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By C. E. Tsoutrelis

A new method for determining rock drillability in diamond drilling is discussed; the method takes into consideration both penetration rate and bit wear. The method is based on drilling a rock specimen under controlled laboratory conditions using a model bit. The technique used for determining the experimental variables is extremely simple, quick, and reliable. Drillability is then determined by the mathematics of drilling. In considering the different factors that affect diamond drilling performance, the nature of the rock to be drilled is of outmost importance since it affects significantly the drilling costs and such other variables as bit type and design, drilling thrust, and bit rotary speed. Many attempts have been made to study this effect by correlating actual drilling performances either to certain physical properties of the rock being drilled1-? or to test drilling data obtained under laboratory conditions.7-13 These attempts were aimed at providing a reliable method of predicting by simple means the expected rock behavior in actual drilling, thus giving the engineer a tool to use in estimating drilling performances and costs in different types of rock. The purpose of this paper is to describe such a method by which rock drillability (a term used in the technical literature to describe rock behavior in drilling) could be determined in diamond drilling. It is believed that the proposed simple and reliable method will cover the need of the mining industry for a workable method of measuring the drillability of rocks. It should be emphasized, however, that since drill-ability depends on the physical properties of rock and each drilling process (diamond, percussive, rotary) is affected by different or partly different rock properties,14-l6 the proposed method of determining rock drillability cannot be extended to the other drilling processes. The results presented in this paper form part of an extensive three-year research program carried out by the author in the laboratories of the Greek Institute of Geology and Subsurface Research. During this period the effects of the physical properties of rocks and of such operational variables as drilling thrust and bit rotary speed in diamond drilling were investigated in detail. DRILLABILITY CONCEPT The literature is not devoid of drillability studies. While there are a number of investigators1,3,5-7,9-0,12-13,17 who have attempted to establish by direct methods (i.e., drilling tests under laboratory conditions) or indirect (i.e., through a physical property of rock) an index from which the drilling performance in a given rock may be estimated, very few6-7,9,12, of the proposed methods seem to be of much practical value to the diamond drilling engineer and none to date has been universally accepted. Commenting on the proposed methods for assessing rock drillability, Fish14 remarks that "for a measure of drillability to be accepted it is essential that penetration rate at a given thrust and bit life are elucidated as otherwise the method is of little value." This statement should be examined in more detail by making use of the penetration rate-drilling time diagram obtained in drilling a rock under constant operational conditions. Furthermore, the merits of using this diagram to describe rock drillability will be pointed out. At the same time reference will be made to this diagram when discussing some previously proposed methods. Fig. 1 illustrates such a diagram for three rocks,A, B, and C, which have been diamond drilled under identical conditions. It is assumed here that rocks A and B have the same initial penetration rate, i.e., VOA = Vog, but since rock B is more abrasive than A, rapid bit wear occurs and as a result the fall of its penetration rate with respect to time is more vigorous than in rock A. This is shown graphically by a steeper V = f(t) (0 curve in this rock than in rock A. Rock C has a lower initial penetration rate, due to higher strength properties16 but since it is not very abrasive, only a slight fall of its penetration rate occurs during drilling (in this category are some limestone and marbles with compressive strength above 1000 kg per sq cm). It follows from the foregoing considerations that the characteristic for each rock curve (I) is a function of (i), the penetration rate of the rock Vo recorded at the instant of commencing drilling, which determines the starting point of the curve (1) on the y-axis and (ii), the abrasive rock properties which determine the rate of fall of Vo with respect to time. Thus, curve (I) provides an actual picture of the rock behavior in drilling for given operational conditions, and it can be used with complete satisfaction to assess rock drillability. It can be seen clearly from Fig. I that proposed methods for assessing rock drillability by measuring the

Jan 1, 1970

By W. G. Oldham

By monitoring the capacitance of abrupt p-n junctions it is possible to follow the motion of substitu-tional impurities. A p-n junction is formed by growth of silicon from an Al-Si alloy on an n-type silicon sutstrate at a temperature in the range 650" to 750°C. The diodes are etched and sorted for consistent V-I and capacitance behavior and separated into groups. After irradiation, each set with an unirradiated control set is annealed to various temperatltres for 10 mm and the capacitance remeasnred. For very heavily doped diodes (-1019 per cm3) observable capacitance changes occur at neutron fluences of >1015 per cm 3. The results may be interpreted in seceral ways, the simplest of which is to assume simple vacancy diffiision with small impurity -racancy interaction (at the diffiision, i.e. annealing temperature of 700°C). In this interpretation it is found that a typical vacancy makes about 1024 jumps and travels about 10-5 cm before disappearing. The required effective annihilation center density is about 1016per cm3 . Estimates of the vacancy-impurity interaction can be made and the above numbers correctecl, but for arty reasonable assumptions the number of vacancy sinks connot be much reduced. ThE complete annealing of radiation induced defects requires that the vacancies and interstitials either recombine, travel to the surface of the crystal, or travel to an annihilation center, e.g., a dislocation or a precipitate. If the interstitial is ignored except as a possible vacancy annihilation center at low temperatures,* the motion of vacancies may be followed by monitoring the corresponding motion of substitutional impurities. pfister2 has measured the enhanced diffusion of impurities in an asymmetric shallow diffused silicon structure by optically monitoring the junction movement. In these experiments we monitor instead the capacitance of a heavily-doped deep symmetric p-n junction. The sensitivity for this method is several orders of magnitude higher than in Pfister's technique, mainly for two reasons: 1) the junction capacitance of a heavily-doped junction is sensitive to impurity movements in the Angstrom range* com- and 2) the junction may be far from the surface which is a major annihilation center for vacancies. THE EXPERIMENT A p-n junction is formed by the epitaxial growth of silicon from an A1-Si alloy on a silicon substrate at a temperature in the range 650° to 750°C. The technique used is the transport of an aluminum melt through a temperature gradient.4 A 10-mil thick aluminum disc is sandwiched between two silicon wafers and the assembly raised to about 650° C with a temperature gradient normal to the sandwich. After about 8 hr the upper (hotter) wafer has been entirely transported and deposited epitaxially on the substrate wafer. The substrate and overgrowth resistivity are measured with a 4-point probe. The as-grown structure is lapped until the wafer is about 1/2 mm thick with the junction in the center. Contacts consisting of electroless nickel covered by electroplated rhodium are applied to both the p and n sides. The wafer is diced into square dice 1/2 to 1 mm on a side and the dice are etched sufficiently to remove approximately 1 mil of silicon. The following results are all for aluminum (p-side) and antimony (n-side) doped specimens with NA =3x 1018 per cm3, ND = 2-8 x 101A per cm3. The diodes are sorted for consistent V-I and capacitance behavior and separated into groups. After irradiation, each set with an unirradiated control set is annealed and the capacitance remeasured. A special capacitance measurement method is used to insure a low sensitivity to shunt resistance. The diode is voltage driven and the current monitored by a phase lock amplifier. It is possible to adjust the detector phase to a point where shunt resistances as low as 100 O have no effect on the reading. The diodes in this study have a capacitance in the range 1000 to 5000 picofarads and a shunt resistance in the range 100 to l06 O depending on the stage of the anneal. THEORY The theoretical problem is twofold: 1) The computation of the amount of impurity diffusion and hence the impurity profile resulting from a given amount of vacancy motion, and 2) the computation of the capacitance from the impurity profile. A comparison of the theoretical and experimental capacitance (in particular the changes) yields the amount of vacancy motion. Vacancy Motion. A convenient parameter to measure the total amount of vacancy motion is Jv the total number of vacancy jumps per unit volume. Although this parameter varies with position in the crystal, owing to vacancy annihilation at the surfaces, it is approximately independent of position far from the surfaces, i.e. in the junction region. In terms of the number of vacancies per unit volume Nv and the vacancy diffusivity given by

