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By C. D. Tedmon, D. P. Ferriss

THE yield stress, o of low-carbon steel has been shown to vary with the average grain diameter, d, according to the relation1-3 where o is taken to be the lower yield-point stress Of is the friction stress on an unlocked dislocation, and ky is a constant. The interpretation2,4 of ky in terms of dislocation theory relates this constant to the stress to unlock a source across a grain boundary. cottrel14 predicted that ky would increase with decreasing temperature. This was observed to be the case by Adams and coworkers5 in their investigation of niobium (columbium). However, petch6 and Backofen: both working with low-carbon steel, found ky insensitive to temperature. In his work with high-purity niobium, Johnson' found ky equal to zero. Evansg showed that k, was essentially zero for niobium containing nitrogen in an appreciable concentration range. The present experiments were designed to check this apparent anomaly in the value of ky in another Group V metal. Yield points were determined as a function of grain size at several temperatures for tantalum and a tantalum-tungsten alloy. The material used was double are-melted tantalum and a double are-melted alloy of 90 pct Ta and 10 pct tungsten (by weight), both obtained as unannealed, swaged rod. The impurity content of the materials is given in Table I. The tantalum was annealed at 1325"C. in a vacuum resistance furnace using a tantalum boat. The alloy was similarly annealed at 1660°C. Annealing times varied from 15 min to 2 hr, depending on the desired grain size. Nominal pressure in the furnace was 3 X 10~4 mm of Kg. Metallographic examination showed that the annealing treatment produced grain sizes ranging frorn 0.021 to 0.200 mm in the tantalum, and 0.060 to 0.160 mm in the alloy. Tensile bars were made by centerless grinding the annealed specimen;, and then electropolishing to remove all grinding marks. The specimens were than pulled :it 2 1/2 pct per rnin in an Instron testing machine. The tantalum specimens were tested at 77", 195", and 300°K. The alloy was tested at 300°K only. All specimens exhibited a yield-point phenomenon at all temperatures. Typical load-elongation curves at the three test temperatures are shown in Fig. 1. The lower yield stress is plotted as a function of (grain size) in Figs. 2 and 3 for tantalum and the 90 pct Ta-10 pct W alloy, respectfully. The position and slope of the curves was determined by least-

Jan 1, 1962

By R. D. Nelson, F. E. Bowman

Evidence has been found for a (010)a?(111)B[102]a /,11[341]/B crystallographic relationship between the monoclinic a and B phases of plutonium during the a?B transformation. The results of an X-ray diffraction study, where [010] fiber textured a samples were used in the absence of suitable single crystals indicate that the (OIO)a planes become (111)B planes upon transformation under near-equilibrium conditions. The transformation strain along the fiber axis, which was the [010] direction, was measured dila-tomekically; the measured 8.5 pct expansion compares favorably with the 8.44 pct expansion in the in-terplanar spacing represented by the (010)a?(111)B relationship. From plots of the atom positions in each of the related planes, a correspondence was deduced between the [102]a, direction and the [341]B direction. Further analysis of the two lattice structures in the light of this relationship revealed a rotation about the [102] direction of 1 deg 43 min and a slight shearing in this same direction of about 30 min. THIS paper discusses the (B crystal structure of plutonium and the orientation relationship existing between the monoclinic a and B phases during the a?ß transformation. The kinetics of the a?ß and (3 — a transformations have received extensive consideration, and because of the crystallographic complexity of these phases, the question of the mechanisms by which these transformations occur is especially intriguing. Nelson and Shyne1 evaluated the existing experimental evidence and concluded, from the indirect evidence available, that both the ß ? a and a ? ß transformations occur by a martensitic process. Their data reveal the anisotropic nature of these transformations which suggests the existence of specific crystallographic relationships between the parent and product phases. In this paper, we are concerned with the confirmation of the existence of such a relationship resulting from the a ? ß transformation and the derivation of the crystallographic details necessary to specify it. EXPERIMENTAL RESULTS X-ray diffraction and dilatometric data were obtained from samples of a plutonium having a [010] fiber texture. These cylindrical specimens, approximately 1 cm in diam, were prepared by transforming the ß phase to a under the influence of a uniaxially applied compressive load.' The [0l0] direction is parallel to the direction of applied stress; it is also perpendicular to the (010) planes. This correspondence between the plane normal and the direction having the same indices is, in the monoclinic a plutonium structure, restricted solely to this (010)[010] combination. Such a specimen was mounted in an evacuated, elevated temperature specimen holder on an X-ray dif-fractometer so that the diffracting surface was perpendicular to the fiber axis. The a diffraction pattern, Fig. 1, taken at about 115ºC, revealed the predominance of the (020) reflection. This monoclinic, P 21/rn space group yields no (0k0) reflections when k is odd. The temperature was raised slowly to 160°C to effect the complete transformation to the phase; then it was lowered to 120°C so that a diffraction pattern of the ß could be obtained near the a = ß equilibrium temperature for direct comparison with the a at the same temperature. The (3 diffraction pattern, Fig. 2, obtained under these conditions showed a (222) reflection relatively much more intense than in the random pattern. The other reflections appearing with sig-

