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By P. Ramachandrarao, T. R. Anantharaman

EVER since the technique of quenching metals and alloys from the melt (splat cooling) was perfected a decade ago, it has been recognized that the grain size of products solidified by this technique may be extremely small.' The further observation that fcc metals quenched from the liquid state contain very few dislocations has led to the inference2 that metals are subjected to negligible or no stresses during the rapid solidification characteristic of the "gun" or "piston-and-anvil" technique. Evidence for the incidence of appreciable densities of stacking faults has, however, been obtained in case of some splat-cooled fcc and hcp alloys,3 although not for pure metals. In the light of these earlier observations it was considered desirable to study X-ray line-broadening effects, if any, in fcc metals rapidly cooled from the melt. In the present work pure silver (>99.99 pct), aluminum (>99.99 pct) and lead (>99.9 pct) were quenched from the liquid state from temperatures about 50°C above the melting point by the "gun technique" and the resulting foils were subjected to X-ray examination in a Philips Diffractometer. The quenched foils (up to -10 u thick) did not generally stick to the substrate surface and could be easily transferred to the Diffractometer without introducing any plastic deformation. The profiles of the first five reflections from the foils were recorded in each case with Cu Ka, radiation at the slowest available scanning speed of 1/8 deg per min. To correct for instrumental broadening, profiles were also recorded from the metals annealed in vacuo at suitable temperatures. The integral breadths of the X-ray reflections were arrived at by a procedure described earlier.' There was a distinct suggestion of preferred orientation in the recorded intensities of reflections from aluminum and lead foils. Such an effect was not observed in case of silver. In addition, the integral breadths of X-ray reflections from splat-cooled aluminum and lead were not significantly different from those recorded for the annealed metals. The analysis was therefore continued only for silver where the X-ray line broadening was appreciable. The pure diffraction broadening, B, was evaluated for each X-ray reflection (hkl) from silver from the observed, B, and instrumental, b, breadths with the aid of each of the three equations due to Scherrer,5 Anantharaman and Christian,6 and Warren and Biscoe,7 respectively: Bs= B-b BAC=B- b2/B Table I gives the values of particle size, 71, the lattice strain, E, arrived at by the use of the following well-known relations and on the assumption that all observed diffraction broadening could be attributed to lattice strain or particle size, respectively: E = 1/4 cos ? n= B cos ? where A is the wavelength of X-radiation and 0 is the Bragg angle. As no significant peak shifts or asymmetry could be detected in the profiles from the foils, the possibility of any significant contribution due to twins or stacking faults was ruled out. The absence of faults is by no means surprising since pure silver is known to develop stacking faults only on severe deformation and the stacking fault densities recorded so far for even silver filings have been extremely low.' The very low values for percentage mean deviation from the mean value for the particle size in Table I strongly suggest that all observed broadening in splat-cooled silver can be attributed only to small particle size. This conclusion receives further support from the lowest mean deviation recorded for data computed from the Scherrer equation based on Cauchy profiles that are considered characteristic of particle size broadening. Further analysis for separation of particle size and lattice strain effects was considered unnecessary in view of the very large mean deviations obtained for strain values and also the earlier results suggesting absence of even detectable strain in metals and alloys quenched from the melt. It is to be stressed in this connection that the particles are actually grains and not cells formed by walls of high dislocation density usually encountered in deformed samples. As such, the absence of strains is not surprising. The present results are probably the first to record X-ray line broadening due only to small particle

Jan 1, 1970

By K. W. Smith, E. A. Thomas

Various grades of synthetic mullite have been developed in recent years to replace or supplement natural sources of mullite deriued from the mullite group of minerals consisting of sillimanite, kyanite, and andalusite. Raw materials and heat treating processes used in making synthetic mullite are described. Chemical and physical data are given for typical grades and crystalline structure is illustrated with micrographs. Use of synthetic mullite as a refractory material in the glass and metallurgical industries is discussed. Mullite (3A12O3.2siO2), the only stable compound formed in the alumina-silica system, is usually present to some degree in all aluminum silicate ceramic products. The formation of mullite is considered beneficial to give rigidity to the structure and is dependent upon the ratio of Al2O3 to SiO2 in the original composition, particle size, degree of mixing, firing temperature, cooling rate, and the presence of auxiliary glass-forming fluxes. Mullite may also be formed at the reaction interface of fire clay or alumina-type refractories in contact with glass or slag melts. The term synthetic mullite is commonly used today to identify a class of sintered and fused aggregates or grains in the alumina-silica system having a highly developed mullite structure but derived mainly from raw materials other than the sillimanite group of minerals. Within the past 15 years extensive research has been done to develop economical processes to form sintered synthetic mullite aggregate to replace calcined Indian kyanite in super-refractories. Severa1 brands of such mullite are now being produced in commerical quantity and finding extensive use in refractories. Based on the service results of such refractories in many applications throughout the metallurgical, ceramic, and glass industry these developments have been considered successful and suitable substitutes for Indian kyanite now appear assured. EARLY DEVELOPMENT The conversion of kyanite, sillimanite and anda-lusite minerals of the sillimanite group to mullite and their use in refractories and porcelain have been discussed quite extensively in the literature by peck,' Grieg,' Riddle and Foster,3 Bowen and Grieg,4 and others and will only be mentioned here for reference to compare properties with synthetic mullite. In 1928, curtis5 reported on the development of a high temperature gas-converter process for forming synthetic mullite. The raw materials were derived mainly from lumps of high alumina clay of the correct natural composition or blends of clays and alumina that was interground and briquetted to form a suitable charge to maintain a surface combustion firing within the converter. Curtis was, no doubt, the first to illustrate by micrographs in natural color the crystalline structure of mullite derived from kyanite and mullite derived by sintering clay and alumina mixtures at temperatures above cone 32 (3123°F) and by electric fusion. In 1937, sei16 was issued a patent covering the use of a mixture of alumina-silica minerals and alumina in the proportion to form a mullite-yielding material at temperatures in excess of 3100' F. During the period from 1930 to 1940, economic conditions were not favorable for the production of synthetic mullite mainly due to an adequate supply of good grades of Indian kyanite ore suitable for conversion to mullite. Uncertain conditions on availability of the Indian kyanite during the early stages of World War II fostered further study on the development of synthetic substitutes. In 1943, McVay and wilson7 reported on an extensive investigation of domestic substitute materials. Their work covered essentially the use of mixtures of electric furnace mullite, calcined topaz, and calcined domestic kyanite. Compositions were found that gave equivalent or better hot load strength than Indian kyanite in mullite-type brick compositions; however, the calcining of the topaz presented certain physical and chemical problems on the disposition of silicofluoride and hydrofluoric acid while the high cost of electric furnace mullite was a limiting factor. In this work it was pointed out that water-quenched fused mullite was found to be unstable on reheat and gave poor hot load strength due to excessive glass present whereas the slow cooled or annealed mullite contained large crystals of mullite and corundum with little glass and gave superior results.

Jan 1, 1961

By L. D. Lash, J. R. Ross

Discovery of scandium in the Vitro solvent extraction plant for uranium led to commercial recovery of the byproduct. Micro amounts of scandium were extracted with uranium by dodecyl phosphoric acid, but failed to follow ura-niuminto the hydrochloric acid strip solution and were eventually concentrated in the organic extractant. A fluoride strip system was developed to recover scandium from the solvent in concentrated form. High purity scandium oxide was then prepared in multi-pound lots by chemical separation techniques. The plant recovery operation, final product purification, and analytical procedures are described. Scandium is a pseudo-rare earth which is truly rare and expensive. It has special properties which may make it desirable even at the present price of $2750 per lb. Recently the price was lowered from $5000 per Ib which had prevailed since 1952, and it is anticipated that usage will be stimulated because of the lowered price. This metallic element is distributed widely in trace amounts in the rocks of the earth's crust. In addition to micro-amounts found in most uranium ores, concentrations of 50 to 100 ppm have been found in Colorado ferberite ore, lateritic nickel ore, heavy sandstone from Utah, Wyoming, and New Mexico, and various zircon sands and monazites from the western part of the U. S. Scandium has been found as an essential constituent of very few minerals, the most important being thortveitite, a scandium silicate. At the present time, this mineral commands a price more than twice that of gold. Chemically, scandium is in group 3A of the periodic table. It is closely associated with yttrium and the rare earths which it strongly resembles in its reactions. It has a valence of three and will form an insoluble hydroxide, fluoride, or oxalate under proper conditions, similar to the rare earths. Eight years before its discovery, scandium was predicted by Mendeleef who ascribed his eka-boron with properties nearly identical to the actual properties of scandium. Its position as the element with Atomic No. 21 and Atomic Weight 44.96 places it between calcium and titanium in Period 4 of the chart. The successful commercial application of scandium must depend on unique properties to justify use of this high cost substance. Greater consumption would allow additional price reductions, but scan- dium will remain a relatively high-priced commodity because of its inherent scarcity. Research reportedly has been oriented toward use of scandium as an agent to achieve high-temperature, low-density alloys with magnesium and tantalum.' Also, the U.S. Air Force sponsored a project for production of research amounts of pure scandium metal.' The oxide has been used experimentally in electronics, ceramics, and metallurgy. The various aspects of scandium are well covered in recent publications.s-5 CONCENTRATE RECOVERY Small amounts of scandium exist in uranium ores and are dissolved during an acid leach yielding up to 0.001 gpl Sc2O9. When Vitro converted their uranium plant from phosphate precipitation to solvent extraction: scandium was found to follow the uranium into the dodecyl phosphoric acid solvent (DDPA). However, scandium did not strip with uranium from the DDPA in hydrochloric acid, but remained in the solvent. Therefore, a concentration of scandium built up in the organic phase. Residues from the solvent were spectrographed by the U.S. Bureau of Mines and found to contain scandium. As a result of this discovery, provisions were made in the plant for recovery of scandium-bearing concentrates. Solvent extraction of uranium was added to a conventional acid leach process in a typical installation? The ore was crushed and ground, and then leached with dilute sulfuric acid. Addition of an oxidant such as sodium chlorate insured conversion of uranium minerals to a soluble form. At this point, the slurry was chemically reduced by a sulfide, such as sodium hydrosulfide, to remove substances such as ferric iron and molybdenum which were partially extracted by the solvent. The solids-liquid separation was accomplished by a four-stage counter cur rent decantation (CCD) thickener circuit. The uranium was extracted from pregnant liquor with 0.1M DDPA in kerosene and stripped with ION

