pct heavy mineral. There is an interesting feature in the spirals installation. An adjustable splitter mounted on the discharge boxes splits out a mica fines product containing very little heavy mineral. The mica product is cleaned by spiralling and screening. Thus the spirals recover two products; mica, and a heavy mineral rougher concentrate. Table Treatment The rougher spiral concentrate goes to a Deister Plato table, modified to receive a Deister-Overstrom No. 6 rubber cover with sand riffles. The table is operated with a 5/8 in. stroke, 270 strokes per minute, and a slope of 1/2 in. per ft from feed to tailings side. There is no slope adjustment from motion to concentrate end. Wash water consumption is relatively high, since the large spodumene grains tend to report with the fine heavy minerals. A middling band about 4 in. wide is maintained in order to produce clean concentrate. The middling, representing about 10 pct of table feed, is recirculated by air-lift. A band of concentrate grade coarse spodumene occurs just below the middling. This is removed and delivered to concentrate storage. The table tailing, containing approximately 0.7 pct heavy minerals, is returned to the spodumene feed preparation circuit. The heavy mineral table concentrates are approximately 45 pct cassiterite, 33 pct columbite, 14 pct pyrrhotite and 8 pct monazite, together, with some rutile, pyrite, and copper from blasting wire. Concentrate is collected at 24 hour intervals. and dried. If the concentrate remains in wet storage appreciably longer surface oxidation takes place which seriously interferes with the subsequent magnetic separation process. About 150 lb of heavy mineral concentrate is produced per 24 hours and shipped to the company's plant at Exton, Pa. for final separation into tin and columbium concentrates.

Jan 1, 1952

By Joseph L. Gillson

IT is a somewhat curious circumstance that the newest of the Institute's several awards should be conferred in the oldest of our several professional fields—for there is little question that geology and mining have antedated metallurgy and petroleum. Perhaps so did geophysics. After all, one geophysical instrument, the magnetic compass, has been successfully employed for many centuries. Young in years the Jackling Award may be, but in distinction—whether in terms of the title it bears or in terms of the first three medalists (Reno Sales, E. D. Gardner, and the late Father MaceIwane)—the Jackling Award is already one of the ranking awards of the Institute. The name of the 1957 medalist will bring added luster to an already illustrious roll. J. L. Gillson was born and brought up in Evan-ston, Ill., in an area characterized by singularly flat and uninspiring topography, and devoid of ore deposits and even of bedrock—a most unlikely environment from which to expect a future Jackling medalist to emerge! On graduating from high school he enrolled as a chemistry major at Northwestern University. At the end of his frkshman year his scholastic prowess had won him a prize of two chemistry books. But these went unread, for about this time he came under the spell of U. S. Grant, that distinguished and enthusiastic geologist who for many years was head of Northwestern's geology department. From thence forward Joe was a dedicated geologist. After a Navy interlude in World War I, he went to MIT for graduate work, substituted for the late Professor Palache for one year at Harvard in mineralogy, received his doctorate at MIT and stayed on as a meniber of the MIT faculty, where the geology department was headed by that great dean of all economic geologists, Waldemar Lindgren. In 1926 Joe spent a summer looking into barite deposits for the du Pont Co., and since 1928 he has been du Pont's chief geologist. Do men who lead such active lives in our exploration organizations generally have permission to publish their observations? Do they generally find time to publish, even if they have permission? Alas, no. But in Joe Gillson's case, yes. His bibliography runs to well over two score papers, including one of the very first papers in this country on the applications of petrography to problems of Portland cement. He has written on such topics as the origin of talc and the genesis of ilmenite, fluorspar, and alkaline rocks. Each year for a number of years his annual reviews of industrial minerals in the Mining Congress Journal have been eagerly awaited. - Do men who do so much to advance their science have anything left to give to the advancement of their profession? In Joe Gillson's case, yes. He has been a vice president of the Mineralogical Society of America and has been active in the councils of the Society of Economic Geology, particularly in their research programs. This year he is president of the American Geological Institute, currently perhaps the most challenging post to which a geologist may be elected. His contributions to AIME scarcely need documentation, so I shall mention only three—his chairmanship of the Committee on Democratization of the Institute, a committee whose work and recommendations brought a new and hopeful leaven to AIME at a time when this was sorely needed; his chairmanship, a few years ago, of the Industrial Minerals Division; and his current place on the Board of Directors as Vice President of the Institute. Such' a catalogue of contributions and achievement, even as condensed as I have had to make it, certainly merits the Jackling Award. Yet, implicit although not often expressed in the conferring of most awards is the hope that besides recognizing a distinguished career, it will provide stimulus for further effort. In the present instance, such an expectation is already well on the way to fulfillment. Only recently Joe Gillson has undertaken the editorship of a new and greatly revised edition of the Institute's Seeley Mudd volume, Industrial Minerals and Rocks. And so, Mr. Chairman, it is with pleasure and enthusiasm that I present Dr. J. L. Gillson for the 1957 Jackling Award.

