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By I. B. Cadoff, J. C. Bilello, R. Rosenberg

Diffiusion of magnesium into the surface of LiF crystals to controlled depths and subsequent heat treatments provided a wide range of surface zone harahesses and structure, The bend strength of the LiF crystals was increased by as much as an or-dev of magnitude. Ductility was achieved when dislocation generation occurred in the diffusion zone or when dislocations penetrated to the surface from the intevior. A critical surface hardness of 130 to 140 kg per sq mm was found helozu which generation could take place in the diffusion zone and ahoue which the zone was impenetrable, This hardness was obtainable by several methods, among them the aging of quenched MgF2 -LiF solutions to produce MgF, precipitation. Maximum hardness was ohtained in quenched specimens with no visihle evidence of MgF,. Diffusion-zone formation followed a parabolic rate law and an activation energy of 20.9 kcal per mole was obtained for the process. RECENTLY, the properties of ionic crystals as related to surface condition have been receiving much attention, specifically the transitions between ductile and brittle behavior. Originally Joffe 1 showed that NaCl crystals could be made ductile by immersion in water and related this to the elimination of surface microcracks. Aerts and DeKeyser 2 and Gorur 3' have subsequently shown that ionic crystals are inherently ductile and are embrittled through contact with air. Machlin and Murray4 hypothesized that a layer of NaCIO3 produced by contact of ozone with NaCl induced embrittlement by acting as a barrier to outward dislocation flow. westwood,' Rosenberg and Cadoff,9 and Bilello and cadoff' have reported surface strengthening of LiF crystals by coating with a magnesium compound and then heat treating for adherence. The major effect of the coat was to inhibit dislocation-slip lines from reaching the specimen surface. westwoods showed microcrack formation and fracture to be caused by slip-band interactions at the surface. The material presented in this paper is an extension of the work reported earlier by Bilello, Rosenberg, and cadoff'6,7 and illustrates the wide range of surface properties and bulk behavior obtainable by use of heat-treated magnesium-diffused surface regions in LiF crystals. EXPERIMENTAL PROCEDURE The LiF single crystals were obtained from the Harshaw Chemical Co. Some batch to batch variation was observed; therefore all specimens for a given test series were cleaved from the same crystal. The typical dimension used was 1 by 0.1 by 0.40 in. Surface damage resulting from cleavage was removed by chemically polishing in a 2 pct NH4OH solution. Each group of specimens was given a vacuum anneal at 700°C for 4 hr to provide a base standard for measuring comparative effects of various surface treatments. To produce the reacted surface zone, the annealed specimens were immersed in a boiling suspension of MgF, in doubly distilled HzO, agitated slbwly for 30 sec, removed, and dried at room temperature. Uniform coatings of MgF, were deposited with a thickness of approximately 5 mils. It should be noted that this technique can be modified for use with crystals which are soluble in water by using boiling absolute alcohol as the dissolving medium. This was found effective for the coating of NaCl with MgF2. The diffused surface zone was obtained by annealing the coated samples at elevated temperatures in a vacuum of lob4 mm Hg. Penetration depth was controlled by varying the annealing time from 1/2 to 28 hr. After heat treatment, the samples were tested for bend strength and hardness. Load was applied by four-point bending in a hard-beam testing jig. Four-point rather than three-point bending was used to provide a wide area of constant stress and to minimize the effect of localized inhomogenities in the specimen. The deflection rate was 8 x min-' and the distance between knife edges was 1/4 in. Load-time curves were obtained from a chart recorder coupled to the machine and converted to resolved shear stress on the shear plane vs deflection, as plotted in the figures. The unstressed portions of the sample outside of the two outer knife edges were used for the microhardness studies. Microhardness measurements were made with a Bergsman tester attached to a Reichert metallograph. All hardness impres-

Jan 1, 1964

By R. Bakish, M. A. Badiali, N. W. Kirshenbaum

One pound of ultra pul-e molybdenum has been produced containing both metallic and nonmetallic impuvities close to or less than the limits of detection. various purification methods were investigated; althouglz the use of move than one purification step was consideved, it was found that a single, caefully-controlled sublimation of MoCl5 yielded a highly puvified product without prior treatment or recourse to repeated sublimation. Hydrogen reduction of MoC1, to metal was attempted at atmospheric pressure; however, reduced pressure was necessary to obtain substantial yields. The tubular deposits of metal were consolidated into bulk fovm by electron beam melting undev high vacuum yielding a very low gas content. Boblems involved in monitoring the puvity of these materials and analytical results obtained are also presented. THE pronounced effect of even trace amounts of impurities upon fundamental properties of materials is well known to metallurgists and solid-state physicists. Consequently, groups interested in basic studies of metals have in recent years immensely stimulated the preparation and production of numerous ultra-pure metals. Increased demand by scientists for these high purity materials has necessitated development of facilities to prepare them in significant quantities; the procedures reported here were devised to produce significant quantities of ultra-pure molybdenum. Previous work performed in the field of vapor phase purification and hydrogen reduction of several other refractory metal chlorides had demonstrated valuable techniques applicable to molybdenum.' Various purification and reduction steps were individually investigated. Those procedures which showed the most favorable results with respect both to attainment of high purity and to ease of operation were then incorporated in the process utilized to produce the metal.' STARTING MATERIALS It is well known that because of differences in volatility, chlorides may be separated by fractional distillation. It was presumed that distillation of molybdenum pentachloride offered a simple and straightforward method of purification due to its relatively low boiling point. Alternatively, sublimation of the solid chloride also appeared feasible since MoC15 has both a reasonably narrow temperature range in which it exists as a liquid (a property typical of refractory metal chlorides) and a low enthalpy of sublimation. Pertinent thermochemical data of MoC15 are given in Table I. It should be noted that this compound must be handled with care as it is extremely hygroscopic. Anhydrous MoC15 was obtained from the A Metal Climax Co. METHODS OF PURIFYING MOLYBDENUM PENTACHLORIDE Distillation. It was expected that distillation methods, while affording an efficient purification, would prove simple to control and would have a higher production rate than sublimation processes. Also considered was the possibility of effecting a high degree of purification by using both these volatilization methods in conjunction—possibly a distillation followed by sublimation of the solidified condensate. Distillation of MoC15 was investigated using a single stage distillation column packed with chemically resistant glass beads. Heating coils were wound around the column and collection tube (condenser). As-received MoCl5 was charged into a flask connected with the column using a side loading arm under an argon flow. After the column and condenser were brought to about 270" and 210°C, respectively, the apparatus was lowered until the flask was fully immersed in a constant temperature fused salt bath maintained at about 285 °C. Distillation was continued for about 10 or 15 min until 50 to 70 g of distillate had been collected. Analyses of these distillations indicated that several elements, e.g., Cu, Fe, Ni, Cr, and Mg, were lowered in quantity although not all were removed to the same extent. The occurrence of Na, B, Si, and A1 in the distillates appeared to be due to contamination, possibly from corrosion of the pyrex glass. An improved distillation system of larger capacity and longer distilling column was built. Improvements were effected in lowering the amounts of such impurities as B, Mn, Ni, Na, Mg, Cr, Cu, and Fe. These studies were pursued concomitantly with efforts to purify by sublimation; it was subsequently found that although improvements in purity were obtained by distillation, sublimation processes were simpler to control and effected a high degree of purity.