Jan 1, 1961

By William Y. Holland, Roger M. Cook

In view of the increasingly widespread deterioration of concrete structures as the result of the interaction of the alkalies sodium and potassium released by hydration of portland cement and susceptible rocks and minerals in aggregates, it is believed that a paper summarizing the geographic distribution of these aggregates will be of interest to producers and users of concrete, concrete products, and concrete-making materials. THIS paper reviews the problem of alkali-aggre-gate reaction in concrete and describes the geologic and geographic occurrence and distribution of alkali-reactive sand and gravel in western United States. It includes no discussion of crushed stone or synthetic aggregates. Most deposits of sand and gravel are accumulations of particles of rocks and minerals from a variety of sources, and it is not unusual for at least one or two varieties of the rocks to contain some form of reactive material. Examination by petro-graphic methods of many sands and gravels, as well as manufactured aggregates, has shown that a comparatively high proportion of the deposits does contain, in greater or lesser degree, rocks and minerals known to be deleteriously reactive with the alkalies of cement. Fortunately the amount of reactive materials is commonly less than that necessary to cause deleterious effects in concrete. As investigation of unsound concrete structures progresses, it becomes evident that the alkali-aggre-gate reaction is even more widespread than supposed, Figs. 1 and 2. Even though some parts of the country appear at present to be immune, further investigations will probably show that the effects of alkali-aggregate reaction can be seen in many structures in these areas, although only on a small scale in most of them. Many concrete structures will, of course, have lived their useful life before disintegration from this cause is serious, and in others the alkali-aggregate reaction may never become significant even though the microscopic evidence of reaction is present. The alkali-aggregate reaction first was reported to be a cause of deterioration of concrete in 1940 when Stanton1 described expansion of concrete pavements in California. Similar expansion and deterioration of concrete was recognized during succeeding years in concrete structures located in many parts of the country, but particularly in the western states. A number of concrete laboratories2 became interested in the problem. It was soon determined that only certain combinations of aggregate and cement caused the alkali-aggregate reaction to take place, and moreover that the reaction progresses only in the presence of water. Further research proved that cements containing more than 0.60 pct total alkalies (pct Na,O + 0.658 x pct K2O), when used with aggregates containing appreciable amounts of reactive ingredients, caused the reaction to take place, usually with subsequent deterioration of the concrete. During the last few years this limitation has been adhered to in both government and private construction as the maximum allowable alkali content of cement to be used with aggregates of known alkali reactivity. Because of this limitation, it appears that deleterious reaction either has been reduced or eliminated in many recently built structures in which it probably would otherwise have occurred. Recent tests have shown that the degree of expansion obtained with any particular cement-aggre-gate combination depends not only on the alkali content of the cement but also upon the relation of this alkali content to the amount and degree of reactivity of reactive constituents in the aggregate.' In laboratory mortar bars, opal and cements with alkali content of as low as 0.2 pct (as equivalent of Na2O) have produced deleterious expansion as the result of alkali-aggregate reaction. These experiments demonstrate that aggregates containing even 0.1 pct of opal are deleteriously reactive. It was soon determined that alkali-silica gels were formed by the interaction of the alkalies of the cement and the reactive aggregate, Figs. 3 and 4. Osmotic or swelling pressures produced by the continued hydration of these gels cause expansion of the concrete with resulting cracking, warping, and dislocation. Evidence of the alkali-aggregate reaction can be seen by a petrographic study of the deteriorated concrete. Among the first structures studied by this method was Parker Dam on the Colorado River, California-Arizona. In the concrete from this dam pebbles of rhyolite, andesite, siliceous limestone, and chalcedonic chert were found to be reactive.

Jan 1, 1954

By R. E. Reed-Hill, W. H. Hartt

High-purity magnesium single crystals, oriented with basal plane parallel to stress axis, were deformed in tension at room temperature so as to form second-order (1011)- (1012) twins. Investigation by optical and replica electron microscopy revealed that these twins can support very large internal strains approaching 1000 pct and that fracture follows as a direct consequence of these strains. At low strains the basal plane within (10i1)- (10i2) twins rotates with increasing deformation until it becomes approximately parallel to the twin boundaries. This rotation is not consistent with deformation by basal slip in the double twin, but may be rationalized in terms of nonbasal slip. Observations also indicate that basal slip in the primary (1011) twin, prior to second-order twinning, may contribute to this rotation. Deformation markings that are difficult to interpret in terms of slip on previously observed systems were noted in the twin bands. A possible means of rationalizing these markings is to relate them to grain boundary shear. The fracture associated with these twins is thought to initiate by formation of voids at the twin boundaries. These grow into microcracks, with ultimate fracture occurring by tearing of the interconnecting regions. THE significance of deformation and fracture along second-order (10i1)-(10i2) twins in polycrystalline magnesium1-' and many magnesium alloys4 was discussed in a previous paper.5 It was noted that this double twinning mode effectively controls the room-temperature deformation and fracture of magnesium single crystals, oriented with the basal plane parallel to the tensile axis. Reed-Hill and Robertson6 observed that, although these crystals may fracture at a macroscopic strain of less than 1 pct, shear strains up to 1000 pct could occur within (1011)- (10i2) twin bands. They concluded that the fracture was "ductile" and resulted from concentrating the deformation into a very small volume. The present research was undertaken to obtain a better understanding of the deformation and fracture associated with these twins. EXPERIMENTAL TECHNIQUES The experimental procedure involved straining high-purity magnesium single crystals in tension at room temperature. Specimens were oriented so that the applied stress direction was within 2 deg of the [1010] crystal axis. The specimen cross section was rectangular with faces closely parallel to (1210) and (0002). The specimen preparation and testing procedures have been described in detail elsewhere.5 Second-order (1011)- (1072) twins nucleated during straining were studied using optical and replica electron microscopy techniques. For the latter, cellulose acetate-carbon double replicas were employed. Observations were made on the (1210) crystal surface, which is the plane of shear for twins of this type. In addition to the single crystals, some investigations were carried out on longitudinal polycrystalline specimens. These were obtained from high-purity magnesium plate with a texture in which the basal planes of the grains tended to be nearly parallel to the specimen axis. All. polycrystalline specimens were annealed prior to testing in order to produce a coarse grain structure, permitting Laue back-reflection X-ray photographs to be obtained from grains of interest. EXPERIMENTAL RESULTS a) Deformation Within ( 101 l )-( 1072) Twins. Fig. 1 is an optical micrograph demonstrating the extent of the plastic deformation that can occur in (1011)-(10i2) twin bands. Notice at the lower left corner of the photograph the large displacement of the dark band (a polishing step) where it crosses the twins. The shear strain in the twin band at this position was computed to be 700 pct, using the ratio of step width to twin thickness. It was previously shown5 that (1011)- (1012) twin bands are often composed of small, separate twins aligned close to the macroscopic habit plane. Fig. 2 is an electron micrograph from near the upper end of the twin band in Fig. 1. This illustrates that the twin habit often does not coincide exactly with the macroscopic band habit, but may be inclined at a slightly smaller angle to the matrix basal plane. Figs. 3 through 6 are electron micrographs of the twin band in Fig. 2 illustrating successive steps in the development of deformation inside the band. A twin band such