Jan 1, 1958

By G. T. Davis, C. C. Mattax, M. O. Denekas

The effects of crude oil cornponents on the wellabil-ities of sandstone and limestone were investigated. Fractions containing cornponents differing in molecular weight and molecular structure were obtained from crude oils by distillation, extration and chromatography. Individual fractions were then tested for their effects on rock wettability. Tests indicate that sundstone wetta-bility may he changed by a complex variety of surfactants varying both in molecular structure and molecular weight. Limestone appears to be particularly sensitive to basic, nitrogenous surfactants. INTRODUCTION Investigations in recent years have shown that petroleum reservoir rock wettability can exert a significant influence on the efficiency with which oil can be produced by water flooding. While most reservoirs are presumably water-wet, they niay range in their degree of water-wettability from near-neutral to strongly water-wet.'" Reservoir wettabilities other than strongly water-wet are likely to be induced by adsorption of surface-active components froni the crude oil on the pore walls of reservoir rock.:' Little is known, however, about the nature of the surface-active materials which are likely to be adsorbed by the reservoir rock. Due to the complexity of crude oils. attempts made in the past90 isolate these surface-active components have met with only limited success. It is probable that many different types of surface-active materials arc indigenous to crude oils and that many of these may be adsorbed to varying degrees by reservoir rock. This was cxolored in the studies discussed in this paper. The over-all objective in these studies is to ascertain whether the wettability of a given reservoir can be determined by examining the surfactant content of the reservoir crude. To this end, crude oils were examined to determine the variability of indigeneous surfactants with regard to chemical type and molecular weight. Crude oils were separated by distillation into fractions differing principally in molecular weight, by chroma-tography into fractions containing compounds differing in polarity, and by solvent extraction into nitrogenous and non-nitrogenous fractions. Individual fractions were then tested for their effects on the wettabilities of sandstone or limestone rock samples. EXPERIMENTAL PROCEDURES Fractionation of the Crude Oils Samples of Miocene, Eocene and Jurassic crudes were distilled at temperatures not exceeding 200°C. The final stages of distillation were completed in a molecular still at pressures down to three microns of mercury. Fifteen to 30 fractions were obtained from each crude oil. These cuts were sufficiently broad that separation can be considered to have been effected principally on the basis of the molecular weights of the constituents of the crude oil. A considerable portion (20 to 40 per cent) of the crudes would not distill under these conditions. The residues were recovered and tested with the other fractions. Fractions differing in polarity were separated from a crude of Pennsylvanian age and an extracted sample of Miocene oil by chromatography, using a solid adsorbent. Since surfactants are, for the most part, polar compounds, chromatography should separate many of the surfactants from the crude oil. Such a separation should provide fractions containing compounds differing in molecular structure. Nitrogeneous compounds were extracted from Miocene crude oil with a solution of sulfuric acid in meth-anol. The residual oil was further processed by chonia-tography. Each of the fractions obtained by thesc procedures was dissolved in a non-polar solvent (xylene) and diluted to its original concentration in the crude oil. No attempt was made to maintain an anaerobic atmosphere above the samples while they were being dissolved. These solutions of the fractions were then tested for their effects on the wettability of sandstone and limcstone as discussed in the next section. Measurement of the Effects of Crude Oil Fractions on Rock Wettability No entirely satisfactory method for measuring rock wettability has yet been developed. All methods used are empirical. The imbibition test was used in these studies. This test is based on the tendency of a rock to imbibe the wetting phase spontaneously. For example, if a strongly water-wet rock is first saturated with oil and then placed in water, the water will quickly invade the rock by capillarity and much of the oil will be displaced. If the rock is slightly water-wet, water irnbibition will proceed more slowly and, in many instances, considerably less oil will be displaced. A water-saturated, oil-wet rock will imbibe oil. The initial rate with which water (or oil) imbibition takes place indicates, qualitatively, the degree of water (or oil) wettability of the rock.

Frank Owen, El Perú Venezuela (communication to the Secretary): Mr. Cragoe's accurate description of the rich and extensive mines of the Frontino and Bolivia Co. is of much interest to those acquainted with Colombian mining. While the labor in that part of Colombia is, of course, admittedly far inferior to that of white miners, it is,. nevertheless, decidedly superior to that available in other parts of the republic, and in the northern mining regions of South America generally. The Autioquenos have been miners for several generations, and many of those employed at the Frontino Co.'s works have been brought up at the mines, which is a distinct advantage. The ground encountered in the surface-workings of that district being very treacherous, they are skillful timber-men, every miner being able to put in his own timber in tunnels, stopes, etc., so that, except for the main shafts, where sawn timber is used, special timber-men are not required. In the shallow workings it is the custom for a miner to come out of the mine into the thickly-wooded bush and select and cut the timber he requires, which he will then take into the mine and put in