Jan 1, 1963

By F. C. Langenberg, J. Chipman

New data on the distribution of silicon between slag and carbon-saturated iron at 1600oand 1700oC are presented which, in combination with previously published data, permit the determination of silica activities over a broad range of compositions in the CaO-Al2O3-SiO2 system. The distribution of silicon between graphite-saturated Fe-Si-C alloys and blast furnace-type slags in equilibrium with CO has been described in previous publications.1"3 In this past work the silica-silicon relation was established at temperatures of 1425" to 1700°C for slags containing up to 20 pct Al2O3. This paper presents the results of additional studies at 1600" and 1700° C which extend the silicon distribution data at these temperatures for CaO-A1203-SiO2 slags over a range from zero pct A12O3 to saturation with A12O3, or CaO.2A12O3. The upper limit of SiO, is set by the occurrence of Sic as a stable phase when the metal contains 23.0 or 23.7 pct Si at 1600" or 1700°C, respectively. The activity of silica over the expanded range is determined directly from the distribution data.3 Recently, 4-7 other investigators have studied the activities of SiO, and CaO, principally in the binary system, using different methods and obtaining somewhat different results. EXPERIMENTAL STUDY The experimental apparatus and procedure have been fully described in previous publications.1, 3 Six new series of experimental heats have been made, four at 1600° and two at 1700°C. Master slags of several fixed CaO/A12O3 ratios were pre-melted in graphite crucibles, and these were used with additions of silica to prepare the initial slag for each experiment. Slag and metal were stirred at 100 rpm and CO was passed through the furnace at 150 cc per min. The initial sample was taken 1 hr after addition of slag at 1600°C or 1/2 hr after addition at 1700°C. The run was normally continued for 8 hr at 1600°C or 7 hr at 1700°C, and the final sample was taken at the end of this period. Changes in Si and SiO2 content indicate the direction of approach to equilibrium, and in a series of runs where the approach is from both sides this permits approximate location of the equilibrium line. Fig. 1 shows the results of such a series of 15 runs at 1600°C for slags of CaO/Al2O3 = 1.50 by weight. Figs. 2 and 3 record other series at 1600°C and Fig. 5 a series at 1700°C with fixed CaO/Al2O3 ratios. The results of the experiments at 162003°C have been reported in part in a preliminary note.3 In the experiments recorded in Figs. 4 and 6, the slags were saturated with A12O3 (or with CaO.2A12O3 within its field of stability) by suspending a pure alumina tube in the melt during the course of the run. The final slag analyses were used to establish the liquidus boundaries8 in the stability fields of CaO.2Al,O3 and of A120,. ACTIVITY OF SILICA The free-energy change in the reaction has been calculated by Fulton and chipman2 from recent and trustworthy data including heats of formation, entropies, and heat capacities. The more recent determination by Olette of the high-temperature enthalpy of liquid silicon is in satisfactory agreement with the values used and therefore requires no revision of the result which is expressed in the equation: SiO, (crist) + 2C (graph) = Si + 2CO(g.) [1] &F° = + 161,500 - 87.4T The standard state for silica is taken as pure cristobalite and that of Si as the pure liquid metal. Since the melts were made under 1 atm of CO and were graphite-saturated, the equilibrium constant for Eq. [I] reduces to K1 = asi /asio2 The value of this constant is 1.77 at 1600°C and 16.2 at 1700°C. Through K1, the activity of silica in the slag is directly related to the activity of silicon in the equilibrium metal.

Jan 1, 1960

By J. O. Brittain, E. P. Lautenschlager, F. Felberbauer

This investigation was undertaken to evaluate the effect of a dispersed phase in a iron upon the strain hardening and the stress dependency of dislocation velocity as inferred from the strain-rate sensitivitv. Experiments were made in a-iron specimens with controlled amounts of carbon and/or A12O3. They were tested at various temperatures between 195' and 373 'K under a variety of conditions oj-concentration, strain rate, and quench aging. The resulting yield strength, flow strength, and strain hardening increased with addition of Al2O3. The parameter m, measured from changes in strain rate, was xsed to describe the stress dependency of the dislocation velocity. m was found to increase with additions of A12O3, increasing carbon in solution, and with increasing temperature. When applied to a recent model for yielding based upon dislocation multiplication and velocity characteristics, the values of m alone did not successfully predict yielding for the materials of this investigalion, but had to be adjusted with a consideration of the number of unlocked dislocations nucleated heterogeneously at discontinuities or inclusions. The change of yield strength with Al2O3 Interpar-ticle spacing appeared to obey a theory of Orowan. EVER since the concept of dislocations has been introduced to explain plastic deformation in crystalline materials, the origin of dislocations and the source of the number of dislocations required to account for plastic deformation have been persistent questions. Ruling out the possibility of homogeneous nucleation,' Gilman2 drew attention to the various cases of heterogeneous nucleation as the source of dislocations, whereas Frank and Read3 introduced the Frank-Read source. However, Gil-man found that the Frank-Read sources did not play a dominant role in the deformation of LiF crystals, but that small precipitates are often, if not always, associated with the nucleation of dislocations. In LiF crystals, however, most of the dislocations arose through the multiplication of moving dislocations in a mechanism described by Koehler4 and Orowan,5 Thus, relatively few precipitates could account for a large number of dislocations. A similar observation of dislocation nucleation at inclusions of precipitates was made by Stein and LOW' on Si-Fe crystals. Their crystals contained