Jan 1, 1969

By R. W. Snyder, H. J. Ramey

This paper presents the results of applying the Buckley-Leverett' displacement theory to petroleum reservoirs consisting of a finite number of layers. The layers are assumed to communicate only in the wellbores, and the reservoir may be represented as a linear system. Most previous investigations of this nature were limited by assumptions and by inconsistent calculation techniques. This study improves on previous work by applying the Buckley-Lev-erett displacement theory to a noncommunicating layered system where permeability, porosity, initial saturation, residual saturation and relative permeability vary from layer to layer in a logical and consistent manner. Gravity and capillary-pressure effects are neglected. A modification of the Higgins-Leighton calculation method was used in this study. Waterflood predictions were made with all properties varying, and then with only permeability varying using several inability ratios. These results were compared with the Stiles and Dykstra-Parsons predictions. It is shown that the latter methods generally give poor values for the breakthrough recovery and pessimistic predictions for the performance after breakthrough. Similar results were obtained for a gas-displacement case. lNTRODUCTION Field experience with immiscible displacement usually shows constant producing conditions until breakthrough of the displacing fluid. Then oil production continues at increasing displacing-to-displaced fluid ratios until the economic limit is reached. Three different ideal mechanisms are known that will produce this behavior: (1) relative permeability effects as described by Buckley-Leverett frontal advance theory,' (2) vertical stratification as considered by Stiles,2 Dykstra and Parsons5 and others and (3) different path lengths involved in areal (two-dimensional) flow between wells as described by Dyes et al.4 Without question, a combination of these factors modified by formation heterogeneity and other known and unknown factors actually does control the behavior of real systems. This paper presents results of an investigation of certain factors that should affect performance but which have received little attention to date. In 1944, Law5 demonstrated that porosity and perme- ability are often found to have normal and logarithmic-normal distributions, respectively. throughout cored intervals in natural formations. This led to the concept of the noncommunicating, multilayered reservoir model for immiscible displacement. This model assumes that the reservoir is composed of a number of layers that communicate only at the wellbores. Each layer is individually homogeneous, but may be different from every other layer. Stiles' presented one of the earliest applications of this model to waterflood performance. In addition, Stiles assumed that the initial saturations and relative permeabilities were the same for each layer, porosity was the same. displacement was piston-like, fluids were incompressible and injection into each layer was proportional to that layer's permeability capacity (permeability-thickness product). The last assumption would be true if the mobility ratio for the displacement were unity.21 Dykstra and Parsons" used the same model as Stiles, but rigorously included mobility ratios other than unity for piston-like displacement. Dykstra and Parsons used their general result to produce charts for log-normal permeability distributions between layers. Similarly, Muskat6 Pub1ished analytical solutions for linear and exponential permeability distributions. In 1959, Roberts' described a scheme for calculating water-drive performance for the noncommunicating, layered reservoir model which considered two-phase flow in the displaced region. Roberts used the same model and assumed that the injection rate into a layer was proportional to that layer's permeability capacity, but that flood front locations could be evaluated from the Dykstra-Parsons results. These assumptions are inconsistent, and a material balance cannot be maintained except for a mobility ratio of unity. At the same time, Kufus and Lynch8 coupled Buckley-Leverett displacement theory with the layered model to provide an improvement of the Dykstra-Parsons method that was consistent. In 1960, Higgins and Leighton9 resented a numerical method for calculating waterflood performance also considering two-phase flow in the displaced region. The result was used to investigate variation in absolute permeability and oil viscosity. An excellent, detailed history of using the noncomrnunicating, layered reservoir model was presented by Nielsen.'" The preceding techniques (and many related ones) were similar in that differences in initial saturations, residual saturations and relative permeabilities from layer to layer were neglected. It is well known that the irreducible water saturation is an important function of absolute permeability. Calhoun11 showed that the irreducible water saturation

By M. J. Marcinkowski, E. N. Hopkins

An investigation has been made of the ß(fcc) — a(hexagonal) transformation which occurs in lanthanum using both electrical resistivity and transmission electron microscopy techniques. It has been shown that the ß phase can be retained below the transformation temperature by rapid quenching but that the sample immediately begins to transform to the a phase. The transformation is observed to nucleate in the vicinity of inclusions. Based on the above observations, a detailed model of the transformation has been advanced which involves the nucleation of an extrinsic stacking fault bounded by a pair of Shockley partial dislocations in the vicinity of some heterogeneity, i.e., an inclusion. The stress field of the resultant dislocation pair acts to nucleate extrinsic faults in adjacent planes and leads quite naturally to the B-a conversion with a minimum of strain energy induced in the crystal. LANTHANUM possesses an fcc structure ß) (8) upon cooling transforms to a hexagonal modification (a) in much the same way as cobalt. The one exception, however, is that the stacking sequence of the closest packed planes in a La is ABAC ABAC, and so forth,1 whereas in cobalt it is ABAB, and so forth, i.e., hep. Mainly on the basis of transmission electron microscopy techniques, there seems to be little doubt that the 0 — a transformation in cobalt involves a dislocation mechanism2 although its exact nature still remains obscure. Although the ß - a transformation in lanthanum is somewhat more complex than that occurring in cobalt, it was thought that its very uniqueness would be helpful in understanding fcc — hexagonal transformations in general. Such a general understanding of these transformations is important since they represent what are perhaps the simplest of the martensitic class of transformations. The experimental techniques used were those of electrical resistivity and transmission electron microscopy. EXPERIMENTAL PROCEDURE The lanthanum used in this investigation was prepared by the calcium reduction of lanthanum fluoride in a tantalum crucible under an argon atmosphere as described by Spedding et al. The residual calcium was removed by vacuum remelting in a tantalum container. Portions of the metal were then analyzed by emission spectroscopy as well as vacuum fusion. The amounts of the various impurities that were found are listed in Table I. A portion of the lanthanum ingot was swaged at room temperature into 0.030-in.-diam rod for the resistivity samples while the remainder was rolled into 0.010-in.-thick sheet for the transmission electron microscopy phase of this investigation. In order to eliminate the plastic deformation induced in the samples during fabrication, they were sealed in evacuated tantalum lined quartz capsules and annealed for 1 hr at 700° C. Specimen resistances were measured using the conventional "four-wire" technique described by MacDonald, 4 employing a type K-3 Universal Potentiometer and a standard 0.001-ohm resistor, both manufactured by Leeds and Northrup Co. By taking into account all of the possible errors in the apparatus, it was felt that the absolute resistivities of the approximately 0.87-in.-long specimens measured are reliable to 3 pct. Resistances from room temperature to 700°C were measured using a vacuum furnace. In order to avoid sample contamination by the thermocouple, chromel-alumel leads were spot-welded into a tantalum shield which in turn was welded to the lanthanum specimen. Resistances below room temperature were obtained by transferring the sample to a helium gas-filled quench tube and slowly dripping liquid nitrogen into a surrounding dewar flask. A steady reduction of temperature to about —190°C was completed in about 23 hr, and the resistances were measured at various temperature intervals. As will be shown shortly, rapid quenching from above about 350°C was sufficient to suppress the B -a transformation initially but subsequent annealing at lower temperatures leads to a partial ß --a conversion. To investigate this aspect of the transformation, the samples were suspended in the hot zone of a helium-filled furnace from which they could be rapidly dropped into the quench tube mentioned previously which was now