Jan 1, 1899

By H. A. Bourne, E. L. Haden, D. R. Reichmuth

A circumferential-toothed bit with novel tooth form gave improved penetration performance. In this design the exterior flank of all teeth were vertical when in rolling contact with the hole bottom. Rock chips were generated by the interior flank of the tooth displacing the rock inwardly and downslope toward the center of the hole. A unique two-cone laboratory bit assembly enabled evaluation of numerous cone and tooth configurations. Some of the variables investigated, in addition to weight on bit, rotary speed and rock type, were tooth interference, percent tooth, hole bottom angle, attack angle and relief angle. Most tests were conducted dry on a brittle synthetic sandsone or a ductile quarried limestone. Tooth configurations were found to be more significant in the ductile material. This was attributed to the deeper tooth penetration before rock failure. These studies showed that the attack angle (angle beween interior flank of the tooth and rock surface) was the controlling variable; changing the tooth configuration from the assymetric or semi-wedge to the more conventional symmetric or wedge form reduced penetration performance; and penetration performance of circumferential-type cutters was directly proportional to rotary speeds up to 200 rpm. INTRODUCTION Much of the published literature on rock-chisel interactions describe experiments wherein symmetrical wedges are vertically loaded or impacted against a smooth rock surface.1-6 are is usually taken to insure that the indentation is not made near the edge of the rock specimen less erroneous data be obtained. The literature describes relatively few studies in which the investigator deliberately attempted to take advantage of an edge or free surface. In contrast, anyone who chips ice or breaks up a concrete sidewalk almost always works near an edge. Chisel "indexing," which has been considered by some investigator1,2,6,7 makes limited application of an edge or free surface. Probably the best documented investigation into applying this idea to drilling was that of Drilling Research Inc. at Battelle Memorial Institute.' Their "annular wing" percussion bit consisted of paired asymmetric chisels oriented so as to produce and move chips to the center of the hole. They predicted that the lowest energy requirement for chip generation would be achieved with a stepped hole bottom having a median angle of 45" to the horizontal. Results from limited tests showed that approximately 50 percent of the rock fragments were large and semi-circular in shape, as would be expected by a chisel impact near an edge. The remaining 50 percent were fine chips produced by the chisels in re-establishing the steps or ledges. Initial penetration rates with this bit were high, but they rapidly decreased. This was the result of excessive tooth wear caused by the constant friction on the gauge surfaces. The basic idea — circumferentially placed asymmetric chisels — still appears to have merit. If the concept could be applied to a rolling cutter bit, two of the shortcomings of the fixed chisel design could be overcome: (1) reduction in tooth friction, and (2) greatly increased cutter surface. Adapting asymmetric chisels to cutters rolling on an inclined hole bottom is restricted by bit geometry. The basic elements of roller rock-bit construction prevents the practical attainment of a 45" hole bottom angle. Nonetheless, experimentally it was considered desirable to investigate the influence of hole bottom angle to at least 40". This paper describes the laboratory studies conducted in evaluating the circumferential-toothed roller cutter rock bit. EXPERIMENTAL APPARATUS AND PROCEDURE BIT ASSEMBLY The cost of constructing a sufficient number of conventional three-cone rock bits to investigate circumferential cutter performance was prohibitive. Instead, a novel two-cone laboratory assembly which used an external bearing system was designed and constructed. The external bearings made it possible to alter the journal bearing angles and thus allow a wide flexibility in cutter configuration. Fig. 1 shows the laboratory bit assembly, the various bearing mount plates and the appropriate roller cutters for drilling shallow holes having hole bottom angles of 0, 10, 20, 30 or 40". The bit was limited to a drilling depth of 1 1/2 in. at the gauge teeth and a hole diameter of 43/4 in. This more or less intermediate size bit was chosen because it gave a more realistic match between bit teeth and the rock than would a microbit. Also, the rock sample size required was convenient and easy to obtain. CIRCUMFERENTIAL CUTTERS The tooth configuration used in our initial studies is shown in the upper half of Fig. 2. All cutters used in this series had the same tooth form — 43" included tooth angle, 2" positive relief angle and a horizontal tooth flat width of 1/32 in. Each cone cuts alternate rows except for the gauge row. The row-to-row spacing in view was 1/4 in. Static loading tests conducted earlier with asymmetrical chisels had been used to establish this spacing. These tests showed energy requirements for chip production increasing rapidly as the distances to the edge increased beyond