Jan 1, 1970

By C. H. Lee, R. Maddin

The diffusion rates of Ag110 in cylindrical single crystals of 99.99 pct pure silver, which were twisted to a total surface strain of 0.91 during the diffusion anneal at temperatures of 700°, 750°, and 800°C, were measured by sectioning and counting as a function of the strain rates. The ratio of the diffusivities while strain ing occurred (Ds) to those of the unstrained specimens varies linearly with the rate of twisting and attains values of near 100 for some of the rates used. The enhancement of diffusion by straining is inversely proportional to the temperature at which diffusion occurs. The activation energy for diffusion determined from the data plotted as a function of the rate of twisting decreases from 44,090 cal per mole for zero strain, to an asymptotic value of 21,000 cal per mole for the strain rates of 22 x it)"5 see-l. Qualitative explanation for the observations based on the generation of nonequilibrium number of defects by plastic deformation will be discussed. The initial research of Buffington and cohen1 on self-diffusion in a iron under compressive stresses contributed the first quantitative information concerning the effect of applied stresses on diffusion. These results were obtained from radioactive Fe55 plated on one of the horizontal surfaces and compressing the large-grained specimens while the diffusion-anneal was occurring. Enhancement of diffusion of a maximum of seventeen times was observed provided the strain was in the tertiary stage of creep and the rates of straining were at least as fast as rates used in the normal creep test. On the other hand, Darby, Tomizuka, and Balluffi,2 extending silver single crystals up to 30 pct elongation at rates of straining about equal to those used by Buffington and Cohen observed no effect. For the past two and a half years at the University of Pennsylvania, we have been investigating the effect or torsional strains on self-diffusion in silver single crystals. If enhancement is observed as has been reported1 a possible explanation may be based upon the generation of fairly large numbers of point defects and their role in the diffusion process. Hence, since torsion should produce an abundance3 of point defects, an increase in the diffusivity while the crystal is being twisted should easily be measured. EXPERIMENTAL PROCEDURE Our research uses single crystals of silver prepared from 99.99 Ag by the Bridgman method in a dynamic vacuum of less than 25 µ. As grown, they are about 25 cm long by 1.3 cm in diam. The crystals are cut into 7.5 cm lengths with a jeweler's saw and machined to the shape shown in Fig. 1. The test length of the crystal is machined to a 0.6 cm diam after which the ends are masked and the test section etched heavily in HNO3, and KCN:(NH4),S2Os , solution to remove the effects of machining. The specimen is then annealed in vacuum for 8 to 12 hr at 800°C to remove any residual stresses and also to recrystallize the end sections. The recrystallized ends are necessary since experiments showed that single-crystalline end sections are too soft to transmit the desired torque. Occasionally, recrystalliza-

Jan 1, 1960

By D. C. Ganow, N. J. Grant, I. R. Silver, A. R. Chaudhuri

The structural changes that result when a metal is "cold worked" lead to higher values of yield and tensile strength on subsequent deformation at room temperature. Further it has been shown that the beneficial effects of cold work are, to some extent, maintained even at elevated temperatures. The strength improvements from prior cold work decrease as the temperature is raised and are a function of grain size, amount of cold work, and strain rate (or time of test). If recrystallization occurs during test, the cold-worked material may even show weaker stress-rupture properties than the annealed material. A question that arises is whether there is a significant effect on the subsequent creep behavior if the prior deformation is performed under creep conditions at high temperatures not too different than the test temperature, but at significantly different strain rates and for various amounts of strain. An answer to this question was sought in the work described in the present paper. PROCEDURE Two materials were used in this work, high-purity aluminum and a solid-solution A1 2 pct Mg alloy. The compositions are shown in Table I. The grain size in the two materials was 0.2 to 0.3 mm. The deformation for both the prestraining and for the creep tests was at constant stress. The procedure adopted was to prestrain a specimen to the desired elongation, remove the load, and cool to room temperature rapidly by spraying. the test bar with cold water. The specimen was then placed in a creep machine, held at the test temperature for less than 5 min, and loaded. Less than 15 min was required to bring the specimen to temperature. The creep stress was based on the diameter resulting from the prior strain, and values of elongation at fracture listed in the tables do not include the respective elongations resulting from the prestrain. The choice of the stresses for the prestrain and for the creep tests was made so that the tests could be completed in relatively short times to maximize any effect of prestrain. The specimens had a gage length of 1 in., the pure aluminum specimens having a diameter of 0.150 in. and the alloy specimens a diameter of 0.125 in. For pure aluminum, prestrain was at 400' and 600°F with testing at 500°F; for the alloy, prestraining was at 700°F and testing at 600°F. RESULTS The prestrain conditions for the aluminum and the alloy specimens are shown in Tables I1 and IV. In addition to showing the time required to achieve the desired prestrain, the expected rupture Lives are given which would have resulted had the creep prestrain been continued to fracture. The prestrained and the annealed specimens were then tested in creep to fracture; the temperature and stress for the pure aliminum specimens being 500o F and 1800 psi and for the alloy, 600' F and 3400 psi. The creep curves for the prestrained and the annealed specimens of pure aluminum showed all three stages of creep; hence in addition to the effect of prestraining on the rupture life, it was also possible to determine the effect of prestraining on the minimum creep rate, and on the time and elongation at the end of each of the three creep stages. The results are shown in Fig. 1 and Table 111.