Jan 1, 1964

By Anton Sawatzky, Erich Vogt

By means of mathematical solutions to the appropriate diffusion equations, we describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various temperatures and concentrations encountered in a heavy water moderated reactor. When the hydrogen concentration is below terminal solid solubility only the a Phase is present. Redistributions are then described in terms of the characteristic functions of the difhsion equation. For higher concentrations both the a and 6 phases are present. We assume the two phases to be always in equilibrium. For moderately small hydrogen concentrations exact solutions of the two-phase equation approach the the approximate solutions derived by Sawatzky and for all concentrations the exact solutions exhibit the qualitative features of his result: the two-phase concentration increases with time, everywhere; in the absence of a hydrogen current at the hot end of the sample an a-phase region always exists there; the interface of the a + 6 , a-phase boundary moves toward the cold md of the sample and the hydrogen concentration is discontinuous at the interface. Simultaneous solulions of the a and a + 6 hydrogen distributims and of the concomitant interface motion are obtained and compared to the observations of Sawatzky and Markowitz. The kinetics of the hydrogen diffusion process are shown to lead to m apparent heat of transport of the a phase which is lower than the actual value (even for samples with long anneals) thus resolving at least partially the disparity between experimental measurements of this quantity. A number of recent papers1"4 have reported measurements on the diffusion and redistribution of hydrogen in Zircaloy-2 under temperature and concentration gradients. These studies were instigated by problems arising from increasing use of Zircaloy-2 as a fuel element cladding material in pressurized-water power-reactors. The Zircaloy-2 picks up hydrogen during the operation of the reactor: the consequent precipitation of zirconium hydride in the Zircaloy-2 has pronounced effects on its mechanical properties. The Purpose of the present Paper is to describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various hydrogen concentrations and temperatures likely to be encountered in reactors. When the hydrogen in the Zircaloy-2 is entirely in the solid solution phase (a phase), the differential equation for thermal diffusion is well known and the redistribution can be described by standard mathematical methods some of which are given in Section 11 below. The treatment of the a + 6 (hydride) region differs from the earlier treatment of sawatzky3 by taking into account several modifications of the two-phase diffusion equations as suggested to us by Markowitz4 and Kidson.5 Even with the modifications the results obtained in our more complete treatment are substantially the same as those found by Sawatzky. As we show, the difference between the results of sawatzky3 and kIarkowitz4 is largely due to the difference in the geometry of their experiments. In the next section we derive the modified two-phase equation for arbitrary geometry. The exact solution of this equation is given in Section III for linear and cylindrical geometry. It is shown that Sawatzky's approximate solution is quite accurate for almost all the temperatures and hydrogen concentrations which are actually encountered. In Sawatzky's approximate theory the hydrogen concentration everywhere in the two-phase region increases continuously. As his paper pointed out, this result, together with hydrogen conservation, implies that in a sample with no hydrogen current flowing into the hot end a two-phase region is always accompanied by a single-phase region at the hot end of the sample. The net hydrogen gain in the two-phase region is supplied by the decrease of hydrogen in the single-phase region and by the movement of the (a, a + 6) boundary toward the cold end of the sample. Hydrogen conservation at the (a, a + 6) boundary leads to a discontinuity in the concentration and its derivative there. In Section IV it is shown how these qualitative features of the thermal diffusion kinetics arise from the simultaneous solution of the a-phase differential equation and a + 6 phase equation. Methods derived by us previously for the solution of the redistribution in both phases and the accompanying motion of the boundary are used to obtain approximate solutions valid for large times. The solutions account well for the observed redistributions of Sawatzky and Markowitz. It is shown how the continuing motion of the (a, a + 6) boundary leads to measured values of the heat of transport lower than the actual value, even for specimens with relatively long anneals.

Jan 1, 1963

By G. E. Keller, G. D. Coe

Several methods have been devised for rapid determination of sulfur in coal using a high-temperature combustion furnace. The fundamental principles of the various methods are similar but the techniques vary widely. The method described herein is no different in principle from some of its predecessors but varies considerably in technique. Originally devised to overcome the low-accuracy criticism leveled against the others, the tube-furnace method has proved successful for limited applications. Work is being done to widen the applicability of the technique. Subsequent to the work of A. Vita1 in 1920, a number of investigators have published data dealing with the rapid determination of sulfur in coal using a high-temperature combustion furnace.2-5 These, together with several unpublished methods, involve wide differences in technique although they are all similar in principle. Investigation of typical details of procedure showed that poor precision or accuracy could be attributed to one or more of the following: 1) inadequate quantity of sample to be representative, 2) a delivery tube temperature too low to confine condensation to a washable area of the tube, 3) no provision for back washing the delivery tube, 4) incomplete absorption of the sulfur compounds due to inadequate bubbler, and 5) the false assumption that all of the sulfur is evolved as sulfur dixoide. The method herein discussed is no different in principle from some of its predecessors; the differences are in technique. Although the method is rapid—a determination can be completed in 5 min— accuracy has riot been sacrificed in order to achieve speed. MATERIALS AND EXPERIMENTAL WORK Fig. 1 shows the arrangement of the equipment. A metered volume of oxygen is passed through calcium chloride for removal of moisture, then through Ascarite for removal of carbon dioxide, and thence through a glass tee to the feed end of the combustion tube. Connected to the side arm of the glass tee is a rubber tube that is closed with a pinch clamp during combustion of a sample. The products of combustion are expelled through a Vycor bubbler, the end of which is submerged 3 cm below the surface of a 1 pct hydrogen peroxide solution contained in a 300 ml high-form beaker. At the completion of the 4-min combustion period the contents of the beaker are titrated to a yellow end point, using a methyl red indicator, with 0.05 N sodium hydroxide (or sodium tetraborate). The pinch clamp on the tube leading from the tee in the oxygen line is then opened and mouth suction applied to draw the hydrogen peroxide up into the bubbler past the ell, almost to the rubber tube connecting the bubbler to the combustion tube. This washing of the bubbler is repeated until no further acid reaction with the indicator is obtained. The hydrogen peroxide-sul-furic acid solution is then titrated to the final yellow end point. Test work conducted at the Robena Laboratory disclosed the following critical conditions that had important bearing on the precision of the method: Weight of Sample: Several series of tests wherein the sample weight ranged from 0.1 to 0.5 g of -60 mesh coal showed that the lowest variance (standard deviation squared) resulted from the use of 0.5-g samples; the variance was slightly greater when 0.3-g samples were used, and with less than a 0.3-g sample weight the variance increased rapidly with decrease in weight. Although the use of a 0.5-g sample invariably resulted in a very slight explosion as soon as the sample entered the hot zone of the combustion tube, this did not detract from the precision of the method. Temperatures: Mott and Wilkinson5 found that a combination of low temperature (1250°C) and low oxygen flow rate (less than 700 ml per min) tended to give high results due to formation of oxides of nitrogen. Although the method herein employs a much higher oxygen rate than 700 ml per min, as an additional precaution to assure accurate results, 1315°C (2400° F) is recommended as the most desirable furnace temperature. The temperature of the elbow of the bubbler should be at least 75°C to minimize condensation