By F. W. Bloecher

S. Mortsell and J. Svenssofi (Royal Institute of Technology, Stockholm, Sweden)—Bloecher states that the apparatus described by him should be a suitable instrument in the mineral dressing laboratories for determining the specific surface of such granular products that are generally investigated. We want to express a somewhat different opinion, as we doubt that the gas adsorption method of surface measurement really is the most suitable method in mineral dressing laboratories. It is well known that the surface area, as measured by this method, does not coincide with the surface area calculated from the size, shape, and number of particles, i.e. the superficial surface of the particles. It can be seen easily from Mr. Bloecher's own determination on ilmenite-leucoxene concentrate that the surface area measured according to this method may be several hundred times larger than the superficial surface. It is supposed that the surface of cracks, fissures, and pores within the particles also is included in the measured surface. However, this is an assumption which scarcely can be proved and certainly has not been proved. We believe that the mineral engineer could better use a method giving the superficial surface of the particles, as in most cases this surface only is of importance to him. Such is certainly the case when calculating the resistance of the fluid flow through granu- lar materials and the capillary forces of such materials, problems which are of great importance in connection with dewatering, filtration, and pelletizing'" etc. The same may also be the case when studying flotation problems, partly since the quantities of the introduced reagents usually are so small that they can only cover the most accessible surface of the particles, and partly since the molecules of at least the collecting reagents are so large that they cannot enter the smallest cracks and pores. As to the surface, which is of consequence in the application of Rittinger's law of crushing, one is inclined to believe, from theoretical reasons and from the work by Gross and Zimmerley, that the total surface here is the most important one. However, it seems as if in that case the superficial surface was as important as the total surface. Other reasons making the gas adsorption method less suitable for use in the mineral dressing laboratories are that the granular materials there very often are too coarse to be measured by this method, that the experimental technique is rather difficult, and that it takes a long time to measure the specific surface of a sample. Besides, the validity of the method must still be considered questionable. It is thus well known that with different gases one usually gets different values of the specific surface of the same sample, which values, even with such an ideal material as metal foils, can differ as much as about 50 pct.'" Still more serious

Jan 1, 1952

By E. H. Bronson

PROPERTY of Malartic Gold Fields Ltd. is situa-ated in the great clay belt in the northern part of the Province of Quebec. This belt represents the floor of the glacial lake Barlow-Ojibway. The clay blanket has a gently rolling, almost flat surface, with here and there projecting knobs and ridges that outline the large irregularities of the surface on which the clay was deposited. At irregular intervals glacial eskers dominate the landscape. The ore-bearing country rock is covered by strata of clay, sand, and silt to a depth varying to 40 ft. There are serious structural problems when it is necessary to place loads of unequal intensities on this surface to support buildings and machinery for a modern mining plant. Earlier mining companies and their engineers paid little attention to the science of soil mechanics, partly because they believed it unnecessary and partly because they knew little of the subject. The results are evident in some of the tottering structures in older camps. Careful analysis of soil problems is well worth-while, since cost of foundations may vary from 20 to 50 pct of the final cost of a structure. Low operating and maintenance costs can be achieved only in this way. If it is definitely established that a plant will be in operation for only a few months, this limited time factor will probably influence the design of the foundation, and rightly so. If sensitive and complickted equipment is to be mounted on these foundations and the plant is to operate for several years, there should be a thorough study of foundations and a very careful design. A familiar problem is presented by the difficulty of operating a permanent plant originally designed for a few months' work. The engineer must beware of these hazards and disassociate himself from them if he cannot prevail on the promoter to spend the proper amount for a thorough foundation study. Laws of certain provinces and states hold the engineer equally responsible with the contractor for any 'damage that may be caused to building through inadequate study-ignordnce of the facts is no excuse in the eyes of the law. Types of Soil: The engineer should be familiar with such terms as silt, clay, peat, and varved clay, as well as perpafrost, especially if he is to work in the far northern reaches of the country. He should also be familiar with soil attributes such as porosity, texture, consistency, permeability, compressibility, consolidation, and shearing resistance. The design of any foundation requires an accurate knowledge of the physical properties and location of the soils involved. Older textbooks on the subject outline various empirical methods to determine the carrying power of soil. Tables are given in reference books. The modern ehgineer should be wary of these modes of thinking. He should analyze his problem carefully, calculate to what depth of soil the loads may be transmitted, and then check the bearing value of all soils to that or greater depths. If the strata are water-carrying, he must determine the possibility of this water being accidentally re-

Jan 1, 1958

By J. Charles Miller

THE expansion of facilities for rapid transportation of perishables by train, truck and airplane has necessitated consideration of refrigerants of a minimum weight and volume per pound of cooling and has stimulated the use of solid carbon dioxide commercially. The gas probably has not had wide application in the past in air-cooling equipment for mines, theaters or buildings, owing to its thermodynamic properties, as will be deduced from examination of Table 2. However, consumption of the liquid in carbonating beverages remains a dominant factor. In addition to these uses, carbon dioxide is employed to a limited degree as an explo-sive in the liquid form, as a freezing agent in plumbing, in laboratories for low-temperature work, and in the manufacture of golf balls. SOURCES The principal sources of the gas at present are coke ovens, lime kilns, breweries and other fermentation plants, all of which are within easy reach of markets. Natural sources, however, have not received the consideration they merit, mainly because of their isolation. It is asserted by some manufacturers that the carbon dioxide gas produced from wells is unsatisfactory because it often contains impurities that are difficult to remove, while that produced as a byproduct is much purer or contains impurities that are easier to remove.