Jan 1, 1960

By S. M. Brisbane

THE life of refractory linings in rotary cement kilns can be shortened by uneven or inadequate support of the kiln and its shell and by variations in the conditions of operation. Alteration of these factors may, according to their nature, bring about mechanical deterioration of the lining or promote chemical attack. Chemical attack has been described elsewhere.1-4 The distortion of cement kilns has been discussed in a general manner by Rochow,6 ho indicates the amount of distortion which may occur in an unlined shell, and by Rosenblad: who states that the deformations of the shell are greatest above the trunnions. The present article indicates the extent of the distortion of a kiln to an oval shape in certain selected positions and the deviation from a straight line of the kiln along its length between two supports. The cement kiln is a long, hollow, rotating cylinder consisting of steel plates which may be either welded or riveted together. This shell is supported on tires, frequently 60 ft apart, which roll on trunnions. The large mass of the kiln causes distortion of its cross-section; it becomes slightly oval, i.e., diameters lengthen as they become horizontal and shorten as they become vertical. There is also a tendency for the shell to bow between supporting tires; this bowing may be upwards or downwards depending on the position of the weight forces and the supports. The extent of the deviations from the ideal kiln shape was investigated. Observations described in this paper were made on the shell of the clinkering zone between the first and second tires of two of the kilns at the Geelong works of Australian Portland Cement Pty. Ltd. The kilns were both 400 ft long and 10 ft diam with a welded enlarged burning zone 11 ft 6 in. diam. The shell was fabricated from mild steel and in this section its thickness was 1 in. It was lined with 41/2 in. of chemically bonded magnesite-chrome bricks which were jointed with mild steel plates. The kilns operate on a 4 pct slope and the speed may be varied between 0.75 and 1.68 rpm. The wet process is used; kilns are coal fired and are fitted with integral coolers. Temperatures within the kiln are difficult to determine with any accuracy because of the absence of black body conditions, but surface temperatures are probably in the range 1420° to 1470°C. Average shell .temperatures at the two positions at which the deformation studies were made were 370°C and 355"C respectively. Methods: In determining the ellipticity it was necessary to measure the lengths of the vertical and horizontal diameters while the kiln was in operation; data obtained from a stationary kiln would not have the same practical significance. For this purpose the four points V, W, X, and Y at the ends of two mutually perpendicular diameters were marked on one kiln. The point X is shown in Fig. 1. For the measurement of the length of the vertical diameter a vertical column, to which a horizontally aligned telescope was attached, was placed 10 ft from the kiln. The telescope could be racked up and down in a vertical plane. Two sets of readings were taken, one set when each of the points V, W, X, and Y was at its maximum height above the

Jan 1, 1957

By R. L. Skaggs, D. T. Peterson

The effect of carbon in solid solution on the plastic behavior of thorium was studied by measuring the flow stress of Th-C alloys from 4.2" to 573°K and at several strain rates. Carbon was found to strengthen thorium primarily by increasing the thermally activated component of the flow stress. The strengthening due to carbon was directly proportional to the carbon content and decreased rapidly with increasing temperature up to 423" K. The flow stress also increased with increasing strain rate. The strengthening appears to be due to a strong short-range interaction between carbon atoms and dislocations. A yield point was observed in the Th-C alloys which increased with increasing carbon content. JTREVIOUS study of the mechanical properties of thorium has been confined largely to the measurement of the engineering properties. Work prior to 1956 has been summarized by Milko et al.1 who reported that additions of carbon to thorium sharply increased the room-temperature strength. In addition, the yield strength was observed to decrease rapidly over the temperature range from 25" to 500°C. In 1960, Klieven-eit2 measured the flow stress of thorium containing 400 ppm C. He found that over the temperature range from 78" to 470°K the flow stress was strongly dependent on temperature and rate of deformation. A drop in the load-elongation curve, or a yield point, was observed over most of the above temperature range. Above 470°K, the flow stress was nearly independent of temperature and strain rate. This strong temperature and strain rate dependence of flow stress is not generally observed in fcc metals. It is, in fact, more typical of the behavior reported for bcc metals. Bechtold,3 Wessel,4 and conrad5 have pointed out the striking difference between the commonly studied bcc metals and fcc metals in regard to the effect of temperature and strain rate on the flow stress. Zerwekh and scott6 studied the plastic deformation of thorium reported to contain 12 ppm C. They found that this material did not obey the Cottrell-Stokes law as expected for fcc metals. In addition, they found values of the activation volume smaller by an order of magnitude than expected for an fcc metal. They concluded that thorium was strengthened by a randomly dispersed solute. Thorium differs from many other fcc metals that have been studied extensively in that it shows a relatively high carbon solubility at room temperature. Mickleson and peterson7 report the solubility limit at room temperature to be 3500 ppm C. The lowest value reported is that of Smith and Honeycombe8 who report the limit to be 2000 ppm C at 350°C. The pres- ent investigation was a systematic study of the flow stress and yield point phenomenon of thorium over a broad range of carbon content, temperature, and strain rate. EXPERIMENTAL PROCEDURE The thorium used in this investigation was produced by the reduction of thorium tetrachloride with magnesium as described by Peterson et a1.' Chemical analysis of the original ingot after arc melting and electron beam melting is shown in Table I. Alloys were prepared by arc melting this thorium with high-purity spectrographic graphite. Threaded specimens with a gage length 0.252 in. diam by 1.6 in. long were used for the constant stress or creep measurements. These specimens were machined from rod which had been cold-rolled and swaged to % in. diam. Tensile specimens were prepared by swaging annealed 3/8 -in.-diam rod to 0.102 *0.001 in. The as-swaged wire was cut to lengths of 2 in., annealed, and the center 1-in. gage length elec-tropolished to 0.100 ±0.001 in. The specimens were gripped for a length of 3 in. at each end by a serrated four-jaw collet which was tightened by a tapered compression nut. No slipping occurred in the grips and negligible deformation was observed outside the 1-in. gage length. Both the creep and tensile specimens were annealed at 730°C under a vacuum of 1 x X Torr. The resulting structures consisted of equiaxed recrystallized grains with a grain size of 3200 grains per sq mm for the tensile specimens and 2200 grains per sq mm for the creep specimens. After the specimens were prepared, samples were analyzed for nitrogen, oxygen, and hydrogen. The results of these analyses are given in Table 11.