Jan 1, 1970

By H. K. Birnbaum

The effect of 1ow-temperature stabilization anneals on the structure of the 0 phase Au-Cd alloys and on the diffusionless transformations observed in these alloys was examined by X-yay diffraction techniques. A phase separation in the ß-phase region was proposed to account for the experimenta1 results. The effects of quenching from elevated temperatures on the transformation behavior of these alloys were shown to be consistent with the proposed mechanism. IT has been shown that the high-temperature ß phase (CsCl structure) of the Au-Cd alloy system transforms to a phase having an orthorhombic (D2) ß&apos; structurel1-3 for compositions near 47.5 at. pct Cd and a tetragonal (4/m, m, m) ß" structure* in the vicinity of 50.0 at. pct Cd. Both transformations are diffusionless, crystallographically reversible, and occur on cooling at about 60° and 30°C respectively. The temperature interval from the beginning to the end of the transformation is of the order of 5°C in each case. Although the transformations are normally athermal, some of them have been reported to occur isothermally.= wechsler6,7 has shown that the effects of quenching a 49.0 at. pct Cd alloy from elevated temperatures are consistent with the retention of a nonequilibrium number of lattice vacancies. Annealing of these quench effects results in a broadening of the X-ray reflections.8 After a suitable quench, the 47.5 at. pct Cd alloy transforms to a phase having not the p&apos; orthorhombic structure but another structure which has properties similar to that of the ß" tetragonal structure.5.9 This change in the type of transformation has also been obtained after long anneals in the ß-phase region at about 70oC10 The present investigation was primarily concerned with the structural changes accompanying the above transformation phenomena. The change in transformation product and accompanying physical changes during an anneal in the ß phase have been termed stabilization effects. Experimental Procedure —The results reported in this investigation were obtained with the use of a Norelco diffractometer fitted with a temperature-controlled cryostat. The specimen temperature was controlled to better than ± 0.l°C during the measurements. CrKa radiation monochromated electronically with the use of a scintillation counter and pulse height analyzer was utilized. Specimens containing 47.5 and 50.0 at. pct Cd were prepared by sintering filings obtained from homogenized ingots of the proper alloy composition. (Gold of 99.999 pct purity and cadmium of 99.98 pct purity were used). All heat treatments were carried out with the specimens capsulated in vacuum ( < 10 % mm Hg) or in a He-H gas mixture. The quenching technique used in these experiments was to drop the pyrex capsule which contained the specimen from the annealing furnace into water, the temperature of which was controlled. The pyrex capsule shattered on contacting the water resulting in a relatively rapid quench. After the heat treatment, the specimens were mounted in the diffractometer and were left undisturbed in the diffractometer specimen holder during each sequence of measurements. EXPERIMENTAL RESULTS A) Low-Temperature Annealing—The transformations which were considered "normal" for these alloys were those obtained athermally during furnace cooling at approximately 50°C per hr after an elevated temperature anneal. Under these experimental conditions, the specimens were observed to transform to phases having structures whose diffraction patterns could be indexed as the ß&apos; orthorhombic structure for the 47.5 at. pct Cd and as the 0" tetragonal structure for the 50.0 at. pct Cd alloys. The transformation temperatures on cooling were approximately 60" and 30°C, respectively. Under the "normal" conditions both transformations were observed to go to completion, i.e., the entire volume of the ß phase was transformed to the product phase. In some specimens an extremely weak ß 110 reflection was observed at 20°C indicating that a small amount of retained ß was present. The effect of low-temperature annealing on the nature of the diffusionless transformations was examined for the 47.5 and 50.0 at, pct Cd alloy. The specimens were annealed in evacuated capsules at temperatures in the vicinity of 600°C (as specified in Table I) for 24 hr and were then cooled to 100°C at a rate of 50°C per hr. The specimens were then removed from the capsules and mounted in the diffractometer without allowing the specimen temperature to drop below 80°C. Annealing at the low temperatures was accomplished in the diffractometer by means of the cryostat which was mounted around the specimen. During the low-temperature anneals the lattice parameter, integral breadth of the reflections, and ratios of the integrated intensities of the fundamental and super lattice reflections for the 0 cubic phase were periodically determined. After annealing for the required time, the specimens were slowly cooled in the diffractometer and the diffraction patterns were recorded as a function of temperature. The specimens were cooled until the phase transformations were completed, following which the specimens were heated and diffraction

Jan 1, 1960

By W. C. T. Yeh, T. G. Oakwood, A. A. Hendrickson, R. H. Hammar

The objective of the research is to determine whether solid-solution strengthening effects observed in dilute solutions of silver can be accounted for by the influence of the solute addition on the dislocation structure oj- the crystals. The additions of both tin and indium produced only small changes in the dislocation densities and arrangements in silver crystals. However, as found previously, small solute additions have large effects on the tensile properties; the inj-luence of the tin and indium additions on the temperature dependence of the flow stress and the easy-glide range is especially strong; It is concluded that the indirect strengthening effect of the solute due to variations in the dislocation density as proposed by Seeger is of minor importance and that solute atom-dislocation interactions are responsible for the observed strengthenirzg effects. The experimental results were combined with those of Rogausch to test the concenlvatiorz dependence of solute strengthening. Both the first and one-half power dependences of the critical resoleed shear stress on concentratiorz fail in very dilute solutions. THE objective of the research is to determine whether solid-solution strengthening effects observed in dilute solutions of silver can be accounted for, at least in part, by the influence of the solute addition on the dislocation structure of the crystals. It is recognized that the addition of solute atoms may influence the strength properties of a metal through both "direct" and "indirect" effects. The former refer to the strengthening mechanisms that result from the interaction of solute atoms with dislocations; in the latter case, the strengthening effects arise as a result of solute&apos;s influence on quantities such as dislocation density, dislocation arrangement, stacking-fault energy, diffusivities, the elastic constants, and so forth. It is clear that the correct interpretation of solid-solution strengthening phenomena cannot be given until the importance of indirect strengthening effects is properly evaluated. In the particular case of close-packed metal crystals, Seeger showed that solute strengthening effects in dilute solutions of copper and silver might be accounted for by an increase in dislocation density due to the addition of the solute. Seeger&apos;s argument was that the strengthening effects extrapolated from more concentrated solutions indicate that small concentrations of impurities raise the critical resolved shear stress much more than is predicted by a concentration-independent dislocation density. The above idea was a very reasonable one. The dislocation theories of work hardening of Taylor,2 Cot-trell, 3 Mott, 4 and seeger5 had already associated the increased flow stresses with increased dislocation densities in deformed metals; investigations of the dislocation structure of metal crystals had provided a logical basis for expecting an increased dislocation density in crystals containing impurities (see for example, Ref. 6). The numbers involved seem reasonable, too. It can be expected that the flow stress of the crystal would increase as the one-half power of the dislocation density.&apos; Solute additions of 1 at. pct to metal crystals result in strength increases by factors in the range of three to ten. If one assumes that the strengths of the pure metal crystals are determined by their dislocation densities, then dislocation-density increases of one to two orders of magnitude as a result of solute addition would be required to account for the observed strengthening—not an unreasonable expectation. In addition to the effect of the solute addition on dislocation density, one might also anticipate important strengthening contributions to result from the solute&apos;s influence on the dislocation arrangement. Parker and washburns have reviewed a number of experimental evidences which show important strengthening effects due to the presence of subboundaries. Further, lattice strains due to impurity segregation would be expected to influence the distribution as well as the dislocation density of the as-grown crystal. As pointed out in the reviews of Chalmers,6 Elbaum,9 and winegard,lo micro segregation of impurities occurs at all interfaces of crystals in cellular growth; the impurity gradient results in lattice strains which can be reduced with the presence of dislocation arrays in the region of the impurity gradient. Hence, one would expect the presence of a solute to favor the formation of dislocation subgrain structures and that the subgrains would have an important influence on the strength of the crystal. The experimental observations that concern the possibility of an important strengthening contribution through the influence of the solute on the dislocation density or arrangement are not in agreement. Haasen has reviewed the observations of Meakin and Wils-dorf,12 Howie,13 and Bocek 36 and concluded that the solute&apos;s influence on dislocation density is not sufficient to account for strengthening effects in concentrated solutions but might, as seegerl suggested, make an important contribution in very dilute solutions. On the other hand, Hendrickson and Fine 14 concluded that changes in the dislocation density and dislocation width accounted for the solid-solution strengthening effects observed in silver-based aluminum solid solutions. Goss et a 1.I5 observed dislocation arrays in Ge-6 at. pct Si, Ge-0.2 at. pct Sn, and Ge-0.2 at. pct B crystals that were not observed in germanium crystals of