Jan 1, 1936

By R. W. Heckel, H. W. Paxton

The growth of grain boundary films and Widmanstiitten plates of proeutectoid cementite in hypereutectoid steels ulas considered quantitatively in three plain carbon steels and one "pure" iron-carbon alloy. Growth was found to take place at a slower rate than would be predicted on the basis of a model invoking rate control by long range diffusion of carbon. The films in the pure alloy grew faster than those in the plain carbon steels. A possible explanation is suggested. In 1904, Nernsst' and Brunner2 postulated that ionic crystals growing in supersaturated aqueous solutions grew at rates determined by diffusion through the solution to the growing crystal interface. The gradient down which the diffusion took place was assumed to be fixed by the supersaturated bulk solution concentration, the concentration dt the crystal surface and some arbitrary distance. The flux of material to the crystal was described as Flux where D is the diffusion coefficient, A the crystal surface area, Ci the bulk solution concentration, Co the saturated solution concentration, and 6 the thickness of the diffusion zone. It is obvious that the expression is an adaptation of F+ick's3 first law of diffusion (steady state). This was the initial formulation of what will be defined here as "diffusion controlled growth," i.e., growth limited by the long range diffusion of a component either to or from the advancing interface assuming both phases at the interface to be in equilibrium. This idea of equilibrium interface concentration implies an infinite reaction rate at the interface. Volmer, Zener,' and 11schner6 have derived expressions for the diffusion controlled growth of spherical precipitates in metallic systems. These analyses agree that the growth in a given direction should be parabolic with time. Brown and Hawkes7 observed that graphite, formed both from the decomposition of cementite and from the decomposition of eutectoid austenite in cast irons, grew according to a parabolic relationship and, therefore, concluded that the laws of diffusion controlled growth, as defined above, were obeyed. They, among others, failed to consider, however, that parabolic growth is a necessary, but not sufficient, condition for diffusion controlled growth. Mehl and Dube"' have pointed out that equilibrium may not be realized because the concentration at the interface cannot change instantaneously from that of the bulk to the saturation value. Furthermore, they propose that an equilibrium solute concentration in the parent phase adjacent to the precipitate would remove the thermodynamic activity gradient across the interface and, thus, stop the growth process. Frisch" has also emphasized the importance of interface concentrations that vary throughout the growth of a new phase. The variation in activity across an interface, as discussed by Onol' and Cahn and Hilliard,12 is of fundamental importance to this question. Ham13 considered the data of Turnbull14 on the growth of barium sulfate in aqueous solutions. He concluded that the data could be analyzed in terms of a radiation-type boundary condition. Flux across interface = K (c, - C,) [21 where C, is the concentration in the solution at the interface, Co the saturated solution concentration, and K the proportionality constant. The edgewise growth of Widmanstlitten plates, frequently referred to as the rate of lengthening, was first considered by Zener.'' Basing a mathematical analysis on steady-state (constant velocity) growth he concluded that where G is the growth rate, D the solute diffusivity, Ci the concentration in the bulk, Co the equilibrium interface concentration, C, the concentration in the precipitate, a a constant, Y the radius of curvature of the edge of the plate, and rC the critical radius, i.e., the radius which would increase the activity of solute at the interface at equilibrium under the influence of capillarity to that of the bulk. Zener1'

Jan 1, 1961

By John C. Martin

The discovery of a new gas reservoir demands that the planning of a sottnd well-spacing program be initiated early in the development stage. It is the purpose of this discussion to illustrate by actual field examples the application of basic well-spacing principles, previously developed for oil reservoirs, to the problem of well spacing in natural gas fields. These studies are presented for the field use of geologists and engineers who are concerned with the initial planning of the proper development of the newly discovered gas reservoir. INTRODUCTION The phenomenal growth of a vigorous natural gas industry emphasizes the increasing importance of natural gas as a source of energy, fuel, and raw materials to our nation's economy. Since 1945 marketed production of natural gas for the U. S. has increased 21/2 times to a record high of 10.6 trillion cu ft during 1957. As major participants in the gas industry, we share an added interest to develop and produce our natural gas reserves with constantly improved efficiency. The subject of well spacing is vitally important to the gas industry, for the well itself plays a significant role in the development of the natural gas reservoir and in control of the recovery process. Maximum utilization of wells is an integral part of sound conservation practices. The discovery of a new gas reservoir demands that careful choice of well location and well spacing be made and that the planning of a sound well spacing program be initiated early an the development stage. With the drilling of the first development well, efforts of the geologist and engineer must be directed toward acquisition of adequate technical evidence upon which a firm recommendation for a spacing program may be based. With this technical appraisal as a foundation, operators and state regulatory agencies jointly can go far in providing a framework for sound development of gas fields to achieve a program of conservation that avoids the unnecessary well. WELL-SPACING CONCEPTS Through laboratory and field investigations of the mechanism of the recovery of oil and gas, of fluid behavior, and of effective control of reservoir and well, a crystallization of ideas regarding reservoir behavior has emerged as a well-developed technology. Associated with a better understanding of the fundamental principles underlying reservoir and well behavior has been the growth of concepts concerning the role of wells and their spacing in the development and operation of an oil or gas reservoir. In addition to serving as outlets for the withdrawal of fluids from the reservoir, wells are recognized as having two other important functions: (1) providing access to the reservoir to obtain information concerning the characteristics of the reservoir and its fluids, and (2) serving as a means by which the natural or induced recovery mechanism may be effectively controlled. Beyond a minimum number of wells required to fulfill these two functions, additional wells will not increase recovery. With particular emphasis upon well spacing in oil reservoirs, many studies of the well spacing-recovery relationship have evolved the concept that the ultimate oil recovery is essentially independent of the well spacing.' These fundamental concepts are no different when regarding the role of wells and their spacing in the natural gas reservoir. They are equally applicable to the consideration of well spacing in gas reservoirs. For the gas reservoir, the problem of well spacing then revolves around the question of drainage and the degree or extent to which a well may drain gas from its surrounding reservoir environment. Theoretical and Experimental Work During the past 30 years, theoretical and experimental work carried on to study the physical principles involved in the flow of fluids through porous media has shed light upon the matter of drainage. Fundamental mathematical equations have been derived to describe the mechanism of flow of oil and gas through porous rocks. With the recent advent of high-speed digital computers, attempts have been made with mounting success to develop solutions, employing numerical techniques, to mathematical expressions that describe more rigorously the physical behavior and mechanism involved in the unsteady-state flow of compressible fluids, such as a gas, through porous rock. In 1953, Bruce, Peace-man, Rachford and Ricez published a stable numerical procedure for solving the equation for production of gas at constant rate. The results of these calculations are significant with respect to this matter of drainage, for they indicated (1) that depletion of the gas reservoir resulted in a drop in pressure at the extremity of the