Jan 1, 1969

By C. T. Wei, A. Kelly

USING a recently developed X-ray method, reported by Schulz,2 it is possible to make a rapid survey of the perfection of a single crystal at a particular surface. This technique has the advantage of allowing a large surface of a specimen to be examined by taking a single photograph and it compares well with other X-ray methods in regard to sensitivity of detection of small angle boundaries. During the course of a survey of the perfection of large crystals of aluminum produced by a number of methods, an examination has been made of a number of single crystals produced from the melt using a soft mold (levigated alumina)." Crystals grown by this method are known, from an X-ray study carried out by Noggle and Koehler,3 to contain regions where they are highly perfect. In the present work, it has been possible to obtain photographs showing directly the distribution of low angle boundaries at a particular surface of these crystals. single crystals were grown from the melt using the modified Bridgman method with a speed of furnace travel of -1 mm per min. These were about 1/10 in. thick, 1 in. wide, and several inches long. The metal was 99.99 pct pure aluminum supplied by the Aluminum co. of America. The crystals were examined by placing them at an angle of about 25° to the X-ray beam issuing from a fine focus X-ray tube of the type described by Ehrenberg and Spear4 and constructed by A. Kelly at the University of Illinois. A photographic film was placed SO as to record the X-ray reflection from the lattice planes most nearly parallel to the crystal surface. The size of the focal spot on the X-ray tube was between 25 and 40 u, and the distance from the X-ray tube focus to the specimen (approximately equal to the specimen to film distance) was -15 cm. White X-radiation was used from a tungsten target with not more than 35 kv in order to reduce the penetration of the X-rays into the specimen. Exposure times were approximately 1 hr with tube currents between 150 and 250 microamp. The type of photograph obtained from these crystals is illustrated in Fig. 1, which shows a number of overlapping reflections from the same crystal. The large uniform central reflection is traversed by sets of horizontal white and dark lines. These two sets run mainly parallel to one another. Lines of one color are wavy in nature and often branch and run together. Large areas of the crystal surface show no evidence of these lines whatsoever. The lines are interpreted as being due to low angle boundaries in the crystal, separating regions which are tilted with respect to one another. A white line is formed when the relative tilt forms a ridge at the interface and a black line is found when a valley is formed. In a number of cases, the lines stop and start within the area of the reflection and often run into the reflection from the edge, corresponding to a low angle boundary starting from the edge of the crystal. The prominent lines run roughly parallel to the direction of growth of the crystal although narrow bands can run in a direction perpendicular to this; see Fig. 2. Although they may change their appearance slightly, the lines tend to occur in the slightly,Same place in the X-ray image and to maintain their rough parallelism when the crystals are reduced in thickness by etching. Thus the low angle boundaries can occur at any depth within the crystal. The appearance of the lines is unaffected by subjecting the crystal to rapid temperature changes, such as plunging into liquid nitrogen or rapid quenching from 620°C. From the width of the lines on the x-ray reflection, values can be found for the angular misorienta-tion of the two parts of the crystal on either side of a boundary. The values found run from 1' to 10' of arc, but values of UP to 20' have sometimes been found, e.g., the widest lines on Fig. 2. These mis-orientations are much less than those commonly found in crystals possessing a lineage structure. When a number of a and white lines occur, running in a roughly parallel direction across the image of a Crystal, the total misorientation corresponding to lines of one color is approximately equal to that corresponding to lines of the other color. The interpretation of the lines as due to low angle boundaries has been checked in a number of ways. Photographs taken with different specimen-to-film distances distinguish lines due to low angle boundaries from effects due to surface relief of the specimen. Normal Laue back-reflection photographs, taken with the beam irradiating an area of the surface showing a number of the lines, show white lines running through each Laue spot. Black lines are set to see by this method. X-ray photographs were also taken, using the set-up described by Lam-one et al.5 when the beam straddles regions giving rise to lines in the Schulz pattern, split reflections are observed within the Bragg spot. The misorienta-tions calculated from the separation of these reflections and that found from the widths of the lines on the schulz technique patterns show good agreement. An exposure was made with Lambot technique of an area of the crystal showing no evidence of low angle

Jan 1, 1956

By Leonard Bernstein, Harry Bartholomew

MANY of the properties of metals and alloys are structure dependent. Not the least of these is the grain structure. For example, in producing alloy bonds between silicon or germanium and gold-alloy foil at temperatures above their eutectics (which are, respectively, at 370" and 356°C) but below the melting points of the individual constituents, it was found that wetting was more complete with a fine-grain structure than with a coarse-grain structure. In cases where the assemblies were held together for long periods of time at elevated temperatures, wetting was not as critically dependent on the grain structure as was the case for shorter periods of time. When liquid phase forms, it first forms in the grain boundaries due to the fact that most of the impurities are concentrated at the grain boundaries and that most impurities tend to lower the melting point of the gold alloy somewhat. In addition, grain boundaries are at high-surface free-energy levels and are thus in a more favorable condition to initiate good wetting. A fine-grain structure will have more grain boundaries per unit area than coarse-grain structure thereby making wetting somewhat easier. To make the grain structure of an alloy sys- tem visible, a satisfactory method for differentiating between the different grains of which the system is composed must be employed. For the alloy bonding system previously described, the grain structure on the foil surface is of primary interest. Conventionally used etchants for the gold-alloy system will not adequately delineate grain boundaries in their structures. For this reason an alternate method is proposed for those cases where such a determination is necessary. Foil between 0.0005 and 0.005 in. thick has been used in this determination. The equipment used in this investigation was described in a previous publication.' Essentially, it employs a resistance-type filament which can be heated up very rapidly and cooled very rapidly. A thin refractory material is placed on top of the heating element. This refractory material may be molybdenum, tantalum, tungsten, or even ceramic but its thickness should be less than 0.010 in. to minimize the temperature gradient across it. The gold-alloy foil is placed on top of this refractory material. The temperature of the heating filament is raised to 900°C and cooled down to below 100°C in 5 to 10 sec. During this cycle, the foil can be observed to plastically deform due to its own weight. With no further chemical etching, this assembly is then viewed under a standard metallurgical microscope and the grain size measured. Fig. 1 is a Au-1 pct Sb alloy at 400X magnification and Fig. 2 is a Au-1 pct Ga alloy at 130X. This technique has proved to be an adequate means for controlling processing conditions in producing large quantities of gold alloy foil.