Jan 1, 1968

By M. H. Harris

A solution has been obtained to the problem of calculating flow into a cased and perforated well. Equations describing the idealized system were solved by numerical analysis techniques on a high-speed digital computer. Computer experimentation indicated that the results are within 3 per cent of the exact solution. Computed results are presented as an apparent skin effect, on a series of dimensionless working curves. Productivity ratios can be rapidly calculated from these data for the wide range of wellbore and reservoir properties actually encountered in field practice. Any reasonable vertical unisotropy ratio can be included in the computation. Productivities can be calculated for wells perforated in a regular pattern, a single horizontal plane or a vertical line on one side of the casing. Solutions for asymmetrical perforation patterns can he easily obtained from the working curves. Solutions for flow into sells completed with a horizontal notch are also provided. Results show that productivity can be increased by extending perforation penetration. This is especially true for shallow penetrations. The highest productivity is obtained when perforations are arranged in horizontal planes, as opposed to a vertical line on one side of the casing. Four or five perforations in one plane will approach the maximum productivity. The effect of perforation hole diameter is small, and is rioticeable only in shallow penetrations. INTRODUCTION The perforating method of well completion has been successfully and widely used in most producing areas. In the past, the desired perforation results were achieved by simply shooting numerous large holes in the casing. A perforating scheme for an area, or particular well, was established by evaluating two types of experimental data: the well flow index and the productivity ratio.&apos; 3 The well flow index test is a means of determining the relative flow capacity of perforations in a linear system. This test also gives information on the perforation size, shape and hole damage which can be expected under well-bore conditions. However, relative flow data from this test cannot be accurately tarnsformed into the radial wellbore system. Thus, no true indication of the productive capacity of a perforated well can be obtained from the well flow index test. A well productivity ratio is derived from electrolytic models built to simulate perforated wells. Available productivity ratio data 2,3 are limited in that all important variables are not extensively evaluated. For example, data are limited to well radii of 3 and 6 in., and to maximum perforation penetration of 1 ft. Practically no information is available on the pattern of flow into a perforation. The effect of various perforation patterns on well productivity has not yet been determined and the effect of perforation diameter has not been thoroughly studied. Also, it will be shown that this type of electrolytic model data is probably in error by as much as 10 per cent or more. Modern completion techniques such as limited-entry perforating, single-plane fracturing, steam and hot air injection and chemical consolidation of incompetent formations all rely on injection and/or production from a limited type of completion. These completions may consist of several high-capacity perforations or a horizontal notch which is equivalent to an infinite number of perforations in one plane. Proper design of these new completion techniques requires, in part, accurate estimates of a well&apos;s productive capacity. Data on perforated and notched well productivity have been determined in this investigation. Results are presented as a function of the pertinent variables. Equations describing the idealized system were solved by numerical analysis techniques on a high-speed digital computer. DESCRIPTION OF PROBLEM PRACTICAL APPLICATION The computed results can be applied to wells which meet several general specifications. An external drainage radius of the well must be known or assumed, but the well need not be drilled on a regular pattern. The well must be cased and cemented through the entire producing interval. And, the casing must be perforated with one or more horizontal planes of perforations. The perforation pattern itself must conform to three geometrical requirements. 1. The perforations in a plane must divide the plane into equal angular segments (Fig. 1). Four perforations per plane would be 90" apart. 2. Perforations in a plane must be directly above or beneath perforations in adjacent planes. For two shots per plane, perforations would lie in the BB&apos; plane (Fig. 1). 3. Horizontal planes must have equal vertical spacing and be separated from the top and bottom of the formation by one half the spacing interval. Single planes of perforations should be in the middle of the formation. This is shown in Fig. 2 where h is the formation thickness in a single plane conlpletion or the spacnig interval in a multiple plane completion. The spacing interval at the top and bottom of the formation may vary somewhat without causing an appreciable error in the productivity calculation if the formation is reasonably thick and there are many horizontal planes of perforations. A special provision has been made to calculate the productivity ratios of wells with uneven spacing intervals, or for the case where a single plane of perfora-

Jan 1, 1967

By John J. Gilman

BECAUSE of their layerlike structure, zinc crystals exhibit strong anisotropies for almost all physical and chemical properties. This should, and indeed does, greatly influence the plasticity of zinc for various crystal orientations. At low temperatures, the investigator of this plastic anisotropy is plagued by the great variety of deformation modes that operate. However, at high temperatures (250° to 419°C) only two deformation modes predominate: basal (0001) and prismatic (1010) glide. Furthermore, since strain hardening is virtually absent at high temperatures, the plasticity for these two modes of deformation can be very simply described by means of two equations of state. It is the purpose of this paper to describe the experimental behavior of basal and prismatic glide in zinc crystals, and to interpret this behavior in terms of other physical properties (in particular, the thermal expansion coefficients and the elastic constants) using the theory of dislocations. Fig. 1 defines the two planes of the zinc structure that will be discussed. Glide occurs very readily on the basal planes at all temperatures, and there is a very large literature on this subject. Much of the literature has been reviewed by Schmid and Boas;&apos; it will not be reviewed here. Kolesnikovl was the first to show that if basal glide is circumvented by stressing a zinc crystal parallel to the basal planes (giving zero shear-stress on the basal planes) then, at temperatures above about 320°C, glide on the first-order prism planes occurs. His results have recently been confirmed by Cahn, Bear, and Bell." These previous workers have established the existence and crystallographic elements of prismatic glide; the present paper is concerned with the stress, strain rate, and temperature relations of prismatic glide as contrasted with basal glide. Experimental Methods The crystals were square ones, 6x6 mm, that had been grown in precision Pyrex tubes by a method that is described in detail elsewhere.&apos; Most of the crystals were 99.999+ pct Zn (New Jersey Zinc Co. CP grade). Some were alloyed with 0.1 -+-0.005 atomic pct Cd, and chemical analysis showed that almost all of the added cadmium persisted through the crystal-growing process. For measurements of nonbasal glide, crystals were oriented with their basal planes parallel to both the rod axis and one of the flat faces of the square cross section. However, the orientation of the close-packed directions [1210] with respect to the rod-axis was variable. For basal glide measurements, the angle between the basal plane and the specimen axis was 35". The orientations were measured by the Gren-inger back-reflection X-ray method. The problem of finding a suitable method of gripping the crystals was the most serious experimental obstacle that arose. Because of the large plastic anisotropy of zinc, the usual gripping methods were unsatisfactory. Some methods that were tried were: high melting-point solder, making heads on the ends by locally melting a crystal, and electroplating nickel on the ends to form enlarged portions. For all these methods, the regions of the grips were weaker than the crystals themselves. Finally, two methods were decided upon: bend tests and direct machining of tensile specimens. In the bend tests, specimens were loaded as simple beams so that gripping was not a problem. The beams were 1 in. long and the axis of bending was parallel to the hexagonal axis of the crystals. For the crystals that were machined into tensile specimens, brass bars with slots in them were used to support the crystals, and thereby minimize the distortions due to machining. The crystals were glued into the brass bars with plastic cement which was later dissolved away with acetone. See Fig. 2, left. No clamps were used near the crystals and the machining was done using a milling machine with a fly-cutter. The tool bit was very sharply pointed to minimize burnishing. The feed was less than 1 mil per cut. The depth of cut was 2 mil for roughing cuts, and % mil for the finishing cuts. This machining method produced surface layers of tiny recrys-tallized grains only 2 to 3 mil deep, and the bodies of the crystals were not measurably disturbed. After the crystals had been machined and removed from the brass holders, they were chemically polished until about 5 mil had been removed from all their surfaces. The polishing reagent consisted of equal parts of concentrated HNO,, 30 pct H3O and ethyl alcohol; it is described in detail elsewhere." A typical crystal is shown in Fig. 2, right. The I-shaped faces are normal to the hexagonal axis of the crystal; otherwise the projections at the ends would simply shear off when the crystal was loaded. The cross section in the 2?-in. gage length is 0.215x0.115 in. It was found that the polished