Jan 1, 1961

By K. H. Coats

This paper describes an approximate technique for handling the problem of percolation of evolved gas upwards through the oil column in computer simulation of natural depletion. This technique has been incorporated into a general model for simulating three-phase flow in one, two or three dimensions. The mathematical model for perfonning these calculations is described in detail in a separate article. 1 While vertical gas percolation occurs during natural depletion in a reservoir of any configuration, it is especially pronounced in the pinnacle reel or bioherm. The reel may have an areal extent less than one section with a thickness of up to 800 It. The upward percolation of evolved gas often limits the time step in calculations as little as one day. Using this small time step, computer expense for a single 30- to 40-year simulation on even a one-dimensional basis has exceeded 92,000. The method described here for handling the percolation allows time steps of 60 days or more (depending on reservoir size and production rate), resulting in a considerable reduction in computing expense. The method also allows calculations in which secondary gas caps build up in tight zones of the oil column below the main gas cap. The validity of the method is indicated in connection with an example pinnacle reef field. Calculated results using a 2-day time step (where the method in question is not needed and not invoked) are compared with results using the method and a 60-day time step. The comparison shows good agreement. Results from one- and two-dimensional simulations of the reef are presented along with the corresponding computing times on the CDC 6600 computer. A three-dimensional simulation was also performed and the required computing time is given. INTRODUCTION A general analysis for simulating three-dimensional, three-phase flow in reservoirs has been developed. 1 In applying this model to reservoirs undergoing natural depletion, a time-step restriction was encountered due to the flow of evolved gas upwards through the oil column and toward the gas cap. A remedy for this problem has been incorporated in the analysis and is described here. The time-step restriction is encountered only in calculations which include flow in the vertical or near vertical direction. The restriction occurs to some extent in reservoirs of any geometrical configuration, but it is especially pronounced in the pinnacle reef or bioherm where the ratio of thickness to areal extent is unusually large. This paper describes the problem, a method of handling it, incorporation of the method in the three-dimensional, three-phase model, and, finally, a test of the method's validity in an application to an example pinnacle reef reservoir. THE PROBLEM During the early stages of reservoir depletion, pressure falls below bubble point in progressively lower regions of the oil column. Continuing production results in evolution of dissoived gas throughout the oil column. This gas then percolates upwards toward the top of the reservoir. If the gas encounters a sufficiently low permeability zone in its travel upward, then it can accumulate and form a secondary gas cap. If no zones are encountered which are tight enough to hold gas against the gravity forces, then the gas travels on until it reaches the top of the sand or the main gas cap. Numerical simulation of multiphase flow in reservoirs is generally performed with time steps such that the flow of a fluid into or out of a block in one time step is a fraction (considerably less than one) of the total amount of that fluid present in the block. Use of a time step where the time step's

Jan 1, 1969

By H. H. Podgurski, H. E. Knechtel

Annealed Fe-Al alloys do not react readily to form AlN when held at 500ºC in NH3-H2 gas mixtures, but do so upon the introduction of dislocatims. Nuclea-tion of the nitride phase occurs on dislocation sites. In turn, the growth of the aluminum nitride particles causes the ferrite phase to yield plastically, generating more dislocations for the nucleation process. The nitride phase extracted from an Fe-2 pct A1 alloy nitrogenated at 500°C was identified as stoichio-metric aluminum nitride with a hexagonal crystal lattice. THIS investigation reveals the role that dislocations play in initiating and sustaining the nitriding reaction in Fe-A1 alloys. As early as 1931 the work of Meyer and Hobrock1 suggested that the initiation of the nitriding reaction could involve a nucleation controlled process. Recently Bohnenka2 depicted the gas-phase nitriding process below 600°C as one of mixed control limited by nitrogen penetration through the surface, by nitrogen diffusion, by aluminum diffusion, and by nucleation of the nitride phase, Fig. l(a). In our research in a comparable alloy (0.57 pct Al) at 575ºC, we have observed a nitrogenation which we feel is better described by Fig. l(b). In the case of a 2 pct-A1 alloy partially nitrided at 500°C we propose the profiles shown in Fig. l(c). For a complete and accurate description of the process, a concentration profile of the dislocation density in the test specimen would be needed. EXPERIMENTAL Nitrogenization was conducted between 500" and 575°C in a variety of NH3-H2 gas mixtures on three Fe-A1 alloys: 1) zone-refined iron + 0.16 i 0.2 pct Al—levita-tion melt, 2) zone-refined iron + 0.57 0.02 pct Al— levitation melt, 3) plastiron + 2 pct Al—melted by induction heating. To demonstrate the effect of dislocations on reactivity, both cold-worked and annealed samples were investigated. All nitrogenation rate studies were conducted gravimetrically with a gold-plated invar balance4 contained in a gas-flow system. To avoid contamination of the specimens in the reaction zone of the system, the reaction chamber was constructed of high-purity dense alumina. The activity of nitrogen was fixed by specific NH3-H2 gas mixtures whose compositions were continually monitored by calibrated thermal conductivity gages and checked by chemical analysis. Variations of ± 0.1 pct NH3 could easily be detected by both methods. Throughout this paper the activity of nitrogen is defined as PN3 /PH23/2 , where PNH3, and Ph2 are partial pressures in atmospheres. Electron transmission, density measurements, and chemical analyses were made on specimens before and after nitrogenating in order to reveal structural and chemical changes. Similar studies as well as X-ray diffraction studies were conducted on nitride extractions from the nitrogenated 2 pct-A1 alloy. These extractions were obtained by the use of an anhydrous bromine-methyl acetate solution which dissolves the iron and leaves the insoluble nitrides as a residue. Hardness profiles were obtained on cross-sections of partially nitrided specimens to demonstrate the extent of nitriding through the thickness of the specimens. RESULTS AND DISCUSSION The nitrogen activity in the NH3-H2, atmospheres was never allowed to reach a level capable of producing iron nitride (Fe4N). Hence, the term nitriding as used in this paper refers only to the formation of aluminum nitride whereas nitrogenation refers to the total uptake of nitrogen regardless of how it is distributed throughout the alloy. The weight increases observed during the initial stage of a nitrogenating treatment are due primarily to the solution of nitrogen in the ferrite phase, particularly when starting with annealed specimens. Because this initial nitrogenation rate in the case of the 0.57 pct A1 alloy, see Figs. 2 and 3(a), was most rapid the weight change that occurred thereafter might be attributed to the nitriding reaction with the exception of a small weight increment due to the irreversible pickup of oxygen by aluminum. The oxygen (<70 ppm) came from traces of H2O and 0, in the hydrogen and ammonia gases. On the basis of discrepancies between total weight increase and the increase in the nitrogen content of the sample as determined by chemical analysis, it was estimated and later established by activation analysis, that as much as 200 ppm of oxygen were taken up by a fully nitrided Fe-0.57 pct A1 specimen at 575°C. Most of the oxygen could have been picked up from the nitriding atmosphere on the surface of the samples during cooling to room temperature. Even 50 ppm of water in the gas phase will become oxidizing to iron before the sample has cooled to room temperature. The lack of reactivity* of these alloys in the annealed