Jan 1, 1969

By J. T. Norton, J. G. McMullin

The ternary system of gold-silver-copper is characterized by a solid solubility gap and a two phase region in which copper-poor and silver-poor phases coexist. At about 30 pct gold, the two phases become mutually soluble at temperatures below the melting temperature. As the gold content is increased, the solubility temperature of the alloys decreases until at about 80 pct gold, the two phases are soluble down to the lowest temperature at which the alloys will recrystallize. Although the general form of the two phase region is known, its boundaries do not seem to have been investigated extensively. In an X ray diffraction study, Masing and Kloiberl have outlined the boundaries of this two phase field at 400 and 750°C. Using only microscopic techniques, Pickus and Pickus2 determined a vertical section of the ternary diagram showing the 14 kt alloys (58.3 pct gold). These two reports are riot in complete agreement. It has been shown3 that some of the ternary alloys are susceptible to age hardening and that the hardening is caused by the separation of a homogeneous alloy into two phases at the aging temperature. While the gold-copper binary system is an outstanding example of super lattice formation, Hultgren4 has shown that a few per cent of silver added to gold-copper destroys the tendency for ordering. Because of the age hardening possibilities of these alloys, it seemed advisable to investigate the boundaries of the two phase field more in detail using an X ray diffraction method, so as to permit a better understanding of the aging phenomena and enable predictions as to the behavior of other alloys to be made. This is especially true for the 18 kt alloys (75.0 pct Au) at the lower temperatures since they are known to exhibit age hardening. Twelve ternary alloys were prepared having the compositions shown in Table 1 and graphically in Fig 1. The gold used was fine gold bars supplied by Handy and Harmon. The silver was a bar of high purity silver from the U. S. Bureau of Standards. The copper was a bar of vacuum-treated, high conductivity copper from the National Research Corporation. The pure metals in the form of powder were weighed out in proper proportions and melted in graphite in a high frequency induction vacuum furnace. They were heated to 1100°C and slowly cooled. The ingots were then removed from the crucible, inverted, returned to the crucible and remelted. This remelting procedure was intended to reduce segregation in the ingots. After remelting, the ingots were checked for weight loss. The weight loss in each ten gram ingot was held to less than 25 mg. The remelted ingots were cold rolled and then given a homogenizing heat treatment of 16 hr at 760°C to remove any remaining segregation. Powder specimens were prepared by cutting the ingots with a fine file, one half the required amount of powder being taken from each end of the ingots. When the X ray diffraction pattern showed any difference in lattice constant between the ends of the ingot, the ingot was remelted and given an additional homogenization treatment. All powder samples were sealed in evacuated pyrex tubes for heat treatment. Ordinary pyrex proved satisfactory for temperatures up to 650°C but above that temperature it was necessary to use a special high temperature pyrex glass. Annealing at temperatures below 500°C was done in a salt bath whereas for temperatures of 500°C and above an electric muffle furnace was used. In both furnaces the temperature control was ± 5°C. In all annealing treatments samples of cold worked powder were placed in a furnace which was already at temperature. In this manner the specimens recrystallized directly to the equilibrium structure for that temperature. Time at temperature was selected so as to allow complete recrystallization, but very little grain growth. Specimens were quenched from the annealing temperatures by breaking the pyrex tubes in cold water. X ray diffraction photograms were made of all the heat treated powders using copper radiation and a Phragmen

Jan 1, 1950

By J. L. Huitt, J. L. Pekarek, D. K. Lowe

In a theoretical study of hydraulic jetting, the velocity of the abrasive material relative to the velocity of the fluid in the jet stream is analyzed as the jet stream moves through the convergent and straight sections of the nozzle and the region between the nozzle exit and target. The results revealed that the abrasive material exits from the jet nozzle at a lower velocity than the fluid. The exit pmticle velocity can be increased by increasing either the density of the fluid or the length of the nozzle, and/ or decreasing either the particle density or particle diameter. In the divergent jet stream, there exists a point after which the particle velocity exceeds that of the fluid. The relative velocities were considered in the derivation of an equation to predict cutting rate of a circumferential notch and maximum notch depth. Data of a general nature and data which substantiate the theoretical results were obtained experimentally. INTRODUCTION The use of a fluid containing an abrasive material has been an established technique for cleaning and cutting for many years. In the petroleum industry, the early effort to use this technique1 to perforate and/or to overcome wellbore damage met with only limited acceptance because of the short life of the jet nozzle. With the introduction of improved perforating techniques, and later, hydraulic fracturing, the use of hydraulic jetting as a well completion technique became even less appreciated. It was only in recent years that interest in hydraulic jetting was revived. Once this interest was revived, the results of surface tests stimulated the interest of the industry even more than the state of the technology probably warranted because many of the tests were not appropriate for down-hole conditions. However, because of the stimulated interest, the development of the jet nozzle progressed very rapidly to the point where the nozzle life was no longer a prob- lem. With this accomplished, the use of hydraulic jetting in well completion became an accepted practice in a short time. The purpose of this paper is to present a theoretical analysis of the hydraulic jet stream as it passes through the nozzle and travels to its target. With a better understanding of the jet stream and the effects of various parameters, the performance of the process can be predicted more accurately. Equations are presented for cutting rate as applied to circumferential wellbore notching that relate the jet stream make-up, notch configuration and formation material. Also, experimental data are presented on some factors pertinent to hydraulic notching that are not theoretically analyzed. RELATED STUDIES Most of the studiesl-5 reported in the recent literature have pertained to the more practical aspects of hydraulic jetting; i.e., the effects of certain parameters as interpreted from experimental results, and the application of hydraulic jetting in well completion. In reviewing the effects of various parameters, it is interesting to note the reported depths of penetration obtained under various imposed conditions. In general, the depths vary from a few inches to several feet; however, a depth of penetration of less than 6 in., as reported by Thompson,4 seems more realistic for the usual field practice of hydraulic jetting with sand in water for a period of 20 to 30 minutes. In addition to the practical aspects, the study of Brown and Loper5 included a theoretical approach to hydraulic jetting. Their study resulted in the development of a theoretical expression for the maximum depth of penetration if jetting were continued for an infinite time. An analysis of the equations presented reveals that the initial cutting rate is infinite. The equation expressing centerline velocity is that of Forstall and Gaylord,6 which is applicable for a jet stream exiting in a large stationary medium. Since practically all of the fluid pumped into a perforation (or cut) must flow back through the perforation prior to re-entering the wellbore, a description of the medium as finite and non-stationary seems more reasonable. Thus, in this

By R. E. Zinkham

An investigation has been conducted to compare short transverse and longitudinal fatigue and fracture properties in 4.25-in.-thick, high strength aluminum alloy plates. One plate was produced using standard rolling techniques while the other was pre.forged before rolling. Little difference was shown in fatigue strength of longitudinal specimens taken from mid-thickness of the plate. Howeuer, in the short transverse orientation fatigue strengths at 107 cycles were about 25 and 50 pct less, respectively, for the preforged and standard rolled plate. Differences in fatigue strengths were attributed to grain size and shape as well US orientation of constituents. Fatigue crack propagation rates and fracture toughness were compared at three different stress intensity (K) levels, using a constant compliance, double cantilever, wedge-shaped specimen. In a given plate, comparable fatigue crack Propagation rates were observed in the longitudinal (i9W) and short transverse (TW) orientations. Somezuhat gveater rates were observed in the short transzerse (TR) orientation. The preforged plute gave a lower rate for all three directions. Considerable secondary cracking developed, at times, over portions of the fatigue crack in both plates, particularly at the lower stress intensity levels in the short transverse specimens. Micro structure revealed constituent stringers as possible causes of the crack branching. Fracture toughness was considerably less in both plates in the short transuerse orientation. It is concluded that preforging not only improved directional tensile properties but also the fatigue and fracture properties in general. On occasion, aluminum plates have been milled away for hinges or bolted connections and stressed through the thickness or short transverse direction. Little or no information is available concerning fatigue characteristics or fracture toughness in this loading orientation in aluminum plate, or of the effect of fabrication on these properties. It was the intent of this project to examine, develop, and apply a unique specimen that has been advocated by others to study the fatigue characteristics and fracture toughness of two differently fabricated high strength aluminum plates. Linear elastic fracture mechanics criteria may be applied to the specimen so that the fatigue crack propagation rate and fracture toughness data may be of use for design or inspection applications. Fatigue characteristics are generally measured in the longtudinal or long transverse direction, where fairly large specimens such as center notched panels,' are usually employed. Limitations are evident due to plate thickness, however, in the type and size of specimen that may be tested in the short transverse direction without extensions. Therefore, a specimen that is to be loaded in this direction should, for convenience, be compact. The general type of fatigue crack propagation specimens discussed and employed herein meet this requirement. These specimens are commonly called double cantilever beam specimens and lately "crackline-loaded edge-crack specimens".2 They may vary from a slope of zero (parallel-sides) to a wedge shape, the type employed herein. In general for most specimens the stress intensity KI at the tip of a crack is a function of the load, P and crack length, a. Some varieties of the wedge shaped specimen, however, give essentially a constant stress intensity KI over a considerable range of crack length.' This feature can be a valuable asset in fatigue crack propagation experiments because the stress-intensity can be controlled simply by controlling the load without regard to crack length. MATERIAL AND METHODS Material. A standard rolled (light pass reduction) and a ~reforged and rolled (heavy pass reduction) plate of 7179-T651 material were used for the evaluation. The chemistry, processing history and average tensile properties are shown in Table I. Specimen Selection and Preparation. The specimen selected for the generation of fatigue initiation or S-N data was an axial tension type and is shown in Fig. 1. Specimens were taken from mid-thickness in the longitudinal and short transverse directions from both plates. Specimens were polished with 500 grit paper in a direction parallel to the loading axis. For the fatigue crack propagation tests, the specimen shown in Fig. 2 was used. This is similar to a specimen that has been employed by Mostovoy3 for fracture toughness studies on 7075-T6 aluminum alloy. It also fortuitiously agrees quite well with the dimensions of a specimen for which Srawley and Gross2