Jan 1, 1957

By R. M. Kuralt

CONCESSION from the Chilean government granting the company use of the Rio Salado water stipulates that a minimum of 35,000 metric tons of such salty water must be diverted from the Salado daily, and be disposed of in a manner not to contaminate the Rio Loa to the east of its confluence with the Rio San Salvador at Chacance, Fig. 1. Consequently, the selection of a suitable site for the sulphide plant tailing disposal had the additional problem of the disposal of excess brackish waters. Studies of the terrain in the area directly to the south of the plant indicated that construction of tailing ponds would be costly, and generally unsatisfactory due to excessive slope of the ground, lack of flanking hills, danger of raising the groundwater level thus causing springs along the Antofagasta-Bolivia railroad; and the possibility of creating a dust nuisance at the plant site or at Calama due to blowing sands. Further to the southwest the San Salvador river canyon offered some possibilities and surveys were made at sites A to D, inclusive, Fig. 1. Here again costly dams would have been necessary to impound the tremendous quantity of tailing produced by the new plant, and provision would have to be made to handle a considerable flow of water through the disposal area to the west of the Rio Opache. Additional surveys were made in the area to the southeast of the plant which brought to light the existence of a natural basin of about 14 1/2 square miles, flanked by low-lying hills, and requiring only the most rudimentary dams to close the outlets at the western end. It has been estimated that the Salar de Talabre, as this basin is called, has the ultimate storage capacity of 1 billion tons of tailing with dam heights of only 60 ft. Pipe Line Layout After the decision had been reached to use the Salar de Talabre for the main disposal area various methods were considered for transporting the tailing from the 300 ft diam thickeners to the disposal site, 17.7 miles away. The first plan was to construct a. concrete launder on a 11 pct grade but a survey of this grade line indicated it would not lead directly into the Salar but would terminate somewhat to the north, and from that point on the slope would be considerably less than 1 pct along a natural watercourse. A slope of 2 pct or even 2 ¼ pct in such a rough watercourse or ditch is the ideal, judging from the success of operations at Cananea. Since a simple ditch is the most economical vehicle for the transportation of tailing, it was decided to use one with a 2 ¼ pct grade for as much of the distance as was possible with the existing terrain and to construct a concrete headbox, or forebay, at the terminus of the ditch to supply a steel pipe line leading the rest of the way into the Salar. Referring to the maps of the Chuquicamata area outlining the tailing disposal system, Figs. 1 and 2, one can trace the flow of the tailing from the thickeners to the Salar as follows: The 8-in. spigot pipes from the thickeners (1) discharge into a concrete sump feeding a concrete launder with a 2 pct slope. The launder carries the tailing into a concrete junction box (2) located south of the sulphide plant. The purpose of the junction box is to provide emergency facilities for diverting the tailing flow from the main disposal area to the emergency area. It also provides a junction point for the launder from the sulphide plant&apos;s future east extension. The box is fitted with a pair of radial gates controlling flow into the main tailing ditch (6) or the emergency ditch (3) which terminates on the pampa. All ditches are of the same cross section, namely 4 ft wide at the bottom with 1 : 1 side slopes and with a minimum depth of 21/2 ft. Where the nature of the ground demands it, the ditches are lined with stone rubble. The overflow from the plant&apos;s 10 million gal reservoir (4) is led into the main tailing ditch by way of a spillway ditch (5). The main ditch terminates in a trashscreen fitted, concrete forebay (7) which serves as a headbox for a 24 in. O.D. x 3/8 in. wall, Dresser coupled, steel pipe (10) and a 12 in. x 8-gage spiral welded, wedge-lock coupled, steel pipe (8). The forebay is fitted with two compartments, one for each pipe, and flow into each is controlled by radial gates. Each compartment is fitted with a 6-in. drain pipe controlled by a rubber pinch valve. To protect the forebay from the abrasive effects of the tailing, the sides of the compartments will be lined with old

Jan 1, 1952

By E. J. Ripling, S. I. Liu

IT has been shown in a number of recent publications that much information on the mechanical behavior of metals can be gleaned by first deforming test specimens under one set of conditions, and then evaluating the effect of this deformation by means of a subsequent tensile test. A straining procedure of this type has been applied to study the flow behaviors of a number of metals.1, 2 In these studies the prestraining and testing were both tensile strains, while the straining temperature was varied between the prestraining and testing steps. These data indicate that there is a more or less general flow behavior exhibited by all metals which are pre-stretched at one temperature and then tested in tension at a second temperature. Prestraining a metal at a high temperature produces a lower yield strength during the subsequent low temperature strain than would the same total strain at the lower temperature. On reversing the order of the strains, low temperature prestraining produces a higher yield strength during the subsequent high temperature straining than would a single high temperature strain of the same magnitude. Unlike the flow behaviors, the fracturing characteristics of metals when prestrained under one set of conditions and tested under a second set of conditions is quite material dependent. The fracture behavior of a number of steels2" as well as of a commercially pure zinc,4 have been investigated by these two-step tests and was found to depend upon the position of the transition temperature with respect to the prestraining and testing conditions. Since these fracturing phenomena are complicated by the appearance of the transition temperature, it has been difficult to reliably define the basic effect of a two-step straining procedure in fracturing. Metals crystallizing in the face-centered cubic system do not exhibit transition temperature effects so that the mechanical characteristics obtained on these materials could serve as a base for two-step straining behaviors. Consequently groups of specimens of the aluminum alloy 24s-T4 were prestrained various amounts at room temperature in either tension or compression after which these strained specimens were further strained to failure, or tested in tension, at either room or some lower temperature. Other groups of 24S-T4 specimens were prestretched at various low temperatures after which these were tested in tension at room temperature. These straining techniques then made it possible to compare the behaviors of aluminum with the behaviors previously presented for steels. Material and Procedure The commercial aluminum alloy 24S-T4 in the form of 3/4 in. rods was used in this investigation. The material was subjected to the following treatments before machining: 1—resolution treating at 920" & 10°F for 45 min, 2—quenching in water at room temperature, and 3—aging at room temperature for four days. The re-heat treated material was then machined to either of the specimen shapes shown in Fig. 1. Fig. la shows the threaded-end specimen used for prestraining in compression. Fig. 1b shows the specimen used for both prestrain in tension and final testing. The material subjected to precompression in the form of the specimen shown in Fig. la was re-machined to the specimen shape in Fig. 1b for final testing. Prestraining in tension and final testing were done without any intermediate machining. All straining was performed on a 10,000 1b Riehle tensile testing machine. Tensile strains were conducted in a specially designed concentric fixture which produced an eccentricity of less than 0.001 in." The change in diameter at the minimum section of

Jan 1, 1954

By Irving Cadoff, Kurt Komarek, Edward Miller

THE lead-telluride phase diagram as compiled by ansen&apos; has one intermetallic compound, PbTe, with solid-solubility limits extending from 22 to 45 wt pct Te (31.4 to 57.1 at. pct). Pelzel2 redetermined the solubility limits on the lead-rich side of the compound by measuring the relative areas of the two phases in samples annealed in the liquid + compound region, and obtained data that agreed with that of Hansen. Recent studies of the semiconducting properties of PbTe3 however, have indicated that addition of either lead or tellurium to PbTe does not produce samples having carrier concentrations greater than about 10 19 cm-3. Assuming that each impurity atom results in one ionized charge carrier, this carrier concentration corresponds to a solubility range of less than 0.04 at. pct. Fritts and Karrar4 have also observed two phases in samples containing from 0.15 to 3.0 pct excess Pb. To resolve the discrepancy between these data, the solid solubility limits of the compound PbTe were reinvestigated, using several other techniques. Ten 25-g samples with compositions of 1/2, 1, 3, 5, and 10 wt pct excess Pb and Te and two 100-g samples of 15 and 65 wt pct Te were prepared, sealed in evacuated quartz capsules, and melted at 950oC. The 1 pct excess Pb and Te and the 15 and 65 wt pct Te alloys were homogenized for 96 hr at 450°C; the remaining specimens were annealed 50°C below the solidus temperature reported in Hansen. The specimens were polished and etched with dilute HNO,. All the samples were two phase, the second phase appearing at grain boundaries or as spheroidized inclusions in the grains. In the case of the tellurium rich specimens, the second phase could be identified as a eutectic. Debye-Scherrer powder diffraction patterns of the i, 1, 3, 5, and 10 pct excess samples were obtained using CuKa filtered radiation. The films were indexed as the B1 or NaCl structure. The calculated lattice parameter of PbTe was the same for all the specimens, with an average of a0 = 6.460 ± 0.0005A. Lines due to excess lead or tellurium were very faint but could be clearly seen in all the films. The relative areas of the two phases in the 15 and 65 wt pct Te samples were corrected for the differences in density of Pb, Te, and PbTe, and taken as proportional to the relative volumes of the two phases. The corrected relative volumes agreed with a phase diagram having negligible solubility of both lead and tellurium in lead tellurium. The density of the two specimens was obtained to give a third independent determination of the phase limits. The specimens were broken into small pieces to eliminate any internal porosity, and adherent air bubbles were removed by vigorous shaking under water for several hours. The density of lead (11.34 g per cm3) and of tellurium (6.25 g per cm3) was taken from the International Critical Tables and that of stoichiometric PbTe (8.25 g per cm3) calculated from the lattice parameter. For the 15 wt pct Te samples, the density assuming no solubility was calculated to be 9.89 g per cm3; the observed density was 9.86 g per cm8. For the 65 wt pct Te alloy, the density calculated for the case of no solubility was 7.24 g per cm3; the measured density wag 7.22 g per cm3. These results are consistent with those of planimetry and X-ray. SUMMARY Data have been presented which show that the solid solubility of both lead and tellurium in PbTe is