Jan 1, 1963

By R. S. Silo

A new process for leaching oxidized copper ore (CuO) is presented. Its principle advantage is that it requires low cost raw materials. For large operations the only materials used are sodium chloride (NaCl) and calcium carbonate (CaCO3). In those operations of medium size, sulfur, which is abundant in the North of Chile, is used. However the process may also be applied to small copper plants provided low cost sulfuric acid is available as a substitute for sulfur. That is, it may be applied to those small capacity plants where large additional installations for the regeneration of the leaching solution are not needed. The method is comprised of six stages, namely: Crushing, Leaching, Washing of the Solution, Precipitation, Regeneration of the Leaching Solution, and Fusion. A flow diagram for this process in a large or medium-sized plant is given. LEACHING This process requires hydrochloric acid as the leaching solution for treating copper ores. This is easily produced from sulfuric acid and sodium chloride as follows: A small excess of NaCl is advisable to avoid the presence of free sulfuric acid. The experiments reported here were performed with 36 grams of HC1 per liter of solution to obtain a free acidity equivalent to 50 gpl of H2SO4 (the usual leaching solution concentration). Hydrochloric acid leaching may be done by either of the usual methods; i.e. percolation or agitation. The method selected depends on the characteristics of the ore. No matter which method is chosen, low pressure air can be used either as an air lift for circulation of the solution, or for agitation of the pulp with "Pachuca" tanks. In either case, there are no problems with respect to oxidation. Leaching by agitation produces good recovery; but at times, the problem of high consumption of leaching solution or the overproduction of grinding slimes which interfere with contact between phases negates this advantage. The percolation method was used in this study. Percolation took place in four 15-liter containers, 11 1/2 in. diam. by 12 in. height, having hemispheric bottoms. Each container was fitted with a wooden bottom having 1/4 in- holes. The air lift was a 3/4 in. plastic tube 10 in. high. Air at 6 psi was supplied from a rotating laboratory compressor. 10 kg of ore were charged to the container and counter-current leaching was used. The leaching solutions were fed through the center pipe in order to use the ascending solutions to reject the air in the charge. The solution circulated through the air lift in order to facilitate the movement according to the increase in density produced by the reaction between the phases present. Specific observations made in this report cannot be generalized because the leaching characteristics are dependent on the nature of the ore used, the method of leaching, and the production of primary or secondary slimes while crushing or leaching.

Jan 1, 1967

By Richard M. Foose

MOST of the roofing granules produced in Pennsylvania are made by two companies at three plants. The Advance Industrial Supply Co. has three quarries and a mill at Gladhill Station, in southern Adams County. The Funkhouser Company is actively engaged in mining, quarrying and milling at Charmian, about one mile west of Gladhill Station, and at Delta, in southern York County. These three plants produced approximately 100,000 short tons of granules in 1943. The production of roofing granules in 1937 for the whole country was only about 500,000 tons, generally indicating the large growth of the industry since that time. The fundamentals of producing roofing granules were discussed comprehensively by G. W. Josephson in a paper before the Industrial Minerals Division in October 1943 (Mining Technology, March 1944). The purpose of this paper is to describe the actual methods of mining the rock and milling it to make roofing granules, as practiced by the three Pennsylvania plants. MINING AND MILLING Funkhouser Company (Delta) The Funkhouser Company, near Delta, in southern York County, Pennsylvania, operates three joined quarries and a mine in the Peach Bottom slate. The joined quarries extend 1200 ft. in a northeast southwest direction along the strike of the slate cleavage and are about 200 ft. wide. The working face is about 45 ft. high. The quarrying operation is rather simple: Ingersoll-Rand Jackhamers, 1-in. and 1 1/4-in., with hollow drill steel, are used to undercut the quarry face with10-ft. holes. The face is "blown" and allowed to slump on the quarry floor. Loaded by a Marion electric shovel into trucks, the shattered rock is taken to the primary crusher 2500 ft. away. In addition to the normal quarrying operations, a drift into the northeast wall of the middle quarry was begun about 1935 and has advanced about 2000 ft. since then. Rooms have been driven at angles to the drift along choice beds of slate. The drifts and rooms have a roof more than 35 ft. high and the main drift and rooms are all more than 40 ft. wide. There is no cribbing at any place in the mine. Several of the rooms were driven upward on a 5º slope and in some of them there was stoping. Ingersoll-Rand Jackhamers are used, and only wet drilling is practiced. When visited in January 1940, an electric shovel was operating at the head of the drift, scooping up the slate blasted out of the working face. This, too, is trucked to the primary crusher. Some of the better quality slate is saved for making slate shingles. The primary crusher, which is a No. 30 McCulley gyratory, receives the slate from the trucks and crushes it to about 2-in. size (Fig. I). This product travels by a 30-in. belt conveyor to Niagara vibrating screens with 2-in. holes. The minus 2-in. product moves to a storage silo by bucket