Jan 1, 1970

By J. H. Jackson, J. G. Kura, M. C. Udy, L. W. Eastwood

The melting and casting of any commercial metal depends upon the success with which the problems attendant to the handling of the specific metal are overcome. Common difficulties encountered in the handling of commercial metals are tendencies to burn or oxidize excessively, low fluidity, entrapment of dross, hot cracking, cold embrittlement, cold shuts, and un-soundness caused by gas evolution. Beryllium is not only subject to these same difficulties but is generally more sensitive to them than are the more common metals, thus necessitating more exact founding precautions. Characteristics of Beryllium Certain characteristics of beryllium which make it particularly difficult to handle in the plant or laboratory are as follows: 1. The melting point of beryllium is about 2400°F and pouring temperatures vary from 2600 to 2900°F, depending upon the degree of fluidity required. The extreme chemical activity, combined with the high temperatures, makes necessary the use of inert atmospheres, slags, or vacuum for protection during melting and pouring. Furthermore, beryllium tends to react with the melting crucibles, tools, and molds, thus requiring the selection of suitable materials and proper maintenance of these items. 2. The very marked absorption of gas by molten beryllium and the subsequent evolution of gas during solidification causes a great deal of difficulty with unsoundness. Beryllium castings may also be subject to unsoundness as a result of gas formation by chemical reaction with the mold surface during solidification. 3. The very marked chemical affinity between molten beryllium and the normal atmosphere causes the formation of dross. On relatively quiescent melts, this dross forms a very tenacious film which, if carried over to the mold, can cause defects such as the formation of skins or dross in the interior or on the surface of the casting; folds or defects similar to cold shuts may also be found. 4. During the pour and attendant turbulence, the dross may be mixed into the metal and then carried to the casting. There it may be entrapped during freezing and cause internal defects, or it may float to the surface and cause severe dross defects on the cope side of the castings. 5. Solid beryllium is very weak at a temperature near the solidus line; brittleness is also a problem at lower temperatures. Thus, hot and cold cracking must be guarded against. Scope of the Experimental Work All of these problems have been given consideration in the work at Battelle. Before the work was started at Battelle, it was customary to melt beryllium in a vacuum furnace or under flux in graphite-lined induction furnaces. Because of the difficulty of preventing gas unsoundness in beryllium castings, an investigation was undertaken primarily to study this particular problem and, secondarily, to devise methods of overcoming the other difficulties encountered in the founding of beryllium. The objectives of the laboratory work were multifold: 1. To devise a practical method of melting, other than vacuum melting, by means of which consistently sound beryllium castings could be produced. 2. To obtain fundamental data which would promote a better understanding of the causes of gas unsoundness in beryllium. 3. To develop a casting technique which would permit low melt temperatures, minimize dross defects and hot cracking, and eliminate reaction with the mold surface. Up to the present time, a considerable amount of progress has been made on the first and third objectives, with the result that it can now be safely stated that consistently sound castings can be made by the open-pot melting method, using argon as a protective atmosphere and a proper casting technique. There has been some progress on the second objective of the project, but it cannot yet be safely stated that the problem is completely understood. Most of the experimental work has been conducted in an enclosed melting and pouring apparatus in which very-close control of melting variables has been effected. Findings based on the results of the work conducted in this small experimental apparatus have been applied to large-scale melts which have been made by techniques suitable for duplication on a commercial scale.

Jan 1, 1950

By C. J. Leith

A study of the effect of rock composition, rock structure and degree of weathering on the stability of cut slopes is being sponsored jointly by the U.S. Bureau of Public Roads and the North Carolina Highway Commission. In 58 mountain and piedmont counties of North Carolina the percentage of failed cut slopes is greatest in micaceous metasediments, gneisses, and schists, and in saprolite and soil derived from these rock types. Soil slope failures outnumber rock slope failures by two to one. Joints and similar planes of separation exert a strong influence on size and shape of the sliding mass. They may or may not act as failure surfaces, depending on their orientation with respect to the active forces. Climatological data, though indicative of weathering conditions, do not correlate well with slope failure frequency. Because of the presence of joints and similar planes of weakness in soil and rock materials, conventional methods for analyzing slope stabilities are not directly applicable. Empirically derived modifications of these methods are being investigated. A study of the stability of highway cut slopes, sponsored by the U. S. Bureau of Public Roads and the North Carolina State Highway Commission, began in 1962 at North Carolina State of the University of North Carolina at Raleigh. As part of this study all slides, rockfalls and other types of cut slope failures on Federal and State highways in the 58 mountain and piedmont counties in North Carolina were located and described, and the data catalogued in a punched card file system. A major objective of the project is to relate slope failures to properties and physical conditions of the geological units in which the slopes were constructed, and to correlate soil type and/or geological unit with type and frequency of slope failure. The complexities of the problem of slope stability and the limitations which these complexities impose on methods for analyzing slopes have been recognized for many years. A great variety of factors and processes may lead to slides, often making it almost impossible to analyze theoretically the conditions required for stability of slopes. One of the principal factors determining maximum safe slopes is the shear strength of the material in which the slopes are cut, but unfortunately there are very few data available concerning shear strengths of residual soils. Vargasl tested clay derived from gneiss and granite in southern Brazil; the properties of decomposed granite occurring near Hong Kong were determined by Lumb.2 These data are being used, when applicable, to supplement the test data obtained in the present study by Yorke.3 The locations of the North Carolina slope failures, more than 400 in number, are shown on Fig. 1. This map, adapted from the Geological Map of North Carolina,4 suggests the possibility of a relationship between frequency of slide occurrence and rock type. However, the evaluation of this possibility requires consideration not only of the type of rock, but also of its large and small scale structural features, its susceptibility to and degree of weathering, and the composition and structure of the weathering products. Soil slope failures in thoroughly weathered soil material and saprolite outnumber rock slope failures two to one. INFLUENCE OF ROCK TYPE The agricultural soil type involved in each soil slope failure was identified and each failure was catalogued in terms of the parent material from which the soil was derived. These data indicate that most of the slope failures, whether in the rock or in the derived soil, are associated with metamorphic rocks (see Fig. 2a). The data may be skewed somewhat because of the relative sizes of the total areas underlain by the various rock types, but Leith and Gupton5 have demonstrated that the preponderance of failures in metamorphic rocks is of much greater magnitude than could be accounted for by the areal factor alone. The dominance of metamorphic rocks is emphasized when soil slope failures are considered in terms of the specific rock types from which the soils were derived (see Fig. 2b). In particular, mica schists and mica gneisses account for more slides

Jan 1, 1965

By E. N. Smith, J. C. Redmond

The increasing need for materials capable of withstanding higher operating temperatures for various applications such as gas turbine blading and other parts, rocket nozzles, and many industrial applications, has brought consideration of cemented carbide compositions. The well known usefulness of cemented carbides as tool materials is attributable to their ability to retain their strength and hardness at much higher temperatures than even complex alloys. However, it has been found that the temperatures encountered in cutting operations do not approach by several hundred degrees1 those involved in the applications mentioned above where the interest is in materials possessing strength and resistance to oxidation at temperatures of 1800°F and above. At these latter temperatures, the tool type compositions which are made up essentially of tungsten carbide are found to oxidize very rapidly and to produce oxidation products of a character which offer no protection to the remaining body. As a further consideration, the density of the tungsten carbide type compositions is high, from about 8.0 to 15.0. The refractory metal carbides as a class are the highest melting materials known as shown by Table 1 which summarizes the available data from the literature for the carbides of the elements which are sufficiently available for consideration for these uses. The density is also included in the table, since as mentioned above it is an important consideration in many of the applications for which the materials would be considered. It has been established that in the tool compositions the mechanism of sintering with cobalt is such as to result in a continuous carbide skeleton and that the properties of the sintered composition are thus essen- tially those of the carbide.2 On the hypothesis that this mechanism holds to a greater or less degree in cementing most of the refractory metal carbides with an auxiliary metal, it appears from Table 1 that titanium carbide compositions would offer possibilities for a high temperature material. Titanium carbide has extensive use for supplementing the properties of tungsten carbide in tool compositions. Although the literature contains several references to compositions containing only titanium carbide with an auxiliary metal,3,4,5,6 it may be inferred from the meager data that such compositions were deficient in strength and were considered to have poor oxidation resistance.7 Kieffer, for instance, reports the transverse rupture strength of a hot pressed TiC composition at 100,000 psi as compared to up to 350,000 psi for WC compositions. The work described herein was undertaken to determine the properties of compositions consisting of titanium carbide and an auxiliary metal and to improve the oxidation resistance of such compositions. It appeared possible that the inclusion of one or more other carbides with titanium carbide might improve the oxidation resistance and also that this might be more desirable than other means from the point of view of maintaining the highest possible softening point. Consideration of the available carbides in Table 1 suggests tantalum and columbium carbides because of their high melting points and general refractoriness. The work on improving oxidation resistance was concentrated on the addition of tantalum carbide or mixtures of tantalum and columbium carbide. The auxiliary metals used included cobalt, nickel and iron. It was also desired to learn the general physical properties of these compositions. Experimental Procedure The compositions used in this study were made by the usual powder metallurgy procedure applicable to cemented tungsten carbide compositions. The powdered carbide or carbides and auxiliary metal were milled together out of contact with air. In some cases cemented tungsten carbide balls and in other instances steel balls were used to eliminate any effect of tungsten carbide contamination. A temporary binder, paraffin, was then included in the mix and slugs or ingots were pressed with care to obtain as uniform pressing as possible. The ingots were presintered and the various shapes of test specimens were formed by machining, making the proper allowance for shrinkage during sintering. Thereafter the shapes were sintered in vacuum at temperatures of from 2800 to 3500°F. Final grinding to size was carried out by diamond wheels under coolant. The titanium carbide used contained a minimum of 19.50 pet total carbon and a total of 0.50 pet metallic impurities as indicated by chemical and spectrographic analysis. It was found by X ray diffraction examination with