Jan 1, 1961

By M. Hansen, C. C. Wang

THE 6 phase of the Cu-Sn system (Cu,Sn, = 32.53 pct Sn) was considered to be stable down to room temperature until Owen and Iball showed by X-ray analysis that it undergoes a eutectoid decomposition into the a and e phases at a temperature near 300°C. Their findings have been confirmed by other investigators,2-5 a11 of whom used X-ray diffraction studies of powdered specimens. The transformation temperature has been reported by various authors as lying between 300" and 380°C. To our knowledge, no microscopic evidence of the eutectoid reaction has been published, as yet. It was in connection with other work that longtime annealings at 300°C were conducted with alloys containing 22, 32.6, and 35 pct Sn (nominal compositions) prepared from electrolytic copper and electrolytic tin and cast in a small iron mold. The specimens were first annealed at 700°C for 5½ hr and quenched from 400 °C after cooling to, and annealing at, that temperature for 9½ hr. After this treatment the sample with 22 pct Sn was cold worked for 15 pct reduction in thickness; the 32.6 and 35 pct alloys were too brittle to be cold worked. The final anneal at 300°C was done in a sealed pyrex glass bulb for 63 days. Fig. 1 represents the microstructure of the annealed alloy with 22 pct Sn. It shows primary a solid-solution crystals in a matrix of the (a + 8)-eutectoid formed at 520 °C. The a crystals contain 8 inclusions which precipitated from a due to the decrease in the solubility of tin in copper with fall in temperature. The decomposition of the 8 phase into a (light) and E (dark) can clearly be seen in some areas of the (a + 8)-eutectoid matrix. However, the decomposition is far from being completed, even after the long-time anneal used. Figs. 2 and 3 depict the microstructures of the annealed 32.6 pct alloy, which was intended to consist entirely of 6 phase. Due to some loss in copper on melting, the composition is slightly higher in tin. Accordingly, the sample after quenching from 400 "C consisted of grains of the 8 phase with the e phase arranged along the grain boundaries and as a Wid-manstatten precipitate within the 6 grains. After an annealing time of 63 days, the eutectoid decomposition, 6 + a + e, is still in its early, initial state. The pearlitic type of eutectoid is nucleated at the c crystals, preferably those surrounding the grain boundaries of the 8 phase. The appearance of the (a + €)-eutectoid in the 35 pct Sn alloy was very similar to that shown in Figs. 2 and 3. Again, the eutectoid decomposition nucleated at the 6 phase and proceeded from there into the 8 areas. As is evident from Fig. 2, the rate of decomposition of the 6 phase at 300°C is extremely sluggish: In the representative area shown only about 5 pct of the 8 phase has undergone the eutectoid trans- formation after annealing for 63 days. On the other hand, Owen and Williams2 have reported that X-ray photographs of powdered samples with between 17.5 and 34 pct Sn did not show 8 lines after annealing for only five to seven days at 300°C. This is in accordance with the fact that the rate of reaction in powdered samples is higher than in massive specimens, as a result of the excess free energy of the powder (due to its greater surface area). The authors wish to express their thanks to C. A. Johnson for preparation of the micrographs.

Jan 1, 1952

By J. N. Butler, R. J. Morris

A series of organic collectors has been developed which successfully float synthetic secondary uranium minerals, such as autunite, carnotite, and torbernite. Recoveries up to 97 pct have been obtained. With cleaning of rougher concentrates, ratios of concentration as high as 15:1 are possible on head assays of 0.10 to 0.50 pct U 3 O 8. Additions of certain base metal salts aid in recovery and materially increase the rate of flotation and selectivity of the collectors for the synthetic minerals. Flotation tests on natural uranium minerals have not yet equaled results obtained on the synthetics, although these collectors do give better results than conventional collectors for nonsulfide minerals. RAPID increase in mining and milling uranium ores during the past seven years and the discovery of large tonnages of uranium-bearing material too low in grade to stand the cost of leaching have developed considerable interest in possible methods for beneficiating these marginal ores. Such ores are generally classed as those containing less than 0.10 pct U3O8. Development of a beneficiation method that would give both high recovery and high ratio of concentration would also make possible the beneficiation of higher grade ores and would provide higher grades of feed to existing leaching plants. Although considerable research and testing on physical or physico-chemical beneficiation of domestic uranium ores has been done in the past, to the best knowledge of the authors only a single application of physical beneficiation is now in operation on a commercial scale. Flotation has been attempted on the basis of mineral association rather than by direct concentration of the contained uranium minerals. Flotation studies conducted on this project on certain ores gave recoveries of 60 to 70 pct of the uranium by the use of conventional flotation agents such as oleic acid, but ratios of concentration were in the order of 1.5:1 to 2.5:1. Subsequent cleaning to upgrade the concentrates rapidly increased losses in the cleaner tailings, which were not later refloated in the rougher flotation. Selection of Collector: In selecting desirable organic collectors for these oxide systems, a thorough study was made of the relationship between structural characteristics and collector activity by an examination of the behavior of a number of different functional arrangements present in a variety of organic molecules, (see Fig. 1). It is generally accepted that a collector must have a relatively long-chain hydrocarbon radical and a chemically reactive elec-trophilic center. Such a requirement could be met by a large number of compounds, but steric effects at the uranium mineral surface, solubility, compat-ability with aqueous systems, air avidity, bond strength at the mineral surface, interfacial concentration of the collector, and diffusion rate of the formed complex from the air-water interface eliminated many as unsuitable for this purpose. Preliminary investigations were completed of possible collector designs consisting of aliphatic and aromatic hydrocarbon radicals attached to stable combinations of nitrogen, oxygen, sulfur, and halogen electrophilic centers, Fig. 1.Tests were made to determine melting point spans, solubility of mineral-collector combinations in various solvents, reactions with soluble uranium salts, contact angles, and floatability by semi-quantitative beaker methods.&apos; Contact angle determinations were not too useful because of the fine particle sizes of available mineral samples. From the foregoing study it appeared that nitrogen-sulfur electrophilic centers coupled with straight-chain saturated alkyl hydrocarbon radicals would hold the most promise for floating secondary uranium minerals. As the dithiocarbamate compounds can be made to combine these attributes they were selected for further study. The dithiocarbamates form a parallel structure to the xanthates, with the fortuitous exchange of

Jan 1, 1957

By J. Jones-Parra, J. C. Calhoun

INTRODUCTION The purpose of this paper is to present the results obtained by solving the fractional flow&apos; and frontal advance&apos; equations to obtain oil recovery at water breakthrough as a function of the length of the system being flooded, the linear velocity of injection and the displacing phase viscosity. The method of solution makes use of the stabilized zone concept first presented by Terwilliger, et al3 when calculating saturation distributions in a gravity drainage system. In order to check the calculated results, the equations and method of solution were applied to the system on which Rapoport and Leas&apos; reported experimental data. METHOD OF SOLUTION The solution of the fractional flow equation and the frontal advance equation is obtained by assuming that a water front forms to sweep the oil out ahead of it. There is ample evidence that under the proper conditions a water &apos;front does form. If this water front is not to dissipate, the water saturations which comprise it must have equal linear velocities. These water saturations are said to comprise the stabilized zone. Equation (2) indicates that for all these saturations and hence fw must plot as a straight line against saturation for those water saturations comprising the stabilized zone. The water saturations lying between the highest in the stabilized zone and the highest that can be achieved in the porous medium comprise the variable zone. Regardless of the numerical value of the length of the system, the variable zone must eventually span all of it, so that for long enough systems in Equation (1) will be small enough to be neglected. Hence, for the saturations in the variable zone Equation (1) can be simplified to In order to determine the composite fw function applicable to the entire range of saturations in the porous medium, it is necessary to find the water saturation which separates the stabilized zone from the variable zone. This dividing saturation must be on the curve defined by Equation (4), and a tangent curve at that point must pass through the initial water saturation to satisfy Equation (3). Hence, the valid fw curve is given by a straight line starting at the initial water saturation, tangent to the curve of Equation (4): and along the curve of Equation (4) from the point of tangency on. The point of tangency determines the water saturation dividing the zones. The length and shape of the stabilized zone can be found by solving Equation (1) for Integrating this expression numerically between any two saturations in the stabilized zone gives the distance separating these two saturations. By repeated integration, the saturation distribution of the stabilized zone can be determined. The total length of the stabilized zone is given by The integral appearing in Equation (5) is a function of the viscosity ratio, the capillary properties of the rockfluid system, the relative permeabilities, and the initial water saturation. Considering these variables fixed and designating the value of the integral by writing caw for and v/60 for q/A; Equation (5) becomes The saturation distribution of the stabilized zone can be integrated over its length and divided by the length to obtain the average water saturation The volume of water in the stabilized zone is then given by The average water saturation in the variable zone can be found by extending the straight line segment of (the segment joining Sw and Sw) until it intersects fw = 1.00. The saturation at the intersection is. This method of finding is nothing more than the graphical solution of the equation The volume of water in the variable zone at breakthrough is then given by Assuming no initial water saturation, the recovery at breakthrough expressed as percent pore volume is given by