Jan 1, 1945

By R. L. Slobod, H. A. Blum

A semiquantitative method for measuring the wettability of reservoir rocks has been developed. These data are needed for reservoir analysis and for interpretation of laboratory displacement studies. The wettability of a core sample is measured by the contact angle for the system oil-water-solid. These contact angles are calculated from the displacement pressure (threshold pressure) obtained by use of the centrifuge, using first oil-water and second air-oil in the same core sample. This method is based on the assumption that the air-oil and oil-water interfaces occupy similar positions in the porous medium when desaturation of the wetting phase is initiated. The assumption is also made that the Contact angle for the air-oil-solid system which is close to zero in value does not change appreciably even when the contact angle for the oil-water-solid system experiences marked changes. "Apparent contact angles'' for five different solids ranging from 31" to 82" have been determined, and changes irr the "apparent contact angle" of a given sample with laboratory use from 33" to 53' {lave been observed. INTRODUCTION Reservoir rocks vary in their wettability, 1,2,3,4 some being preferentially water wet while other are apparently preferentially oil wet. The degree of wettability, in theory, is measured quantitatively by the contact angle for the system solid-oil-water, hut in 1)practice this quantity is extremely difficult to determine." The need for obtaining some measure of this quantity has become obvious in recent years as a result of both laboratory. and field observations. Several reservoir.: such as the Bradford Sand in Pennsylvania and the Wilcox' at Oklahoma City are reported to be oil wet. If these report:: correctly reflect the true nature of the surface of the rock in the ground, then these reservoirs probably will not perform as predicted on the basis of a water wet rock. In the laboratory many core samples have been Observed to be oil wet. These samples, while perhaps not correctly representing the reservoir, have markedly different properties from water wet rock. The location of the phases is different (oil is in contact with rock instead of water), and other quantities such as the connate water, the capillary pressure curve; residual oil. relative permeabilities. and the recovery of oil by water flooding are markedly affected by the value of the contact -4 A further complication observed in the laboratory is the chang-ing of the wettability of a rock specimen with use. such changes mean that repeat runs on the same core are not the duplicate tests desired, but represent new experiments on a more oil wet material. The changes in surface characteristics are sometimes so rapid that by the time an experiment requiring several days is completed, the results may not be representative of the core as originally described, The, rock material itself (Silica. carbonates. etc.), whell Clean and uncontaminated, is water wet. There seems b( : little evidence of the presence of oil wet minerals such as heavy metal sulfides. The oil wetness of reservoir samples, therefore, is believed to be caused by the accumulation of an adsorbed film in which the polar group of a large organic. molecule is adsorbed on the surface leaving the organic or hydrocarbon part of the molecule projecting out from the solid. Such a surface is much more readily wet 17" oil than by water. These considerations indicate the need for a method which will provide some measure of tile wettalbility (Contact(angle if possible) for reservoir rock ..samples) The method should be capable of (1.1 distinguishing between tile wettalility of dif. ferent formation,.. (2) detecting (change. ill wettalbility of a core with use. and (3) measuring the changes in Wettability which may be accomplished with cleaning operations. such as the use of sodium silicate for increasing water wrettalbility." A preliminary report on such a method is preseted below. not with the idea that this procedure alone will Solve the wettabil-ity problem. but rather that it may provide encouragement to

Jan 1, 1952

By M. Mathieu

The Rove tunnel is the means by which the canal from Marseilles to the Rhone Riverl penetrates the hills of Nerthe, lying between Mar- seilles harbor and Lake Berre, Fig. 1. The canal will communicate at sea level with both terminals. The original project planned a lock near the village of Marignane; but observations, pursued for more than three years, showed that the water surface gradient would average only 0.015

Jan 1, 1923

By M. Mathieu

The Rove tunnel is the means by which the canal from Marseilles to the Rhone Riverl penetrates the hills of Nerthe, lying between Mar- seilles harbor and Lake Berre, Fig. 1. The canal will communicate at sea level with both terminals. The original project planned a lock near the village of Marignane; but observations, pursued for more than three years, showed that the water surface gradient would average only 0.015