Jan 1, 1950

By H. W. Mossman

Three aspects of magnetite smelting are discussed. The first is the working out of equilibrium conditions for eliminating sulfur. The second is the influence of magnetite solubility on the difficulty of tapping the reverb matte. The third is an approximation of the equilibrium conditions in the reverb gases which govern whether magnetite is mode or reduced in the reverb slag by these gases and by any iron sulfide in the slag. MAGNETITE has had a varied history in the Hurley Smelter since its start in 1939. Magnetite determinations on the smelter products are made regularly only on the monthly composite samples. Variations on the monthly averages are shown in Table I. Magnetite which drops from the slag and matte in the reverb has some slight bottom buildup which comes and goes, but no substantial accumulation from this source has been found at the end of a normal nine months' furnace campaign. However, there has been some low grade magnetite bearing material mixed with considerable A1,0,, which has slid down from the bottom of the sloping flue between the reverberatory furnace and the waste heat boilers. This accretion has required drilling and blasting near the skimming end of the furnace. The magnetite has interfered with tapping at times. When the smelter was first started, tapping trouble from magnetite was extremely severe. Increasing the reverberatory furnace temperature by putting in an air preheater and a Dutch oven has helped greatly, although there still is occasional tapping trouble. When the present series of physical chemistry articles on copper smelting started coming out in 1950, they were read with interest, but no immediate application was seen for them. Results of some laboratory work in 1952 aroused a much stronger interest in this physical chemistry. A series of melts was made on some converter slags, which had magnetite in very large grain sizes, with the object of reducing the grain sizes in the slag, as it was known that it was easier to handle in the reverb in that condition. Anything done in the tests greatly reduced the grain sizes—even in the controls, where nothing was done except melt the slag and cast it. There was more magnetite in the slags after the tests than before, and with wide variations. There were no obvious reasons lor much of what happened in these tests. Much of the base material published in English in this field was made available for study. Recalculations were made on many of the type problems, and part of the data was reduced to local temperatures and compositions. Explanations were found for what happened in the 1952 series of tests on converter slags, and the same principles turned out to be a description of much of what magnetite does in the reverb. This article is to present the results of that study, from the viewpoint of applying the technical material in definite numerical form to the operating conditions in both the converters and the reverberatory furnaces at the Hurley smelter. Table I. Magnetite Variations on Monthly Averages, 1939 to 1955 Pet Magnetite Lowest Highest Average Converter slag 13.6 43.3 25.4 Roverb slaa 2.7 20.9 8.7 Matte 28 15.9 98 In general it was found that magnetite is made or reduced in both the converters and the rever-beratory furnace, depending on variations of temperature, matte composition, and reverb gas composition occurring in ordinary plant operation. Within reasonable limits, the field conditions for formation or reduction can be predicted, and probably can be set up and maintained. Converter conditions affecting magnetite formation can be put into numerical values better than for the reverb from purely technical calculations. The converter can be operated so as to keep the magnetite in the slag down to between 12 and 14 pct and still give satisfactory life for the converter brick. This depends upon having converter flux available which will make a slag with a good separation without raising the temperature too high. In the Hurley reverb and others with similar conditions, it is likely that a compromise of conditions will give a reasonably good control of combustion and still keep the magnetite from building up on the bottom. This discussion consists of three main parts. The first is the working out of the equilibrium conditions in the converter for determining in which direction the reaction 3 Fe,,O, (s) + FeS (1) F? 10 FeO (1) + SO, will go under actual converter operating conditions. The second deals with the influence of the solubility of magnetite in the slag and matte in the reverb on the difficulty of tapping matte. The third is an approximation of the equilibrium conditions in the

Jan 1, 1957

By H. W. Meyer, H. N. Lander, F. D. Delve

A method of calculating the changes in blast-furnace performance brought about by burden and/or blast modifications is presented. Essentially the method consists of three simultaneous equutions derived from materials and heat balances. These equations can be used not only to evaluate quantitatively the effect of changes in process operating variables on furnace performance, but also to provide a useful means of evaluating changes in process variables which cannot be measured directly. It has been customary for a number of years to use simple heat and materials balances as a basis for assessing blast-furnace practice. A good example of the method used to set up these balances is that proposed by Joseph and Neustatter.1 This approach to process assessment has limited utility, however, in that it cannot be used to predict the furnace coke rate or production under new operating conditions. Using an approach based on multiple correlation of blast-furnace variables, R V. Flint2 has developed an equation which may be used to predict the change in coke rate that will result from some changes in operating conditions with a reasonable degree of accuracy. Although this equation has useful applications in production planning, it cannot be used to study the relationships between the operating variables and the fundamental thermochemi-cal characteristics of the process. In attempting to analyze the blast-furnace process quantitatively, the idea of dividing the furnace into zones3 may at first appear attractive. In our present state of knowledge, however, it is not possible to define with any accuracy the physical limits of such zones in relationship to their temperatures or to the reactions which may occur in them. Although its application is restricted, the zonal approach to blast-furnace analysis is useful in some instances. For example, the change in the calculated flame temperature in the "combustion zone" caused by injecting steam constitutes information which is helpful in understanding why the addition of steam to the blast is best accompanied by an increase in blast temperature. The zonal approach cannot, at the present time, be used to establish the relationships between process variables and process performance if the whole process rather than part of it is to be considered. One of the earliest approaches to the problem of relating blast-furnace operating variables to pro- duction and coke rate was that developed by Marshall.4 Essentially Marshall's work showed that it was possible to estimate the performance of a furnace by solving three simultaneous equations which consisted of rudimentary carbon and heat balances plus a further equation relating the production, wind rate, and the carbon burned at the tuyeres. Although these equations did not include all of the chemical and thermal variables of the process, their derivation and application seems to be the earliest attempt which achieved any success in relating prior furnace operating data to the calculation of furnace performance under different blast conditions. Work carried out in Germany has been directed mainly towards prediction of coke rates using material and thermal balances rather than statistical methods. wesemann5 used prior furnace operating data as part of the basis for predicting the change in coke rate accompanying a change in burden composition. This author employed a method of successive approximations to estimate the secondary changes in slag volume and stone rate brought about by the change in coke rate. The most recent analysis, which seems to have been developed concurrently with the thermochemical model presented in this paper, has been described by Georgen.6 This author has succeeded in improving on Wesemann's approach by expressing the total changes in the slag volume and stone rate in terms of the change in coke rate itself. This is accomplished in a manner similar to that used in the thermochemical model described in this paper. Although Georgen makes use of a calculated furnace heat loss, he does not relate the heat loss per unit of hot metal to the production rate as is done in the present work. Georgen's approach may be used to calculate the changes in materials requirements accompanying changes in furnace operation; it cannot be used to assess the resulting changes in production. The fact that blast-furnace behavior can be interpreted by consideration of the heat requirements of the process was demonstrated by Dancy, Sadler, and Lander.7 In the analysis of blast-furnace operation with oxygen and steam injection these authors showed that it was possible to account for the changes in production and coke rate