Jan 1, 1953

By W. F. Hosford

A series of aluminum single crystals was subjected to axially symmetric flow by drawing through dies. The orientation dependence of the drawing stress, which indicates the resistance to this type of flow, compares reasonably with predictions of Taylor and of Bishop and Hill. Measured lattice rotations likewise are generally consistent with theory. The most successful analyses of the plastic behavior of polycrystalline metal and its relationship to single crystal behavior are those of Taylor1-3 and of Bishop and Hill.4-6 The purpose of this paper is to provide a critical test of some of the basic assumptions involved in these theories. Both treatments apply to fcc metals and assume the shape change of each grain in a polycrystal to be the same as that of the polycrystal as a whole. Thus for a randomly oriented polycrystal extended under uni-axial tension each grain is assumed to undergo axially symmetric flow. dey = dez = -1/2dex, deyZ = dezx = dexy = 0 [l] where x, y, and z are a set of orthogonal axes, x being the tensile axis. Although [011.] oriented grains in bcc and fcc metals may depart markedly from this ideal behavior,7,8 the assumption is probably quite reasonable for most grains. Under a uniaxial tensile stress, ox, the work dW per unit volume expended in producing an increment of axial strain dex is, dW=oxdex [21 Since this work is expended in slip, dw =STi dyi 131 where Ti and yi are the shear stress and shear strain on the active slip systems. In both analyses Ti is taken to be the same on all slip systems, and dependent only on the total prior shear strain on all systems, so dw = Tdy [41 where t is the shear stress required for slip and y is the sum of the shear strain yi on all slip systems. Combining 121 and [4] and defining M = oX/T The ratio M is a generalized Schmid factor. It relates the tensile stress required for axially symmetric flow, ox, to the basic shear stress, 7, and it also expresses the ratio of crystallographic strain, y, to the tensile strain, Ex It depends only on the orientation of the crystal. Taylor evaluated M for various orientations by finding the least value of dy/dEx which could satisfy the shape change. Bishop and Hill, on the other hand, found M by considering the relative work (1/T)dW/dEx expended by stress states which could activate enough slip systems to produce the shape changes. The results of both methods appear to be equivalent, although certain omissions were made in Taylor&apos;s original work. The orientation dependence of M, calculated by the second method,9 is shown in Fig. 1. Taylor used the average 2= 3.06 for all possible orientations to predict the tensile stress-strain curve (oxvs Ex) for a random polycrystal from the shear stress-strain curve (t vs y) of a single crystal. Changes in M from lattice rotation were neglected so points on the ox vs ex curve were simply taken at ox = 3.06t and e = y/3.06 from corresponding points on the t vs y curve. Recent extension of the analyses of Taylor and of Bishop and Hill to crystallographically textured metals has been used to relate plastic anisotropy to textures, and to predict the potential texture hardening that could result from texture control.9 Unfortunately there have been relatively few experimental tests of the underlying theory. Taylor found that the tensile stress-strain curve of polycrystalline aluminum did agree reasonably well with that predicted from a single-crystal T-y curve. Had the single crystal undergone easy glide, how-

Jan 1, 1965

By D. L. Martin

THAT small amounts of impurities have a harm-J- ful effect on the malleability of metals and alloys is well-known. One common type of em-brittlement involves the formation of a small quantity of eutectic at the grain boundaries, and is typified by sulfur embrittlement of nickel. Another example of eutectic embrittlement—sulfur embrittlement of cobalt—is described in this report. In the preparation of specimens for a study of Co-Pt alloys, it was observed that the hot swagabil-ity of the alloys appeared to be influenced by the grade of cobalt used as melting stock. The cause of the hot-shortness was not traced to any particular impurity, although sulfur was suspected.&apos; The damaging action of sulfur on the malleability of cobalt has not been generally recognized,&apos;; in spite of the fact that the Co-S phase diagram8 eveals the same basic conditions—low solubility and eutectic formation—responsible for sulfur embrittlement of iron and nickel.7, 8 Apparently sulfur embrittlement has not been a serious problem in the fabrication of cobalt alloys. One related factor is likely the limited commercial experience with high cobalt alloys, since the predominant use of cobalt has been in alloys containing less than 75 pet Co. A series of Co-S alloys was prepared and studied to establish the effect of sulfur on the hot working characteristics of cobalt. Specimens, 5/8 in. diam by 4 in. long, were prepared by vacuum melting in magnesium oxide crucibles and casting in a copper mold. Two grades of low sulfur electrolytic cobalt were used as the basic material for the study, one from Johnson, Matthey and Co. and the other from the International Nickel Co. Each contained about 99.5 pet Co and had a nominal sulfur content under 0.005 pet. The sulfur was added initially as cobalt sulfide powder. Later, some low sulfur alloys were prepared by diluting the high sulfur alloys with cobalt. Trouble was experienced in controlling the sulfur content. Apparently much of the cobalt sulfide powder was lost during melting, as most of the samples contained a lower sulfur content than was added. The alloys were evaluated for hot brittleness by heating to 1000°C in a hydrogen furnace and swaging in air. The results of these tests are summarized in Table I. All the alloys containing less than 0.008 pet S were successfully hot swaged to 1/4 in. diam. The bars containing more than 0.015 pet S could not be swaged because of the formation of intercrystal-line cracks similar to those illustrated in Fig. 1. Examination of the microstructure of the cast bars revealed cobalt sulfide eutectic at the grain boundaries, Fig. 2. The sulfide was not always continuous at grain boundaries in bars that were hot embrittled but, in general, the particles did form a network that could account for the brittleness above the eutectic temperature, 880°C. There is no question about the brittle nature of a specimen exhibiting a continuous sulfide network such as is shown in Fig. 2b, though a sulfide distribution similar to that in Fig. 2a is marginal. This particular bar cracked when hot-swaged. However, other bars with lower sulfur content but with some sulfide phase at grain boundaries were successfully worked. The reduction of area of a hot tensile test specimen was also found to be a sensitive indicator of sulfur embrittlement. The variation of reduction of area with sulfur content is shown in Fig. 3 for specimens fractured at 900°C in an evacuated capsule. The ductility of cobalt is greatly reduced when the sulfur content exceeds 0.005 pet. Similar results were obtained for alloys tested at 800°C, below the eutectic temperature. The upper sulfur embrittlement limit of 0.015 pet, Table I, agrees with the observation of Kalmus8 hat

Jan 1, 1957

By M. T. Hepworth, T. P. Papazoglou

Hydrogen diffusion in hcp and bcc titanium in the temperature range 610° to 900°C was measured by reacting cylindrical specimens of high-purity titanium at constant temperature with small constant pressures of hydrogen of the order of a few Torr. In the range 0 to 6.7 at. pct H in hcp titanium, the diffusion coefficient D in sq cm per sec is given by: where T is in °K and R in cal per g-atom OK. Only three measurements of diffusivity in bcc titanium were made: at 900&apos; : the diffusivity in ß titanium was found to be 1.8 x 10-4 sq crn per sec. McQUILLAN1 has studied the constitution of the Ti-H system and reported the concentration of hydrogen as a function of pressure of hydrogen and temperature. He found hydrogen absorption was reversible and rapid at temperatures above 500°C in both crystallographic modifications, the a (hcp) phase and the ß (bcc) phase, with the latter phase stabilized by hydrogen additions. Wasilewski and Kehl 2 measured the diffusivity of hydrogen in hcp and bcc Ti-H alloys. For bcc alloys, they reacted cylindrical specimens of titanium with hydrogen gas at 1 atm pressure. They measured the rate of absorption of hydrogen isothermally on specimens ranging from zero hydrogen content when above the transformation temperature to hydrogen contents sufficient to stabilize the bcc phase when below the transformation temperature. By integrating Fick&apos;s second law for a cylindrical geometry, assuming a diffusion coefficient independent of composition, they calculated diffusivities as a function of temperature. In the range 650" to 1000°C their results in bcc titanium yielded the expression: where D is in sq cm per sec, T in OK, and R the gas constant in cal per g-atom-OK. Their studies on the hcp a phase were conducted by exposing long cylindrical titanium specimens to hydrogen at a sufficiently high pressure to establish a surface layer of fl phase 80 to 120 u thick for the duration of an isothermal experiment. Concentration profiles were then determined by hydrogen analysis from chips obtained upon machining quenched specimens. The diffusivity of hydrogen was then calculated yielding the expression: The present investigation was undertaken principally to redetermine the diffusivity data on a titanium by a direct absorption from the gas phase at sufficiently low hydrogen pressures to avoid the presence of a surface bcc phase and also to check the diffusivity data at low hydrogen concentrations in the bcc stmcture. EXPERIMENTAL PROCEDURE High-purity electrolytic sponge titanium (99.9 pct) of BHN 91 was arc-melted, forged, rolled, and machined into cylinders of final hardness, upon annealing, of BHN 92. Cylindrical specimens of two sets of dimensions were used: 1.524 by 2.931 cm and 1.905 by 3.663 cm diam and length, respectively. The experimental apparatus used for annealing specimens and for admitting known amounts of hydrogen at constant pressure is shown in Fig. 1. In a typical experiment, a specimen was lightly abraded with fine-grain silicon carbide, washed with water and detergent, and then thoroughly degreased with reagent-grade tri-chlorethylene and acetone. The specimen was suspended by a Chrome1 wire in the center of a quartz furnace tube, without contact with the tube, and heated to 925°C (as measured by a thermocouple adjacent to the specimen, outside the tube) for a period of at least 4 hr under a vacuum of from 10-6 to -7 Torr as measured by an ionization gage. The furnace temperature was then adjusted to the temperature chosen for the particular diffusion study and the specimen allowed to equilibrate thermally. Hydrogen was then ad-