Jan 1, 1923

By N. Mungan, F. W. Smith, J. L. Thompson

Adsorption of polymers and transport, rheology and oil recovery efficiency of their solutions were studied in the laboratory to evaluate the use of polymers in waterflood-ing. While a tenfold mobility reduction was obtained with polymer concentrations as low as 0.05 per cent by weight, the mobility reduction depended on the type of polymer, molecular weight, salinity and pH of water, crude oil and capillary properties of the porous media. Choice of a suitable polymer and a workable concentration will have to be tailored for each application. Little reduction in the residual oil saturation can be expected from polymer flooding. Improvement in the volumetric sweep efficiency is possible hut the extent of the improvement can best be evaluated by properly designed field testing. Some aspects of the field use of polymer floods are discussed. INTRODUCTION Waterflooding is a simple, inexpensive secondary recovery method and is being used widely. Innumerable laboratory studies have been made to unravel the fundamentals of the displacement of oil by water and to find the ways of most efficient oil recovery. These studies and a great many field case histories have revealed that the prime cause of poor oil recovery is the inefficient and incomplete sweep of reservoir volume by the injected water. Sweep efficiency is affected by many factors of which the mobility ratio is an important one. Mobility ratio M is defined here as the ratio of water to oil mobilities: M = (k»/y,r)/(k,JJJJ........(1) In Eq. I, the permeabilities are the effective permeabilities and depend on fluid saturations and, hence, change during the different depletion stages in a flood. A wide practice is to use the effective water permeability at residual oil saturation and the effective oil permeability at interstitial water saturation in Eq. 1. If the mobility ratio is greater than one, the mobility ratio is unfavorable and water, being more mobile than oil, would finger through the oil zone resulting in poor oil recovery efficiency. If the mobility ratio is favorable (one or less) the displacement of oil by water occurs more or less in a pistonlike fashion. In some waterfloods. the mobility ratio is unfavorable and any additives by which the mobility of water can be decreased would favor more efficient oil recovery. The thing to bear in mind, however, is whether or not the improvement in oil recovery is sufficient to more than pay out the cost of the additives needed. For example, materials like sugars, alcohols and glycerine reduce water mobility by thickening the water, but the cost of material requirement precludes any field application. For an additive to be useful in water-flooding, it must bring about a large reduction in water mobility at low concentrations; it must be adsorbed only negligibly; and it must not completely plug up the formation. Some synthetic organic polymers have shown promise of meeting these requirements and have been used in the field.'-W owever, no in-depth studies of the rheological, adsorption and oil displacement characteristics of polymer solutions have been reported. The present work is a study of these properties. EXPERIMENTAL In this work, concentrations are given on a weight per volume basis; 0.5 per cent concentration means 0.5 gm of polymer is dissolved in enough water (or NaCl solution) to make 100 ml. A bactericide, usually 0.1 to 0.2 per cent by volume of 38 per cent formaldehyde solution, was used in the polymer solutions. The NaCl solution was 30,000 ppm. Some properties of the polymers studied are given in Table I. Physical properties of all cores used are in Table 2. Flow behavior of polymer solutions was studied by three consecutive flow tests in cores. First, water (or brine) was injected at constant rate of about 1 ft/D to obtain the water mobility. Then, filtered polymer solution (prepared in water or brine) was flowed through the core. Since the rate was constant, increase in the pressure drop across the core reflects decrease in the mobility. Finally, the core was flooded with water (or brine) to study recovery of mobility. The Alundum cores which were used in

Jan 1, 1967

By F. H. Willcox

THE CHAIRMAN (HENRY D. HIBBARD, Plainfield, N. J.).-This paper is timely because of the changed conditions due to the great war, but apparently its scope is limited to oxidation process steels. Referring to the four numbered observations on page 199: No. 1 seems to ignore Johnson's discoveries about oxygen in cast iron. No. 2 ignores crucible steel. No. 3 ignores red short steel containing enough gas solvents to make it solid, while No. 4 assumes that a deoxidizer is necessarily a gas decomposer or solvent and vice versa, which it not always is. From these observations it is deduced. that the only hole-forming gas in steel is an oxide of carbon (CO presumably is meant), which is not true.

Jan 4, 1917

By Timothy P. Smirnoff

INTRODUCTION The Jones Island Inline Pump Station is a major element of the Milwaukee Metropolitan Sewerage District's (MMSD) Inline Storage Facilities Plan in Milwaukee, Wisconsin. See Figure 1. This underground 6.6 cu m/day (150 MGD) Pumping Station will be located immediately south of the existing Jones Island Treatment Plant at the confluence of the Menomonee and Kinnickinnic Rivers on the Milwaukee Bay, south of the Milwaukee River. [ ]

Jan 1, 1984

By John M. Dealy, Robert D. Pehlke

This note presents a summary of the available literature on activity coefficients at infinite dilution in binary metallic solutions, Table I. These data should prove useful in not only examining the therm-odynamic properties of binary metallic solutions, but also in predicting the activity of a component in a complex alloy. The relationship proposed by wagner1 for expressing the activity coefficient in dilute solution is of the form:

Jan 1, 1963

By A. S. Yue

The movphology of the Mg-32 wt pct Al eutectic has been studied as a function of freezing- rate and temperature gradient. At slow freezing rates a lamellar eutectic was formed; whereas, a rod-like eutectic was generated at fast rates. The inter-lamellar spacing increased as the freezing rate decreased in aggreement with theoretical predictions. Lamellar faults, morphologically similar to edge dislocation models in crystals, were responsible for the subgrain structures in the eutectic mixture. A linear increase in fault density with freezing rate was observed. Fault concentl-ations of the order of 10 per sq cm for a range of freezing rates from 0.6 to -3.0 x 10 cm per sec were estimated. The transformation from lamella?, to rod-like morphologies was determined experimentally to be dependent on the freezing rate and independent of the temperature gradient. Moreover, the number of rods formed per- unit cross-sectional area increased exponentiallv with increasing freezing rote. BRADY' and portevin2 classified eutectic structures into lamellar, rod-like, and globular according to the morphology of the solid phases present. Although this classification is quite descriptive, very little has been reported on the details of the mechanism by which the eutectic structures are formed. Recent work by Winegard, Majka, Thall, and chalmers3 and by chalmers4 on lamellar eutectic solidification suggest that the maximum thickness of the lamellae decreases with increasing rate of solidification due to inadequate time for lateral diffusion. scheilS and Tiller' have shown theoretically that the lamellar widths indeed depend on the solidification rate. However, there has been no experimental evidence to support the theory. Chilten and winegard7 have studied the interface morphology of a eutectic alloy of zone-refined lead and tin. They found that the lamellar width decreased as the freezing rate increased in agreement with the theoretical predictions of scheils and Tiller.' More recently, Kraft and Albright' have investigated the microstructures of the A1-CuA12 eutectic as a function of growth variables. They observed lamellar faults present in the lamellar eutectic, similar to edge dislocation models in crystals. Furthermore, Kraft and Albright reported that they could not designate which extra lamellar was responsible for the formation of a lamellar fault even under electron microscopic magnification. In this paper, the morphology of the Mg-A1 eutectic structure is described. The effects of freez- ing rate on the interlamellar spacing and on the lamellar fault density are presented in detail. The transformation from lamellar to rod-like eutectics is discussed in terms of the freezing rate and the temperature gradient. EXPERIMENTAL PROCEDURE The experimental details of alloy preparation, the decanting mechanism and the determinations of the freezing rate and the temperature gradient have been reported elsewhere. Measurements of plate-edge angles were made with a microscope. The true angles used to determine the interlamellar spacings were determined by a two surface analysis technique.'' Since the decanted interface structure does not represent the true eutectic morphology on the solid,g all measurements were made from an area in the solidified bar behind the interface. Measurements of the apparent interlamellar spacings between the two phases of the eutectic were made on a photographic negative by means of a calibrated magnifier. Each value listed in Table I represents the average of thirty measurements on one negative. In general, these measurements are approximately equal with an error of less than pct. The average rod diameter for each specimen was also measured on a magnified photomicrograph. Each value of the diameter represents the average of fifty measurements. RESULTS AND DISCUSSION The experimental observations and their discussion to be presented here are restricted to the morphology of the eutectic structure and to the effects of the freezing rate and the temperature gradient on the solidification of eutectics. INTERLAMELLAR SPACING It has been shown previouslyg that the micro-structure of the decanted interface and the longitudinal section of the Mg-A1 eutectic is characterized by the presence of both lamellar and rod-like morphologies. The lamellae become more regular as the freezing rate is decreased. A three-dimensional photomicrograph representing a perfect lamellar morphology is illustrated in Fig. 1. The lamellae of the top and longitudinal sections of the specimen are regularly spaced while those in the transverse section are not quite straight and parallel. Their parallelism is slightly distorted because fault lines producing a discontinuity are present. A method for calculating the interlamellar spacings A, is described in Appendix 1. The true