By J. L. Walter

Extra-low carbon iron sheet, when deformed and annealed, undergoes exaggerated or abnormal grain growth in the critically deformed regions of the sheet. This exaggerated pmth occurs, for low strains (3 to 6 pct), only in sheet which has a fine dispersion of precipitates in the subsurface region of the sheet and fewer and coarser precipitates in the sheet interior. These particles have been identified as manganese sulfides. Wing the anneal, grains near the surface are gvowth-inhibited by the fine particles but the grains in the interior are free to grow normally. With the additional driving force provided by the strain energy, the interior grains first grow into the small subsurface pains. Eventually, these growing grains grow completely through the sheet. Calculations of limiting grain sizes at various values of strain indicate that a volume fraction of precipitates in excess of 10-' would be required to eliminate exaggerated growth in material strained to 10 pct. OPEN-COIL annealing has made decarburization of sheet steel both efficient and economically practical. Use of such material for porcelain-enameling stock is one of many possible applications of low-carbon iron since carbon in steel is deleterious to porcelain-enameling properties.' However, the extra-low carbon iron presently available presents another problem, that of exaggerated grain growth in regions where the sheet has been deformed as by bending or stretching. In exaggerated grain growth a few grains start to absorb their neighbors and these may become very much larger than the average grains of the sheet. Other names for exaggerated grain growth are coarsening, critical grain growth, secondary recrystallization, abnormal grain growth, or discontinuous grain growth. While this grain growth does not affect the enameling qualities of the low-carbon iron sheet, their presence results in a marked reduction of tensile-yield strength in the region of the sheet containing the large grains. The loss of tensile yield strength may render the material unsuitable for many applications . This report describes the results of a study undertaken to determine the cause of the exaggerated grab growth in extra-1ow carbon iron and, if possi- ble, to prescribe practical procedures for its prevention. GENERAL THEORY The driving force for exaggerated grain growth is the grain boundary free energy. This driving force is proportional to (l/rl + l/r2) where rl and r2 are the mutually perpendicular radii of curvature of the boundary between the growing grain and the grain being consumed. Thus, the greater the difference in size between the growing grain and the matrix grains, the higher the driving force for grain growth. If, however, the matrix grains are free to grow simultaneously, the driving force for exaggerated growth will be diminished. Stability toward growth of the matrix grains may be caused by a) a strong single orientation texture (texture inhibition),' b) a dispersed second phase,3"5 c) the thickness effect,' or d) intergranular segregation.7"9 As exaggerated growth occurs when growth of the matrix grains has been slowed by the stabilizing processes mentioned above, there must be an additional factor acting to promote growth of a few of the grains to the point where they are enough larger than the matrix grains that boundary energy driving forces are sufficient to cause continued growth. For instance, at the annealing temperature, growth-inhibiting inclusions may slowly dissolve and coalesce. Eventually, a grain boundary becomes unlocked and migration occurs at the expense of neighboring grains. Or, an additional driving force may be supplied to some of the grains if the material is strained. Then, since some grains will be strained less than others, the difference in strain energy between adjacent grains may be sufficient to overcome boundary locking and allow growth of the grains with lower strain energies. In the present study, therefore, such factors as the presence or absence of dispersed phases, the nature of the exaggerated growth, and the effect of strain have been considered. EXPERIMENTAL PROCEDURE I) Material and Processing. Three types of low-carbon iron were used in this study; types A and B were commercial grades, each from a different supplier.* The precise details of the processing of