Jan 1, 1970

By Jr. W. L . Phillips

The deformation and fracture characteristics of lithium-fluoride single crystals stressed in compression at room temperature have been studied. In as-cleaved specimens the stress-strain curves were variable; two types of {110} fractures were observed in the vicinity of kink bands. The stress-strain curves of annealed crystals were reproducible; {100} cracks formed which propagated along the (100) and (110) planes. The deformation and fracture characteristics were affected by quenching and X-ray irradiation. STUDY of the mechanical behavior of nonmetallic materials has received considerable impetus in recent years because of the need to overcome the problem of brittleness before the refractory properties of nonmetallics can be fully exploited. Ionic crystals provide a convenient and simplified starting point from which to study the deformation and fracture processes in nonmetallic materials. Early investigations of the mechanical behavior of non-metals were restricted largely to determinations of the crystallographic indices of the cleavage and fracture planes and the glide and twinning elements. Until recently, only occasional systematic studies of the deformation characteristics of non-metals have been made; and investigations of the forces necessary to initiate plastic deformation and the factors which affect the flow characteristics have been restricted largely to studies of sodium chloride&apos;-7 , magnesium oxides-l3 and lithium fluoride. 14-22 Fracture studies on alkali halide and metal oxide single crystals have been limited despite the fact that these materials have a number of advantages for fracture studies. Because they are transparent, the cracks which form can be viewed in three dimensions instead of in two dimensions as in metals. Also, they exhibit stress birefringence under polarized illumination, which enables the internal stress pattern and, therefore, the distribution of dislocations to be examined in the vicinity of the fracture. Early workers1-4 have shown that ionic crystals with a cubic structure fracture in tension along the (100) plane normal to the applied stress. These fractures were brittle at room temperature and propagated very rapidly across the cross section of the crystal. More recently, Stokes, Johnston, and Lil0 have studied crack formation in compressed magnesium-oxide single crystals. They found that the cracks, which were observed after about 3 pct strain, formed in the region of a kink band and lay on conjugate (110) slip planes instead of the usual(100) cleavage plane. Two different types of cracks were noted: stroh23 and secondary. The Stroh cracks did not exist merely on the surface but extended through the specimen in the form of tiny slits. A secondary

Jan 1, 1962

By S. H. McFarlane, K. H. Zaininger, G. W. Cullen, C. C. Wang, G. E. Gottlieb

Heteroepitaxy of silicon on stoichiometric spinel has been studied. Both boron-doped (p-type) and arsenic-doped (n-type) single-crystal silicon films have been grown by the pyrolysis of silane on sioichiometric spinel (MgAl2O4) substrates prepared by a flux technique. The spinel crystals are free from strain and subgrains, and exhibit no thermal instability at temperatures employed for silicon deposition. The growth parameters of epitaxial silicon have been studied. Effects of substrate orientation, surface preparation, and growth conditions on the silicon Properties have been determined. The silicon-spinel composite was characterized by X-ray diffraction, electron diffraction, electron microscopy, and optical techniques. Information on epitaxial orientation relationship, defect structures and film-substrate interface has been obtained. A parallel orientation relationship was found between silicon and spinel. The silicon films exhibit no subgrain structures. However, growth pyramids, microtwins, stacking faults, and dislocations are the prevalent defects. The deformation of epitaxial silicon was measured by an X-ray technique. It was found that the epitaxial silicon is strained under compres-sive stress due to the thermal expansion difference between the film and substrate. The stress was estimated using the classical plate theory and beam equation. Electrical properties of the epitaxial silicon have been measured, including resistivity, carrier concentration, and Hall mobility. MIS and vertical through diffused junction structures have been fabricated wing silicon-spinel composite. Information on MIS characteristics, minority carrier life time, and junction properties has been obtained. THE achievement of single-crystal growth of large area silicon semiconductor films on oxide insulating substrates is of technical importance to many solid state electronic devices. The semiconductor-insulator composite structure is also of scientific interest because the heteroepitaxy is determined by the spatial relationship between the atomic arrangement in the substrate and that of the atoms in the appropriate crystallographic plane of silicon. The degree of crystalline perfection of the silicon deposits depends also on the physical condition of substrate surface. Epitaxial growth of silicon on commercial flame fusion Al-rich spinel (MgO:3.3A12O3) has been reported by several investigators.&apos;-4 The lattice of spinel of this composition is distorted. The material cracks and exsolves the excess alumina in the lattice at temperatures (-1200°C) used in fabricating silicon devices. Stoichiometric MgA12O4 spinel exhibits neither lattice distortion nor thermal instability. Results are given on the epitaxial growth and characterization of silicon on stoichiometric spinel. EXPERIMENTAL Fabrication of Silicon-Spinel Composite Structures. The MgA12O4 spinel substrate wafers were prepared from bulk single crystals grown at about 1200°C by a flux technique5 using a PbF2 flux. The crystals are free from strain and subgrains, and exhibit a typical dislocation density of less than 50 lines per sq cm. The crystals are thermally stable without cracking and exsolution of alumina to at least 1500°C. The spinel crystals were oriented for cutting by the Laue X-ray back-reflection method.6 Substrate wafers (about 25 mil thick) of (Ill), (loo), and (110) orientations have been obtained bu cutting the X-ray oriented crystals using a standard type diamond wheel. An accuracy of better than 1/2 deg is maintained throughout the operation. The spinel substrate wafers were mechanically lapped and polished to produce the flat and smooth surface which is required for silicon epitaxy. Lapping was carried out with about 30-µ boron carbide abrasives to obtain a flat coplanar surface. The lapped surface was further polished using successively finer grades of alumina, ending with the 0.3-µ grade. After polishing the wafers generally have a flatness of ±0.4 µ per cm, as revealed by interferometry. Fig. 1 shows (111) oriented MgA12O4 spinel wafers of various shapes.