Jan 1, 1962

By M. J. Marcinkowski, D. B. Crittenden, A. S. Sastri

A study co.mbining stress-strain .measurements in conjunction with transmission electron microscoPy has been made with near equiatomic Fe-Cr alloys which were aged for various times at 500°C. Associated with this aging is a marked increase in deformation twinning. The outstanding feature of these twins is that they generate stress fields sufficiently great so as to give rise to spontaneous dislocation loop nucleation nearly normal to the propagating twin. This observation is in agreement with the theoretically predicted elongation of the stress field of a dislocation Perpendicular to its direction of motion as it moves near the speed of sound. Dislocation loop nucleation is more difficult in the longer aged alloys so that this energy absorption mechanism is not effective in hindering twin propagation. Since crack nucleation can readily occur near the tip of a twin, the aged alloys become extremely brittle when deformed in tension. Iron-chromium alloys in the vicinity of the equiatomic compositions become severely embrittled when aged at about 500°C. Fisher et 01.' have shown that this embrittlement is related to the decomposition of the original random Fe-Cr solid solution into a chromium-rich and an iron-rich phase. In addition, Mar-cinkowski et a1.' have shown that twinning becomes an increasingly more important mode of deformation as the aging time is increased. These results have been recently corroborated by the transmission electron microscopy study of Mima and amauchi . The Fe-Cr alloy thus seems ideal for verifying the predictions made in Parts I4 and 115 of this investigation where the behavior of large static or blocked twins and those of large dynamic or propagating twins, respectively, were investigated numerically. It was thus decided to measure the stress-strain curves generated by embrittled alloys that were aged for various times and to examine sections by transmission electron microscopy. EXPERIMENTAL PROCEDURE Electrolytic iron and electrolytic chromium were vacuum-melted and poured into ingot form. The composition of the resulting alloy was found to contain 46.0 wt pct Cr (47.8 at. pct), the remainder being iron. The resulting ingot was swaged above 850°C into 0.250-and 0.400-in.-diam rounds. Compression samples of 0.250 in. diam and 0.400 in. long were cut from the smaller-diameter rounds. These samples were then sealed in evacuated quartz tubes and annealed for 30 min at 1150°C to produce a uniform and equiaxed grain size of mean diameter equal to 1.73 mm. They in turn were rapidly quenched from 850°C so as to preserve the condition of random solid-solution characteristic of the elevated temperature. The samples were then aged for various times up to 300 hr at 500°C in a massive Pb-Bi alloy bath. The samples were next polished and tested in compression at room temperature as described in Ref. 6 using an Instron tensile testing machine. The strain rate used was 0.05 in. per in. per min. The remaining larger round was converted into compression specimens of 0.325 in. diam and 0.500 in. long. This larger diameter enabled wafers of sufficient size to be prepared for examination by trans-mission electron microscopy techniques after subjecting them to a suitable strain. Foil preparation is described in some detail in Ref. 6. All foils were examined in a type HU-11A Hitachi electron microscope operating at 100 kv. RESULTS AND DISCUSSION Fig. 1 shows the effect of aging at 500°C on the room-temperature stress-strain curves of the FeCr alloys. For greater clarity the origin of each curve has been displaced upward. The same origin has been used for both the 0 and the 0.1 curves. It is apparent that with increased aging times a sharp drop in load is observed at the yield stress which becomes more pronounced as aging proceeds. A loud sonic burst accompanies this drop and subsequent metallographic examination shows the sample to contain numerous twins. For intermediate aging times, a number of smaller twin bursts follow the initial large one. The total plastic strain associated with the twinning mode of deformation can be obtained by adding up the contributions AE~ from all i twin bursts, i.e., £,¦££,-, in the manner illustrated schematically in Fig. 2. The contraction of the specimen, as measured from the strip chart of the Instron, after suitably correcting for the elasticity of the machine, was converted into true strain using the assumption that there was no volume change and that the sample remained cylindrical. The dashed lines are all drawn parallel to the

Jan 1, 1970

By H. D. Hodges, J. K. Godbey

In order to better understand the fracturing process, bottom-hole pressures were measured during a number of typical fracturing operations. A recently developed system was used that allows simultaneous surface recording of both the bottom-hole and wellhead pressures on the same chart. The results from six fracruring treatments are summarized on the basis of the pressure data obtained. Al-though no complete analysis is attempted, the value of accurate pressure measurements is emphasized. Important characteristics of the bottom-hole pressure record do not appear at the wellhead because of the damping effect of the fluid-filled column. In four of the six treatments described, the formations apparently fractured during the initial surge of pressure with only crude oil in the well. The properties of the fluids used during the treatments are given and the fluid friction losses are obtained directly from the pressure records. This technique is also shown to be adequate for determining when various fluids, used during the process, enter the formation. INTRODUCTION Hydraulic fracturing for the purpose of increasing well productivity is now accepted in many areas as a regular completion and workover practice. Numerous articles have appeared in the literature discussing the various techniques and theories of hydraulic fracturing'. In general, three basic types of formation fractures are recognized today. These are the horizontal fracture, the vertical fracture, and fractures along natural planes of weakness in the formation'. Any one or all three of these fracture types may be present in a fracturing operation. However, with only the wellhead pressure record as a guide, it is difficult at best to determine if the formation actually fractured, and is almost impossible to determine the type of fracture induced. These difficulties arise in part because the wellhead pressure record, especially when fracturing through tubing, does not accurately reflect the pressure variations occurring at the formation. Several factors contribute to this effect and preclude the possibility of using the wellhead pressure as a basis for accurately calculating the bottom-hole pressure. These factors are: 1. The compressibilities of the fluids which damp the pressure variations. 2. The changes in the densities of the fluids or apparent densities of the sand-laden fluids. 3. The flowing friction of the various fluids and mixtures, which is dependent on the flow rates and the condition of the tubing, casing, or wellbore. 4. The non-Newtonian characteristics of a sand-oil mixture and its dependence upon the fluid properties, the concentration of sand, and the mesh size used. 5. The unknown and variable temperatures throughout the fluid column. Because of these reasons it was determined that in order to obtain a more accurate knowledge of the nature of fracturing, the bottom-hole pressure must be measured along with the pressure at the surface during a fracturing treatment. Even with accurate pressure data, a reliable estimate of the nature of fracturing is still dependent upon knowledge of the tectonic conditions. However, the hydraulic pressure on the formation is basic to any approach to a complete analysis. In order to accomplish this objective a system was developed to record the wellhead and bottom-hole pressures simultaneously at the surface. By recording both pressures on a dual pen strip-chart recorder, it was possible to greatly expand the time scale so that rapid pressure variations would be faithfully recorded. By such simultaneous recording, time discrepancies inherent in separate records are eliminated, thus overcoming one of the most difficult problems associated with bottom-hole recording systems. This paper illustrates the results obtained by using this system during six typical fracturing operations. All of these tests were taken in wells that were treated through tubing. By a direct comparison of the wellhead and bottom-hole pressures, the importance of obtaining complete pressure information during a fracturing treatment is emphasized. THE INSTRUMENTATION AND PROCEDURES The bottom-hole pressure measuring instrument consisted of a pressure-sensing element, a telemetering section, and a lead-filled weight or sinker bar. The pressure-sensing element used was an isoelastic Amerada pressure-gauge element. By using an isoelastic element, no temperature compensation was necessary in the tests described, since the temperature was believed to be well below the maximum temperature limit of 270°F. The rotary output shaft of this helical Bourdon tube element was coupled to a precision miniature potentiometer. The rotation of the pressure-gauge shaft thus changed the resistance presented by the potentiometer

By S. L. Craig, C. Orr, H. G. Blocker

WITHIN recent years gas adsorption methods have been developed for measuring the surface area of finely divided materials and have become extremely valuable in research on the corrosion and the catalytic activity of metals. Rather elaborate apparatus is required, and a single determination is so time-consuming that these methods have not been utilized to the fullest extent; the methods are un-suited for most routine control work such as that encountered in powder metallurgical operations and in processes employing metal catalysts. These difficulties are largely eliminated, and surface area is reduced to a routine determination if the liquid-phase adsorption of a surface-active agent such as a fatty acid can be used. When the affinity of the fatty acid carboxyl group for the solid surface is greater than its affinity for the solvent, a unimolec-ular layer of orientated fatty acid molecules will be formed at the solid-liquid interface in a manner similar to that of a compressed fatty acid film on a water surface. The measurement of surface area is then reduced to a measurement of fatty acid adsorption. This propitious circumstance, first investigated by Harkins and Gans,¹ has been employed with somewhat inconclusive results by a number of investigators in evaluating the surface properties of metals, metal catalysts, and metal oxides. The specific surface area values for nickel and platinum catalysts, determined from the adsorption of a number of fatty acids from various solvents, were found by Smith and Fuzek² to agree with values calculated by the gas adsorption technique of Brunauer, Emmett, and Teller," he so-called BET technique. And recently Orr and Bankston4 have also reported good agreement between nitrogen gas and stearic acid adsorption results in the measurement of the surface areas of clay materials. On the other hand, Ries, Johnson, and Melik5 found only order-of-magnitude agreement between these two methods in studying supported, cobalt catalysts having specific surface areas as great as 420 sq m per g; the reason is partially attributable to the very porous nature of the materials. Greenhill,6 investigating the adsorption of long-chain, polar compounds in organic solvents on a number of metal powders, concluded that a uni-molecular layer of stearic acid was formed on exposure of the solid to the acid solution and that the presence of an oxide or another film did not alter this result. Furthermore, the adsorption process appeared to be the same whether or not the sample was degassed prior to exposure to the solution. Greenhill estimated the surface area of one of the powders he investigated from microscopic diameter measurements, and obtained a rough check with surface area evaluation. Russell and Cochran7 found moderate agreement for alumina surface area results by fatty acid and gas adsorption methods. In addition, they also found that the prolonged heating and evacuating pretreatments previously used by investigators were unnecessary. The present work, however, considerably extends these previous investigations, shows that fatty acid adsorption can be used to determine the surface area of a variety of metals and metal compounds, offers further confirmation of the correctness of gas adsorption methods, and presents a simplified technique for the determination of the metal surface area which is suitable for routine work. Experimental Technique Basically, the fatty acid adsorption method is quite simple. It consists of exposing a sample of the material of which the surface area is desired to a fatty acid solution of known concentration. By analysis of an aliquot of the solution, the concentration after adsorption has occurred may be determined. The difference between the initial quantity of acid in solution and the final quantity is that quantity of acid adsorbed by the sample. The specific surface area of the adsorbent material may be calculated from the quantity adsorbed and the weight of the sample. In agreement with the findings of others as outlined above, it was found entirely unnecessary to degas or pretreat the nonporous materials employed other than by drying them thoroughly. However, precaution was necessary so that the dried sample entered the fatty acid solution with little exposure to moisture. The effect of moisture on the interaction of stearic acid with finely divided materials has been thoroughly investigated by Hirst and Lancaster." They found the presence of water merely reduced the amount of acid adsorbed by powders such as TiO2, SiO2, Tic, and Sic. With reactive materials such as Cu, Cu2O, CuO, Zn, and ZnO, however, water was found to initiate chemical reaction. Only with ZnO was reaction observed when the solid and the solu-