Jan 1, 1962

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

By F. E. Werner, B. L. Averbach, Morris Cohen

THAT bainite formed near the M, temperature bears a striking r esemblance to martensite tempered at the same temperature has been shown by the electron microscope.' By means of electron diffraction,' it has been established that carbide and cementite are present in bainite formed at 500°F (260°C); these carbides are also found in martensite tempered at 500°F (260°C).' The investigation reported here is concerned with an X-ray study of the matrix phases in lower bainite and tempered martensite. These phases have turned out to be dissimilar in structure; the matrix of bainite is body-centered-cubic while that of tempered martensite is body-centered-tetragonal. A vacuum-melted Fe-C alloy containing 1.43 pct C was studied. Specimens of 16 in. diam were sealed in evacuated silica tubing and austenitized at 2300°F (1260°C) for 24 hr. One specimen was quenched into a salt bath at 410°+7 °F (210°+4°C), held for 16 hr, and cooled to room temperature. The structure consisted of about 90 to 95 pct bainite, the re: mainder being martensite and retained austenite. A second specimen was quenched from the austen-itizing temperature into iced brine and then into liquid nitrogen. It consisted of about 90 pct martensite and 10 pct retained austenite. The latter specimen was tempered for 10 hr at 410°+2°F (210°+1°C). The specimens were then fractured along prior austenite grain boundaries (grain size about 2 mm diam) by light tapping with a hammer. Single aus-tenite grains, mostly transformed, were etched to about 0.5 mm diam and mounted in a Unicam single crystal goniometer, which allowed both rotation and oscillation of the sample. Lattice parameters were measured by the technique of Kurdjumov and Lyssak. This method takes advantage of the fact that martensite and lower bainite are related to austenite by the Kurdjumov-sachs orientation relationships Thus, the (002) and the (200) (020) reflections can be recorded separately, permitting the c and a parameters to be determined without interference from overlapping reflections. According to these findings, the matrix phase in bainite is body-centered-cubic and, within experimental error, has the same lattice parameter as ferrite (2.866A). On the other hand, martensite, tempered as above, retains some tetragonality, with a c/a ratio of 1.005t0.002. Most workers in the past have assumed that bainite is generated from austenite as a supersaturated phase, but the nature of this product has not been established. The question arises as to whether bainite initially has a tetragonal structure and then tempers to cubic, or if it forms directly as a cubic structure. If it forms with a tetragonal lattice, it might well be expected to temper to the cubic phase at about the same rate as tetragonal martensite. The martensitic specimen used here was given approximately the same tempering exposure, 10 hr at 410°F, as suffered by the greater part of the bainite during the isothermal transformation. About 50 pct bainite was formed in 6 hr at 410°F. On tempering at this temperature, martensite reduces its tetragonality within a few minutes to a value corresponding to 0.30 pct C.' Further decomposition proceeds slowly, and after 10 hr the c/a ratio is still appreciable, i.e., 1.005. Thus, even if the bainite were to form as a tetragonal phase with a tetragonality corresponding to only 0.30 pct C, which might be assumed to coexist with e carbide, it would not be expected to become cubic in this time. It seems very likely, therefore, that bainite forms irom austenite as a body-centered-cubic phase and does not pass through a tetragonal transition. The carbon content of the cubic phase has not been determined, but it could easily be as high as 0.1 pct, within the experimental uncertainty of the lattice-parameter measurements. It has been postulated that retained austenite decomposes on tempering into the same product as martensite tempered at the same temperature. There is now considerable doubt on this point. The isothermal transformation product of both primary and retained austenite at the temperature in question here is bainite," and the present findings show that bainite and tempered martensite do not have the same matrix. Acknowledgments The authors would like to acknowledge the financial support of the Instrumentation Laboratory, Massachusetts Institute of Technology, and the United States Air Force.

Jan 1, 1957