Jan 1, 1970

By Morris Cohen, Robert C. Ruhl

Fe-Ni-B alloys were inresligated by X-ray diffraclion after splat quenching. Although this rapid cooling did not produce a measurable supersaturation of dissol1ed boron in either binary Fe-B or Ni-B alloys, a marked increase in dissolved boron was achieved by the splal quenching of lernary Fe-Ni-B alloys. Boron additions up to 2.0 wl pcl to Fe-13Ni and Fe-24Ni alloys cause an increase in retained austenite from 0 to 59 pet and to 92 pet, respectively. The martensitic phase in the Fe-13Ni-9 at. pct B alloy is .found to conlain about 0.6 at. pet interstitial boron, as evidenced by the tetragonality of this phase, and about 3.6 at. pct substilutional boron, us deduced from the lattice paratrieler decrease, the balance of the boron being precipitated as (Fe,Ni)aR. The austenitic Fe-Ni-B plznses also contain both interstitial and substitutional boron. Iron-Boron System. The phase diagram and related information about the solid solutions and intermediate phases in the Fe-B system are given by ansen,&apos; Elliott.2 and Pearson.1 The equilibrium solid solubility of boron in both ferrite and austenite is quite small: the maximum solid solubility of 0.02 wt pct B (0.11 at. pct B) occurs in iron at the eutectic temperature of 1150°C. while the maximum solubility in a iron is less than 0.01 wt pct.l There is disagreement in the literature as to whether these solid solutions are substitutional or interstitial. Based on the measured activation energy of boron diffusion in iron, it appears likely that boron moves interstitially in austenite. 4 However, this observation does not rule out the possibility that some of the dissolved boron may also occupy substitutional sites in this phase. Investigations of internal friction of boron in iron have suggested that boron is interstitial there.&apos; Shevelev, 5 on the other hand, reports a decrease in the ferrite lattice parameter with dissolved boron content, thus indicating a substitutional solution. Unfortunately. Shevelev&apos;s methods and analysis are unclear. Goldhoff and spretnak6 have measured the lattice parameters of pure iron and an Fe-0.005 wt pct B (0.027 at. pct) alloy at both room temperature (ferrite) and from 920° to 1200°C (austenite). They reporte: a lattice contraction in the ferrite of 0.0003 ± 0.0002 due to boron, thus indicating a predominately substitutional solution. Appreciable (0.0010 to 0.0060) lattice contractions were found in boron-containing austenites, but these effects were much larger than could be accounted for by the substitutional solution of all the boron present. Nickel-Boron System. Elliott 2 gives a summary of thephase diagram and recent work on this system. The solubility of boron in nickel reaches a maximum of 0.03 wt pct at the eutectic temperature of 1080°C. Iron-Nickel System. ansen&apos; presents the equilibrium diagram for this system and also discusses the metastable austenitic and martensitic phases along with the a=? transformations. The lattice parameters of Fe-Ni ferrites have been recently redetermined by Abrahamson and Lopata.7 Their data, Fig. 1, show an unusual change in slope at about 1.7 at. pct Ni. Very few measurements of the lattice parameters of Fe-Ni martensites are available in the literature. The values of Roberts and Owen8 are considerably higher than those measured in the course of the present work: they find that a, is constant at 2.874? from 8 to 30 at. pct Ni. Both the slope change in the ferrite parameters and the occurrence of a maximum plateau in the marten-sitic lattice parameters vs composition denote the

Jan 1, 1970

By J. D. Price, G. V. Woody

MANY producers of by-product coke have spent considerable time and given considerable thought to the use of a substitute for low-volatile coal as an admixture with high-volatile coking coal for charging high-temperature by-product coke ovens. Generally speaking, there are two principal reasons for this, one being occasioned by the lack, in certain localities, of low-volatile coal delivered at a cost sufficiently low to permit its use, and another being the desirability of finding a substitute product with a delivered cost lower than the cost of the low-volatile coal. It was for the first of these reasons that the Colorado Fuel and Iron Corporation was particularly interested in this subject. This paper deals with the experimental work and the results obtained by that company in producing and using low-temperature char. OVERCOMING DEFECTS IN COKE FROM COLORADO COALS Colorado coking coals are all of the high-volatile type and were all laid down during he Cretaceous period, which makes them something like 80 million or so years younger, geologically, than eastern coals. They behave, when coked alone, something like the Pittsburgh-seam coals. They make a very brittle, highly cross-fractured, fingery coke of fair shatter value but quite low in resistance to abrasion. Mixed with a low-volatile coking coal such as Pocahontas or certain Oklahoma coals, they make a coke that is equal to virtually any of the eastern cokes. The inferior quality of Colorado coke has long been recognized, and a considerable amount of time, effort and money has been spent upon investigations of means for improving its physical properties. While it has been found that some improvement in quality of coke can be secured by the adjustment and control of such variables as pulverization, moisture content, oven temperature and bulk density of charge, and through the addition of certain inert materials such as pulverized coke breeze, pitch, high-volatile noncoking or semicoking coal, the benefits so gained have been comparatively small. There are no low or medium-volatile coking coals available within a reasonable freight-cost distance. Therefore a substitute for low-volatile coal was developed through low-temperature carbonization-or, more correctly speaking, through the partial devolatilization-of high-volatile coals. The blending of this lower volatile char with the high-volatile coking coal distinctly improves the quality of coke made from Colorado coal. There is nothing especially new about this idea. In 1908 a Japanese patent was taken out by Kotaro Shimomura, whose claim was: The method of making a nonfingery coke out of bituminous coals, without using natural coals of low-volatile matter; according to which a certain coal is heated at a temperature between about 300°C. and about 600°C. so as to leave about 15 to 25 per cent volatile matter in the coal; this coal is mixed with the