Jan 1, 1953

By B. B. Rath, Hsun Hu

In wedge-shaped bicrystals of zone-refined aluminum it is observed that (111) pure tilt boundaries migrate under the driving force of their own inter-facial free energy. The boundary velocity is a power function of the driving force. The driving force exponent decreases with decreasing angle of misorien-tation. For example, at 64O°C, the exponent decreased from 4.0 for a 40 deg to 3.2 for a 16 deg tilt boundary. An evaluation of the driving force acting on the boundaries during their motion indicates that for low driv-forces, up to about 2 x l03 ergs per cu cm, the velocity is relatively independent of misorientation, whereas at higher driving forces a 40 deg tilt boundary exhibits the highest velocity. The measured activation energy for boundary migration approaches that for bulk self-diffusion at low driving forces, decreasing from 33 to 27 kcal per mole as the driving force is increased from 1 x l0 to 5 x l03 ergs per cu cm. These results are compared with current theories of grain-boundary migration. In previous experimental studies of grain boundary migration the driving force has been limited to a difference in stored energy across the boundary. This stored energy has been introduced into the crystal either by prior deformation1-3 or by grown-in lineage structure. A part of the energy stored in the deformed crystal is released by recovery either prior to or concurrently with grain boundary migration, thus introducing an uncertainty as to the magnitude of the driving force responsible for grain boundary migration. The grown-in lineage structure, though thermally stable during annealing, neither provides conditions under which different levels of energy may be stored in the imperfect crystal nor provides a control of orientation difference across the migrating boundary of a growing grain. Furthermore, because of variation in the lineage structure, it is difficult to determine accurately the energy stored in the imperfect crystal. Several investigations of grain boundary migration during normal grain growth have also suffered from difficulties in estimating the driving force because of uncertainties in the principal radii of curvature.~ In the present investigation the velocity of pure tilt boundaries in zone-refined aluminum bicrystals of selected orientation (40, 30, and 16 deg around the [Ill] tilt axis) has been measured in the absence of a dislocation density difference across the moving boundary, thus eliminating the previous experimental difficulties. The driving force for boundary migration is derived from a gradient of the total interfacial free energy of the migrating boundary in wedge-shaped bicrystals. A similar method was attempted by Bron and Machlin in a study of grain boundary migration in silver. However, they found that one of the crystals was deformed and consequently the motion of the boundary was partly due to a difference of stored energy across the boundary. The observed behavior of boundary velocities as affected by the driving force is examined in the light of the predictions of the current theories of grain boundary migration.7"10 The effect of boundary misorientation on velocity is compared with the theory of " which is based on a dislocation core model for high-angle boundaries. EXPERIMENTAL METHOD Seed-oriented bicrystals of zone-refined aluminum, 2.5 cm wide, 0.5 cm thick, and 12 cm long, containing tilt boundaries with a common (111) axis, were grown from the melt in the direction of this axis. Spectro-graphic analysis, reported earlier,'' indicated the purity of the crystals to be 99.999+pct. Three such bicrystals containing 16, 30, and 40 deg tilt boundaries were used. Wedge-shaped specimens were prepared from these bicrystals by spark cutting followed by electrolytic polishing. The angle of the wedge was usually 40 deg and the specimens were usually 0.25 cm thick. The intercrystalline boundary was located within 0.2 to 0.5 cm from the tip of the wedge. Fig. 1 shows a section of an oriented bicrystal containing an outline of a wedge-shaped specimen. The crystallographic directions shown in Fig. 1 represent the orientation of one of the crystals (the larger section of the bicrys-tal); the orientation of the other crystal differs only by rotation around the common [lil] axis. The parallel faces of the wedge always corresponded to the common (171) planes in both crystals, whereas the orientation of the side faces varied, depending on the misorientation angle. The bicrystal orientations were determined

Jan 1, 1970

By R. R. Estill

THE rank of the Ruhr coal ranges from a high volatile bituminous coal to an anthracite, depending to some extent on the original depth of the seam. The average Ruhr coal corresponds to a soft bituminous American coal of a coking quality. The average thicknesses of individual coal seams being mined are also comparable (59 in. against 65 in. in the United States). However, consideration of seam conditions and mining conditions other than those just mentioned emphasizes differences rather than similarities with United States soft coal. In general, the Ruhr seams now being mined are much more folded and inclined than American seams. Dips of 20' and 30" are common in seams now being worked, and 30 pct of the coal reserves in the district are in seams dipping more than 35". Only on the tops and bottoms of folds do we find rather flat coal seams. In addition to the folding there is extensive displacement by cross faulting plus a certain amount of strike faulting of an overthrust nature, which results locally in doubling or omission of seams. Because of the long history of mining in the Ruhr, nearly all coal lying near the surface has long since been mined out, and we find that the average depth of mining is at present about 2300 ft below the surface. Deep mining, folding, and faulting result in seam conditions requiring a great deal more roof support than one finds in American soft coal mines. In fact only in the anthracite district and the Rocky Mountain and Pacific coal fields do we find somewhat similar conditions. It is easy to say, therefore, that the problem of mechanization of coal cutting and loading in the German mines is quite different from that which we have so effectively met in America with our mobile cutters and loaders, duck bill loaders, and a room and pillar system of mining our drift and slope mines. Partly because of more limited coal reserves, the traditional German mining system is largely the longwall method, which gives an almost complete coal recovery. Backfilling must be extensively practiced to protect the longwall faces, the over and underlying seams and workings, and especially the surface industrialized areas and barge canals. The German engineers have accordingly concentrated their efforts on the design of cutters, loaders, and conveyors suitable to longwall methods rather than room and pillar methods. Undercutters with cutter bars like American models have been in use in the Ruhr since well before World War 11. In 1941 they accounted for 8.5 pct of the production. This percentage, of course, includes coal which was undercut but nevertheless had to be broken down with air hammers or with explosives. The most common of these cutters is the Eickhoff Standard cutter (see fig. 1). This machine does about 95 pct of the undercutting in the Ruhr today, and is available with either compressed air or electrical power and in at least four different sizes. A variation of the cutter is this one with two cutter bars (fig. 2). At the end of 1947 about 200 of these machines and similar cutters were accounting for 13.2 pct of the total production, a production which was, however, only 60 pct of the 1941 production rate, so that the actual cutter tonnage was only up to a small amount over 1941. In 1941 about 3 pct of the production was accounted for by shearing machines making their cut perpendicular to the longwall face. They were similar to those used in the States. These machines are today considered obsolete and now account for only 0.7 pct of the total production. They are located at only a few mines and at present do not seem to have much of a future in the Ruhr. For the future, the Ruhr miner is looking forward to rather extensive mechanization of face work, with two major types of equipment being developed almost simultaneously. On one hand there is the development of cutter loaders for use in relatively hard coal. They represent the further extension of ideas developed after relatively long experience with the Eickhoff cutter. On the other hand there has been since 1942 an intense interest in the Ruhr in the development of face-stripping methods, particularly by the Kohlenhobel (coal plow) and its modification. At the end of 1947 these cutter loaders, Kohlen-hobels and scrapers together were actually accounting for only about 1.4 pct of total production while air hammers still broke 77.1 pct and as much as 1.2 pct was actually broken by hand picks. However,

Jan 1, 1951