Jan 1, 1963

By Pradeep K. Rohatgi, Clyde M. Adams

An analysis of heal conduction in the freezing of a solution has been performed. The case considered is the semi-infinite mass of solution, bounded by a con-stant-temperature plane with one-dimensional heat flow, Numerical cooling rate and freezing rate distributions hare been calcutated for the particular case of unidirectional freezing of aqueous solutions against. a cold copper chill. The solution at each level parallel to the chill surface is subjected to a spectra of frcezing rates; the freezing rate is inilially lour., passes through a maximum, and then decreases until solidification is camplete. Arange and maximum freeeing rates are inversely proportional to the square of distance from the chill surface. The temperature of the chill surface in contact with the solution remains constant during solidification. Experimentally, it is observed that deudrite sparing increases linearly with distance from the chill surface; in the light of heat -flow analysis this means that the dendrile spacing is imersely proportional to the square root of the maximum freezing rate. SOLIDIFICATION of liquids is accompanied by rejection of latent heat at the solid-liquid interface. The over-all rate of liquid to solid transformation is governed by the rate of heat extraction. Analysis of the heat transfer in the liquid during freezing is important since it determines the freezing rate and resulting structure. A considerable amount of work has been done on metallic systems since solidification is frequently a major step in processing metals. Unidirectional freezing from heat sinks has been treated by several investigators.1-4 Much of the work has been limited to the simpler case of substances such as pure metals which freeze isothermally at a unique transformation temperature. In this case the thickness of the solid zone y, next to a chill surface. is a parabolic function of the time. 8. where a and b are constants. Eq. |1| is a close approximation giving the progress of solidification for the case in which there is a small but finite thermal contact resistance at the interface between the freezing liquid and the chill.' It has been used with some success in connection with large steel ingots4 when the therma1 contact resistance is negligibly small (as is the case when water is brought into contact with the metal chill). The constant, b. becomes zero and Eq. [l] is then exact. even when the thermal properties of the chill and the freezing liquid depend on temperature. Analysis of unidirectional solidification of solutions is more complicated since the latent heat is evolved over a range of temperatures. Next to the all-solid zone in contact with the chill surface there is a solid plus liquid zone in which solidification takes place. Although the equations presented are considered quite general the numerical and experimental results are for freezing of aqueous solutions from a copper chill. I) EXPERIMENTAL PROCEDURE Solutions of potassium chloride, sodium chloride. and lithium chloride have been used. These solutions form a eutectic: a typical phase diagram is shown in Fig. 1. A solution at its liquid us temperature is poured into a tygon tube mounted on a relatively large copper chill. The chill is immersed in a freezing mixture of dry ice and acetone at -70°C. A thermocouple connected to a high-speed recorder was mounted near the top of the chill to measure the fluctuation in the temperature of chill surface in contact with the solution. In this system the progress of solidification can be visually observed through the tygon tube. After the specimens freeze to a desired height they are removed from the copper chill and stripped from the tygon tube. Longitudinal and transverse sections are cut from the specimen for micrographic examination. Specimens in the form of a thin slice are mounted on a transparent glass slide by freezing small drops of water around the periphery. They are then polished on a series of emery papers; the final finishing is done on a soft tissue paper. A Leitz Biological microscope was used for structural observations; photography was