Jan 1, 1969

By Gordon W. Hodgson, Edward Tipman

INT&apos;RODUCTION An appreciable number of the oil fields in Western Canada are accumulations of heavy black oils in more or less unconsolidated sandstones. When the crude oils are produced by conventional means, they are frequently contaminated with both sand and oilfield water. The water is usually present as emulsified water, and the sand and other solid materials are suspended in the emulsions. The presence of the solid material in the crude oils is troublesome and, in general, little is known about the behavior of suspended solid particles in emulsions. The Stokes equation describes the behavior of suspended particles in homogeneous fluids in terms of particle size, density differential, and fluid viscosity. In the case of an emulsion, particle size and density differential introduce no difficulties, but considerable doubt centers around the viscosity term. It has been reported1 that the viscosity of an emulsion is related to the viscosity of the continuous phase by an expression of the type: n = a, (1 + a C) where n is the viscosity of the emulsion, n,, is the viscosity of the continuous phase, a is a constant, C&apos; is the volume concentration of the disperse phase. The value of 17, the coefficient of the concentration term, has been determined for various systems, and has been found to vary from a value of 1 to 4.75. The value of 2.5 has been found to be applicable to a large number of systems, and this is the value that is widely used in the equation which then becomes the Einstein equation for the viscosity of emuls~ons. It is of considerable significance that neither the particle size nor the viscosity of the disperse phase enters the expression; the expression for the viscosity of the enlulsion is based solely upon the viscosity of the continuous phase and the concentration of the disperse phase. For crude oil emulsions the Simha equation and the data presented by Fukushima and lchimurai show a non-linear dependence of the viscosity ratio on the water concentration. While it is undoubtedly reasonable to use these data for predicting the viscosity of a specific emulsion, and while it is equally reasonable to expect the calculated viscosity to predict the settling rate of a solid spherical particle in the emulsion by means of Stokes equation, there seems to be no direct evidence that this calculation is indeed sound for describing the settling rates of solid particles in emulsions of water in crude oils. PROCEDURE A direct approach to the problem was thus indicated. Laboratory equipment was designed and built for the direct determination of the rate-of-fall characteristics of solid particles in emulsions of water in oil. Although the apparatus incorporated the basic design of conventional falling-ball viscometers, the study was concerned directly with the rate-of-fall characteristics of particles in emulsions, rather than with the viscosity of the emulsions as such. The crude oil used in this study was a very heavy black crude oil—the McMurray oil obtained from oil-soaked sands outcropping on the Athabasca River in northeastern Alberta. It was produced from the sands by strip mining followed by hot-water separation of the oil in the separation plant of the Alberta Government at Bitumount&apos;. The primary plant product was a wet crude oil containing about 5 per cent solids and 35 per cent water. The final plant product was only slightly different from the native oil, having lost only about 4 per cent of its bulk as light ends during dehydration distillations. In the present investigation two kerosene dilutions of the McMurray oil were used in addition to the dry plant product. The McMurray oil contained 1.92 per cent solids. Analysis of the solids by X-ray diffraction showed the presence of kaolinite, pyrite, and illite as major constituents. with lesser amounts of quartz. Particle size of the pyrite and quartz was less than 10

Jan 1, 1957

By S. S. Lisnyak, B. D. Lichter

An important question in the study of the "hot corrosion" phenomenon (i.e., accelerated oxidation of Ni-Cr-base and Co-Cr-base "superalloys" in the presence of sulfur) is the condition of formation and physico-chemical properties of different sulfides in the system Ni-Co-Cr-S. seyboltl has observed the presence of ((chromium-rich" sulfides of compositions M3S4, and M2S3 in the scales of superalloys after hot corrosion; however, as he points out, much confusion exists as to the identity of sulfides found on Ni-Cr and Co-Cr alloys. According to the literature,&apos; ternary sulfides, e.g., NiCr2S4, (monoclinic structure) and CoCr2S4 (spinel structure) exist in these systems. Therefore, it is likely that these compounds are found in the scale of alloys undergoing hot corrosion. At present this possibility has not been discussed in the literature. Accordingly, we have begun investigation on the properties of ternary sulfides and their mutual interaction. The magnetic and electrical properties of pure NiCr2S4 and pure CoCr2S2 have been previously determined."-&apos; In the present work we have studied the interaction between these sulfides at high temperatures by means of X-ray diffraction and magnetic susceptibility. The measurements were carried out at room temperature after appropriate thermai treatment of samples at high temperatures. For alloys containing the three elements nickel, chromium, and cobalt this interaction may be of importance in the study of the hot corrosion phenomenon. The compounds NiCr2S4 and CoCr2S4 were prepared from stoichiometric amounts of the elements and CoS in the case of CoCr2S4. Samples were mixed and sealed in evacuated silica tubes, slowly heated to 900&apos; to 100O°C, and held at temperature for a total of 120 hr (NiCr2S4) or 80 hr (CoCr2S4) with intermediate re-grinding~. X-ray diffraction showed a pure spinel structure for CoCr2S4 and a monoclinic structure for NiCr2S4. Samples of mixtures of the two ternary sulfides were prepared with different compositions, see Table I. Samples were heated for a total of 80 hr at 900&apos;C in evacuated silica tubes, with one intermediate regrind-ing. The capsules were slow-cooled to room temperature in the furnace. Samples for X-ray diffraction were prepared by placing powder on a glass slide with vaseline. Dif- fractometer traces were obtained on a G.E. XRD-5 diffractometer using a chromium tube and vanadium filter (40 kv and 31 ma). The size of the spinel unit cell was determined from the eight highest angle peaks (80 deg < 2b < 160 deg). Calculated lattice parameters were plotted vs cos B . ctn 0 and extrapolated to 6 = 90 deg. Measurements of the magnetic susceptibility were carried out at room temperature using the Faraday method in a magnetic field of 3000 G and using a Cahn RG automatic microbalance. The system was calibrated from the well-established susceptibilities of platinum and palladium: (Xpt = 0.968 x 10-6 g-1 and Xpd 7 5.04 x 10~6 g-1). The weight of samples were approximately 0.200 g. X-ray diffraction patterns for unsintered mixtures showed Bragg peaks from both the spinel (CoCr2S4) and monoclinic (NiCr2S4) structures. After sintering no monoclinic peaks were observed in samples containing up to 40 mol pct NiCr2S4. However, the spinel peaks were displaced to higher angles with increasing