Jan 1, 1944

By J Price, M. R. Geer, H. F. Yancey

COAL mine operators recognize coal as an abrasive material, because the wear of drilling, cutting, and conveying equipment is reflected as a cost item for replacement of parts. Similarly, industrial consumers of coal experience abrasive wear on all coal-handling equipment. Operators of pulverized fuel plants are doubtless most keenly aware of the abrasiveness of coal, because under the high contact pressures developed between coal and metal in pulverizers, abrasive wear is increased many fold. Moreover, experience in operating pulverized fuel plants has demonstrated that some coals are much more abrasive than others. Hardgrove&apos; stated that maintenance costs entailed by the wear of grinding elements is often a more important variable than the cost of the power required to pulverize different coals. Craig2 also reports that one coal may cause pulverizer parts to wear several times faster than another. It is apparent, therefore, that those concerned with pulverizing coal could profitably employ a method for estimating the abrasiveness of different coals, just as they utilize standard tests for thermal value, grindability, and ash-fusion temperature to assist in selecting the most suitable and economical coal to use in a particular plant. The objective of this investigation was to develop a test procedure that would be suitable for general use in estimating the abrasiveness of coals. However, few, if any, of the standard tests now used for evaluating the properties of coal are the product of a single investigation or the result of a single investigator&apos;s efforts. Rather, in each case, a testing procedure was devised by one investigator, used by others on a wider variety of coals, and finally refined completely as the result of the joint efforts of a number of interested people. Thus, the test procedure for estimating abrasiveness developed in the course of this work may not be refined sufficiently in its present form for general use, but it may serve as the starting point from which an acceptable test procedure can be developed. The method has been used thus far on only about a dozen coals, and there has been no opportunity to attempt a correlation between experimental results and actual plant experience. Only wider use of the procedure by other investigators and correlation with plant experience can determine to what extent the method will have to be modified to render it suitable for general application. Test Method Although the literature contains no record of an attempt to devise a method for estimating the abrasiveness of coal that could be used industrially, several investigators have tested properties of coal that are closely related to its abrasiveness. The abrasiveness of a material generally is considered to be related to its hardness, and hardness tests for coal have been employed by Heywood,&apos; O&apos;Neill," and Mathes. Also, the resistance of coal to abrasion, a property that presumably is related to the abrasiveness of coal, was measured by Heywooda and by Simek, Pulkrabek, and Coufalik.2 11 these investigators tested only individual pieces of coal. Since coal is a heterogeneous material having components of varying properties, tests of this type can yield results having little more than academic interest. Only a test method that utilizes a representative sample of coal can give results that are useful industrially. The abrasion tests used for various other materials have been considered for adaptation to testing the abrasiveness of coal. The tests used for metals,7-9 paving and flooring,&apos;" and rubber," cannot be used because coal is not sufficiently abrasive.~ The present experimental work was begun before World War II and was conducted by three research fellows"&apos;" working under a joint agreement between the University of Washington and the Bureau of Mines. After a great deal of preliminary work with a variety of apparatus and materials, a test procedure was developed which consisted of rotating a test disk 2Yz in. diam in a steel mortar containing the coal sample. The shaft carrying the test disk at the lower end and a 100-lb load on the upper end was free to move vertically. The bed of coal in the mortar was kept fluid by low-pressure air admitted through a port near the bottom of the mortar. Measurable wear on an Armco iron disk could be obtained in this test procedure, but, despite extensive efforts to eliminate them, several major disadvantages remained in this test method. First, with most coals the amount of wear on the iron disk did not exceed a few milligrams. Second, a single type of disk was not applicable for all coals. A smooth iron disk gave satisfactory results with both bituminous and sub-bituminous coals, but hardly any wear with anthracite or coke. A disk having studs or projections gave more satisfactory abrasion losses with anthracite and coke and presented no operating difficulties with free-burning bituminous and sub-bituminous coals. It could not, however, be used with caking coals because these coals formed a

Jan 1, 1952

By R. C. Craze

This paper discusses the characteristics of the velocity logs now available to the petroleum industry, and some of their advantages and limitations. The velocity log was designed as an aid to the geophysicist to determine velocity layering in the earth and to provide fast, accurate and economical vertical travel time data. After a number of logs had been made, studies were carried out on their use ia correlating strata in adjacent wells. It was found that adjacent strata usually show sufficient velocity contrast to make it possible to correlate these from well to well, even in areas where electric or radioactive logs fail.&apos; In addition, velocity logs have been useful in the determination of porosity and thickness of reservoir rock.&apos; These uses for velocity logs require an understanding of the characteristics of the log in response to the changes in velocity and in borehole conditions encountered normally in logging. GENERAL DISCUSSION OF INSTRUMENTATION The measurement made in velocity logging is more accurately described as a measurement of time rather than velocity. Ideally the log is obtained by measuring the length of time required for compressional sound waves to travel through a fixed distance in the formation. In practice, the time measurement may be made accurately but the distance through which the waves have traveled may vary slightly. Changes in borehole diameter are responsible largely for the difficulty in maintaining a fixed distance, especially if the diameter variations are so abrupt and frequent that the borehole instrument cannot follow contours of the hole. Several service companies have velocity logging equipment available or under development which have different transmitters, receivers, and measuring systems. While these differences are important, there are actually only two systems in use at the present time (Fig. I)."&apos; The first system initiates a pulse at a trans-mitter and detects it at a single receiver. The transmitter and receiver are separated by a fixed distance, called the spacing. The time measured is that between the initiation of the pulse and the first arrival of acoustical energy at the receiver. The second system uses two receivers and a transmitter. The receivers are separated by a fixed distance and the time between arrivals of energy at the two receivers is measured. Here, the spacing is the distance between receivers. The two systems have much in common for it is possible to record both logs simultaneously. Usually the transmitter is an electro-mechanical transducer which produces discrete

By Albert A. Smith

The creep properties of metals have assumed increasing importance in recent years and many investigations have been made on various phases of the problem. In the past year the annual lectures of the Institute of Metals Division1 and the Iron and Steel Division2 were concerned with this subject, and are excellent reviews. For many years the creep properties of lead and lead alloys have been investigated at the Central Research Laboratories of the American Smelting and Refining Co., and it is hoped that the present paper will contribute knowledge of some of the factors that influence creep. Lead, being a metal that recrys-tallizes readily at room temperature, is an excellent material upon which to investigate creep phenomena because of the simplicity of the apparatus needed, and it might be expected that results would apply to some extent to elevated-temperature tests of other metals. Material The creep tests of this investigation were all made on high-purity lead (99.9998+ Pb) in which the only impurity that could be detected by spectrographic and chemical means was approximately 0.0001 per cent Fe. Flat strips, 0.750 in. wide by 0. 100 in. thick, were prepared by extruding 2-in. dia. cast billets at a temperature of 250°C. This gave a material of 2 to 3 mm. average grain size with a tensile strength of j.400 lb. per sq. in. when tested at a straining rate of 5 per cent per minute. With this extremely soft material, great care was necessary in handling the specimens, to avoid distortion and subsequent recrystallization. The creep tests at 30°C. were conducted in a constant-temperature room, specially built for the purpose in the basement of an office building in which there was no moving machinery, and no vibration was detectable under the most severe conditions of shock in the adjacent surroundings. The room was well insulated and heated electrically, control being by means of a de Khotinsky regulator operating a relay. Maximum temperature variation over a period of several years has been ± 1/2°C. Specimens of the extruded strip, 16 in. long, were used for test purposes with no reduced gauge section, thus eliminating any distortion due to machining. The method of clamping and supporting the specimens is shown diagrammatically in Fig. 1. The gauge marker for the measurement of extension consisted of an aluminum strip, 0.050 in. thick by 0.75 in. wide, one end of which was ground and sanded to a precise knife-edge and fastened to the specimen by suitable pins. After the strip was fastened in place a fine scratch was inscribed just below the knife-edge by means of a sharp teasing needle. Just below this gauge scratch a short vertical mark was made so that the same point could be located and read each time. Several hundred specimens have been prepared by this method, and it was found that with experi-