Jan 1, 1968

By L. Delisle

This work represents the first step of an attempt to test the applicability of the electron microscope to the study of subgrain structures in copper. Observations on annealed and deformed single crystals and polycrystalline samples of copper are described. IN the course of study of the structure of fine tungsten wires and tungsten rods with the electron microscope, well defined subgrain structures were observed. The size, size distribution, and orientation uniformity of the etch figures varied widely in different samples. Figs. 1 and 2, electron micrographs of a tungsten wire and of a tungsten rod, respectively, are illustrations of the difference in size and size distribution of the etch figures in different samples of the same metal. The observed differences, as pointed out in a previous paper,' appeared to be related to the heat and mechanical treatments of the samples. They were also consistent with the results reported in the literature on the mosaic structure of metals.' For that reason a program of research was initiated in an effort to obtain more systematic evidence of the possible relation of heat and mechanical treatments to the subgrain structure of metals as observed in the electron microscope. The purpose of this paper is to present observations made on the effect of cold work on the subgrain structure of copper. Procedure Starting Materials: Copper was the metal studied because it can be obtained in a high degree of purity, much information is available in the literature on its properties and its response to cold work and heat treatment, it shows no allotropic change, and it is sufficiently hard to be handled without great difficulty. Two groups of specimens were used: 1—single crystals cast from spectroscopically pure copper and 2—polycrystalline samples of oxygen-free high conductivity copper. Single crystals were studied because it was hoped that the elimination of a number of variables, such as grain boundaries, orientation differences, degree of purity, would simplify the problem and perhaps permit a better understanding of the phenomena that would be observed. The polycrystalline samples were designed to give a general picture of the changes considered. The single crystals were made of copper which analyzed spectroscopically to better than 99.999 pct Cu. They were cast in vacuum, by the Bridgman method, in crucibles made of graphite with a maximum ash content of 0.06 pct. The mold design is shown in Fig. 3. It permitted casting crystals of the size and shape required for the experiments, so that the danger of introducing cold work in the original samples by cutting or other machining would be eliminated. The polycrystalline samples were pieces, 3/4 in. long, cut from a rod of oxygen-free high conductivity copper, % in. in diameter. A flat surface, 1/4 in. wide, was milled along the rods, polished, and etched. The samples were then annealed in vacuum at 850°C for 1 hr. Polishing and Etching: Work previously done on tungsten,' polished mechanically and etched chemically," had shown that: 1—the general appearance of the etch figures of a given sample was not altered by repeated polishings and etchings under similar conditions; 2—variations in the time of etching and the concentration of the etchant changed the definition of the etch figures, but did not alter their general size nor orientation distribution within the limits of observation. Further work confirmed the reproducibility of the subgrain structures observed in, 1—single crystals and polycrystalline samples of copper when polishing and etching were repeated under similar conditions, and 2—specimens of tungsten and polycrystalline copper when electrolytic polishing and etching were substituted for mechanical polishing and chemical etching, respectively. On the strength of these observations, it was felt that, if conditions of polishing and etching were kept constant, changes observed in the subgrain structure of a sample upon deformation and annealing would be attributable to such treatments. For that reason the conditions of polishing and etching were kept as constant as possible. The single crystals were polished electrolytically in a bath of orthophosphoric acid in water, in the ratio of 1000 g of acid of density 1.75 g per cc to 1000 cc of solution, under a potential drop of 1.6 to 1.8 V. Electrolytic polishing was selected to prevent the formation of distorted metal in polishing. The same samples were etched by immersion in a 10 pct aque-

Jan 1, 1954

By A. Steiner, E. Miller, K. L. Komarek

Equations have been derived to calculate the chemical potentials of the components of liquid binary alloys from liquidus and enthalpy data. The equations are applicable to systems with intermetal-lic compounds of limited solid solubility. The liquidus curve of the Mg-Sn system was accurately redetermined, and the melting point of the compound Mg2Sn was found to be 770.5° * 0.3°C. The thermo-dynamic properties of the liquid alloys were calcu -lated from the liquidus data. The activity of tin shows both positive and negative deviations from Raoult&apos;s law and the relative integral entropy is positive. THE phase boundaries in an equilibrium phase diagram are functions of the thermodynamic properties of the coexisting phases. Specifically, the shape of the liquidus curve near an intermediate compound is determined by the properties of the compound and the liquid phase. Hauffe and wagnerl have derived an equation for the chemical potential differences (ui) of the liquid alloys near the congruent melting point when the heat of fusion of the compound and the liquidus curve are known. In their derivation the temperature dependence of the ui value was neglected, and liquid of stoichio-metric composition was chosen as the reference state. To obtain chemical potentials over the ntire composition range of the phase diagram with the pure components as the reference state, equations have been derived which incorporate the temperature dependence of the chemical potentials. Such a thermodynamic analysis can be carried out when the liquidus curve and the enthalpy values are known. The equations have been applied to the redetermined liquidus curve of the Mg-Sn system to obtain the thermodynamic properties of liquid Mg-Sn alloys. The Mg-Sn phase diagram has been studied by various investigators and the results have been compiled and critically assessed by Hansen.2 Preliminary thermal analyses showed that the basic features of the diagram were correct. The system has one congruent melting compound, Mg2Sn, two eutectics, and some solid solubility of tin in magnesium. However, the published liquidus temperatures show considerable scatter. In order to perform an accurate thermodynamic analysis, the liquidus curve between the magnesium-rich and tin-rich eutectic compositions was therefore redetermined by careful thermal analysis using highest-purity starting materials. EXPERIMENTAL PROCEDURE The magnesium metal (Dominion Magnesium Ltd, Toronto, Canada) had a purity of 99.99+ pct with the following impurities (in ppm): 20 Al, 30 Zn, 10 Si, <1 Ni, <1 Cu, <10 Fe; tin (Cominco Products, Spokane, Wash.) contained 99.999+ pct Sn. The graphite crucibles were machined from graphite rods (United Carbon Products Corp., Bay City, Mich.) which had an average total ash content of less than 30 ppm. All the graphite parts were baked out in vacuum at 950" to 1000°C for a minimum of 24 hr to remove volatile organic materials. The graphite crucibles (3 in. long, 1-5/8 in. OD, 1-3/8 in. ID) were tightly closed with a threaded cover (1/2 in. thick) which had a central thermocouple well (2-1/4 in. long, 5/16 in. OD, 3/16 in. ID). Cover and thermocouple well were machined from one piece of graphite. A thin sheath of quartz was inserted in the well to protect the thermocouple

Jan 1, 1964