Jan 1, 1970

By J. Pinto, F. Galasso

THE current emphasis in preparing boron fibers by reduction of gaseous boron compounds on a resistively heated metal wire substrate has renewed interest in the borides of those metals which have relatively high melting points and are available as fine wires. A knowledge of the structures and properties of the borides, which are formed when boron diffuses into the metal core during boron deposition, can be of assistance in the understanding of the boron fiber formation process and the fiber properties. Many of these borides are well-known and their properties have been measured. However, when an unidentified boride is found in the core, it may be difficult to establish its composition because of the small amount of material available, the preferred orientation effects on the reflections in its X-ray pattern, and the possible overlap of X-ray reflections if several borides are present in the core. For example. the proper indexing of the X-ray pattern of WB4, which was formed in the tungsten substrate core during boron fiber formation, was accomplished only after small single crystals of this boride were grown and X-ray precession investigations were conducted.&apos; This note presents the results of a study of the phases formed in the core when tungsten, tantalum, and molybdenum metal wires were used as substrates in the boron fiber preparation process with particular emphasis on the identification and characterization of a higher boride of molybdenum analogous to WB,. Boron was deposited on resistively heated stationary 0.0012-in.-diam tantalum, tungsten, and molybdenum wires at 1050°C for various times up to 60 sec using boron trichloride and hydrogen as the reactant gases. After 60 sec of boron deposition the fibers were approximately 0.006 in. in diam. Examination of photomicrographs of fiber cross sections showed that the boron had diffused nearly to the center of the tungsten and molybdenum cores in 15 and 30 sec, respectively, and only halfway to the center of the tantalum core in 60 sec. X-ray diffraction photographs of the fibers indicated that it was also after 15 and 30 sec deposition times that the tungsten and molybdenum metal reflections, respectively, had disappeared from the X-ray patterns of the fibers. The patterns of the boron fibers produced using tantalum wire as a substrate showed that amorphous boron, TaB2, and tantalum metal were present after a few seconds deposition time and remained even after deposition times of 60 sec. Until a deposition time of 15 sec was reached, the tungsten substrate fibers contained amorphous boron,273 6WB, W2B5, and WB4 as well as tungsten metal, while the molybdenum substrate fibers contained amorphous boron, MoBa, Mo2B5, and molybdenum metal for deposition times up to 30 sec. Just before the molybdenum metal pattern disappeared, a pattern similar to that of WB, appeared, suggesting that a phase, MOB,, isomorphous with WB,, was present in the fiber. This same pattern was obtained from the product formed by heating a mixture of molybdenum metal and excess boron powder in a boron nitride crucible at 1960°C in an argon atmosphere. As was the case with the WBn pattern, this pattern could best be indexed on the basis of a hexagonal unit cell rather than the tetragonal unit cell Chrktien and Helgorsky reported for ~0~4,~ see Table I. The unit cell parameters for MoB4 were calculated to be a, = 5.214A, co = 6.358A. Assuming the space group P63/mmc and positions5 2M01 in 2b and 2MoII in 2c found for tungsten in WB~,&apos; a logical structure for MOB, was determined using geometrical considerations to place the boron

Jan 1, 1969

By Dwight H. Seely, Louis R. Records

A process for low-temperature dehydration of natural gas utilizing Joule-Thomson effect in expansion through a throttling orifice has been tested in a full-scale field installation. The results of these tests are presented in the form of performance curves from which the process may be easily evaluated. The effect of separation temperature on condensate recovery from the process is also shown. INTRODUCTION The transportation of natural gas from producing well to the consumer has always encountered the problem of hydrate prevention. This problem has become increasingly important in the past ten years due to the rapid increase in produced gas volumes, production pressures, transportation pressures and distance from producing wells to consumer. Natural gas, as normally produced from gas or gas-condensate wells, is saturated with water vapor at well-head conditions of temuerature and pressure. The solution of the hydrate problem require; but one basic process — dehydration of the gas to a water content which will result in a water dew-point below the minimum temperature to be encountered from the producing well to the point of consumption. Much of the recent development of gas and gas-condensate reserves in the Gulf Coast Area has been in locations which are accessible only by water. High well-head pressures, pipeline construction and maintenance costs and the desirability of final central gas-condensate separation facilities have stimulated the development of dehydration equipment which can be installed at each well and which will permit hydrate-free transportation of both gas and condensate in the same line to central facilities. There are four types of natural gas dehydration processes now used: 1. Adsorptive processes. 2. Absorptive processes. 3. Chemical reaction processes. 4. Refrigeration processes. The first three of these processes are indirect in that they require use of adsorbents, absorbents or reactive chemicals. These materials require regeneration and part of the total gas stream is consumed in the regenerative process. Indirect processes have a wide range of flexibility as defined by allowable operating pressure and temperature, but most are not easily adapted to automatic operation. The refrigeration process described in this paper was designed for installation at the producing well-head. It requires no regenerative cycle and with normal well-head temperatures no external source of heat. The flexibility of this process is limited only by the pressure drop which may be allowed between well-head and transportation line. THEORY There are three basic physical concepts involved in the low temperature dehydration process. These are: 1. Formation of hydrocarbon hydrates. 2. Joule-Thompson effect resulting from the expansion of gaseous mixtures through a throttling orifice. 3. The equilibrium composition characteristics of water vapor and gaseous hydrocarbon mixture.. The chemical composition and physical structure of hydrate; have been described by several investigators.3,4,5,10 Specific conditions of temperature, pressure and composition as well as the requirements for turbulence and presence of free water necessary for hydrate formation have been described by Katz.6 Natural gas hydrates, as they are found in plugged gas pipe lines, have the appearance of packed snow. The mass of these hydrates has low continuous porosity and permeability. Joule-Thomson effect. or the reduction in temperature which occurs when natural gas is throttled throusll a restrictive orifice, is the basic phenomenon which permits efficient use of refrigeration for the purpose of dehydrating natural gas. Joule-Thomson coefficients for gafeous mixture; of methane with ethane and with butane have been reported by Buder.-I~olzer, Sage and Lacey.2 Brown1 predicted temperature drops for pressure drops from enthalpy-entropy calculations. Aside from this work there were no fundamental data found which would be applicable to natural gas mixtures of varying spe-

Jan 1, 1951

By Dwight H. Seely, Louis R. Records

A process for low-temperature dehydration of natural gas utilizing Joule-Thomson effect in expansion through a throttling orifice has been tested in a full-scale field installation. The results of these tests are presented in the form of performance curves from which the process may be easily evaluated. The effect of separation temperature on condensate recovery from the process is also shown. INTRODUCTION The transportation of natural gas from producing well to the consumer has always encountered the problem of hydrate prevention. This problem has become increasingly important in the past ten years due to the rapid increase in produced gas volumes, production pressures, transportation pressures and distance from producing wells to consumer. Natural gas, as normally produced from gas or gas-condensate wells, is saturated with water vapor at well-head conditions of temuerature and pressure. The solution of the hydrate problem require; but one basic process — dehydration of the gas to a water content which will result in a water dew-point below the minimum temperature to be encountered from the producing well to the point of consumption. Much of the recent development of gas and gas-condensate reserves in the Gulf Coast Area has been in locations which are accessible only by water. High well-head pressures, pipeline construction and maintenance costs and the desirability of final central gas-condensate separation facilities have stimulated the development of dehydration equipment which can be installed at each well and which will permit hydrate-free transportation of both gas and condensate in the same line to central facilities. There are four types of natural gas dehydration processes now used: 1. Adsorptive processes. 2. Absorptive processes. 3. Chemical reaction processes. 4. Refrigeration processes. The first three of these processes are indirect in that they require use of adsorbents, absorbents or reactive chemicals. These materials require regeneration and part of the total gas stream is consumed in the regenerative process. Indirect processes have a wide range of flexibility as defined by allowable operating pressure and temperature, but most are not easily adapted to automatic operation. The refrigeration process described in this paper was designed for installation at the producing well-head. It requires no regenerative cycle and with normal well-head temperatures no external source of heat. The flexibility of this process is limited only by the pressure drop which may be allowed between well-head and transportation line. THEORY There are three basic physical concepts involved in the low temperature dehydration process. These are: 1. Formation of hydrocarbon hydrates. 2. Joule-Thompson effect resulting from the expansion of gaseous mixtures through a throttling orifice. 3. The equilibrium composition characteristics of water vapor and gaseous hydrocarbon mixture.. The chemical composition and physical structure of hydrate; have been described by several investigators.3,4,5,10 Specific conditions of temperature, pressure and composition as well as the requirements for turbulence and presence of free water necessary for hydrate formation have been described by Katz.6 Natural gas hydrates, as they are found in plugged gas pipe lines, have the appearance of packed snow. The mass of these hydrates has low continuous porosity and permeability. Joule-Thomson effect. or the reduction in temperature which occurs when natural gas is throttled throusll a restrictive orifice, is the basic phenomenon which permits efficient use of refrigeration for the purpose of dehydrating natural gas. Joule-Thomson coefficients for gafeous mixture; of methane with ethane and with butane have been reported by Buder.-I~olzer, Sage and Lacey.2 Brown1 predicted temperature drops for pressure drops from enthalpy-entropy calculations. Aside from this work there were no fundamental data found which would be applicable to natural gas mixtures of varying spe-

Jan 1, 1951