Jan 1, 1941

By G. H. Bruce, C. E. Williams

The trend toward deeper drilling, together with the attcndant increase in power requirements for circulation of the drilling fluid, has emphasized the need for a critical examination of the factors affecting the removal of bit cuttings from the hole by the drilling fluid. The ability of drilling fluids to lift cuttings is called their carrying capacity. A series of laboratory and field experiments has been conducted to determine the minimrim annular velocity necessary to remove cuttings, and to investigate the effects of properties of drilling fluids on their carrying capacities. Consideration of the results of these experiments led to the following conclusions: 1. Turbulent flow in the well annulus is most desirable from the standpoint of cutting removal. 2. Low viscosity and low gel are advantageous in removing cuttings. 3. Increase in mud weight is effective in increasing carrying capacity. 4. The carrying capacity is higher when the pipe is rotated than when it is not. 5. If turbulent flow can be maintained, an annular velocity slightly higher than the slip velocity of the largest cuttings to be transported should keep the bore hole clean. This implies velocities of 100 to 125 ft per minute rather than the presently used 175 to 225 ft per minute. INTRODUCTION Power Savings by Reduction of Annular Velocities A large portion of the power expended in drilling operations is consumed in circulating the drilling fluid. An important factor in establishing the rate of mud circulation is the minimum velocity in the annulus necessary to remove bit cuttings. Empirically, it has been found that average annular mud velocities of about 200 ft per minute will remove cuttings. It was not definitely known, however, whether annular velocities of about 200 ft per minute were just above the minimum necessary to remove cuttings, or whether such velocities could be materially reduced without sacrifice of the ability of the mud to remove cuttings. It is apparent that if annular velocities could be reduced without impairment of cutting removal, a considerable saving in power requirements would result. Need for Research on Carrying Capacity The ability of a drilling fluid to transport cuttings is called its carrying capacity. Although it has been recognized that the carrying capacity of a mud is affected by mud properties such as viscosity and density1,2,3,4 there have been various views in the industry as to the effects of these mud properties on carrying capacity. The economic importance of the problem of carrying capacity and the scarcity of information on the subject indicated that research on the problem was needed. THE FACTORS AFFECTING CARRYING CAPACITY Qualitative Determination of Factors The mechanism of cutting transport is closely related to that involved in the separation of material by settling processes. A considerable amount of research has been done on settling problems, and discussions of sedimentation theory can be found in standard texts.5,6 Consideration of the information available from these sources, together with consideration of the mechanism of cutting transport, leads to the conclusion that the factors affecting carrying capacity are the dimensions of the system, the physical properties of the cuttings. and the physical properties of the drilling fluid. system Dimensions and Their Effect The dimensions of the fluid circulating system of importance to carrying capacity are the bore hole size, drill pipe size, pump capacity, and pump speed. These dimensions determine the annular velocity of the drilling fluid. Physical Properties and Their Effects The physical properties involved in the interaction between mud and cuttings are the density and shape of the cuttings and the density, viscosity and gel strength of the drilling fluid. The effect of the density factor on carrying capacity is fairly obvious; high density difference between cuttings and fluid results in a low buoyant force and therefore decreases carrying capacity. The effect of cutting shape is less obvious. Although

Jan 1, 1951

By Frank G. Miller

This report presents developments of fundamental equations for describing the flow and thermodynamic behavior of two-phase single-component fluids moving under steady conditions through porous media. Many of the theoretical considerations upon which these equations are premised have received little or no attention in oil-reservoir fluid-flow research. The significance of the underlying flow theory in oil-producing operations is indicated. In particular, the theoretical analysis pertains to the steady, adiabatic, macroscopically linear, two-phase flow of a single-component fluid through a horizontal column of porous medium. It is considered that the test fluid enters the upstream end of the column while entirely in the liquid state, moves downstream an appreciable distance, begins to vaporize, and then moves through the remainder of the column as a gas-liquid mixture. The problem posed is to find the total weight rate of flow and the pressure distribution along the column for a given inlet pressure and temperature, a given exit pres5ure or temperature and given characteristics of the test fluid and porous medium. In developing the theory, gas-liquid interfacial phenomena are treated. phase equilibrium is assumed and previous theoretical work of other investigators of the problem is modified. Laboratory experiments performed with specially designed apparatus. in which propane is used as the test fluid, substantiate the theory. The apparatus. materials and experimental procedure are described. Comparative experimental and theoretical results are presented and discussed. It is believed that the research findings contributed in this * paper should not only lead to a better understanding of oil-reservoir behavior, but also should be suggective in regard to future research in this field of study. INTRODUCTION In recent years much time and effort has been consumed in both theoretical and experimental studies of the static and . dvnamic behavior of oil-reservoir fluids in porous rocks. Although lack of sufficient basic oil-field data, principally concerning the properties and characteristics of reservoir rocks and fluids, largely precludes quantitative application of research results to oil-field problems, qualitative application has become common practice. In effect. oil-reservoir engineering research is serving as a firm foundation for oil-field development and production practices leading to increased economic recoveries of petroleum. This province of research. however, still poses many perplexing problems. The thermodynamic behavior of two-phase fluids moving through porous media constitutes one facet of reservoir-fluid-flow research that has not received the attention it deserves. This report embodies a theoretical discussion of this subject and a description of a series of related laboratory experiments. The significance of the problem to oil field operations is indicated but in articular the report centers around a theory and method for analyzing the steady. macroscopically linear, two-phase flow of a fluid (a single molecular species) through a horizontal column of porous medium. For simplicity in showing how the thermodynamic behavior of two-phase fluids moving through porous media affects oil-reservoir performance problems, attention is focused temporarily on a particular well producing petroleum from an idealized water-free solution-gas drive reservoir, the reservoir rock being a horizontal, thin, fairly homogeneous sandstone of large areal extent confined between two impermeable strata. The flowing hydrocarbon fluid is considered to exist entirely as a Iiquid at points in the reservoir remote from the well; however. the decline in fluid pressure in the direction of the well causes vaporization of the hydrocarbon to begin at a radial distance r from the well. Upstream from r the fluid moves entirely as a liquid and downstream from r it moves either entirely as a gas or as a gas-liquid mixture depending on the properties of the hydrocarbon and on the thermodynamic process it follows during flow. The distance r would be variable under transient flow conditions. but for purposes of analysis the flow is considered to l~e steady at the particular instant of observation during the flowing life of the well of interest. If the flow were isothermal and the hydrocarbon a pure substance, the fluid would be entirely gaseous downstream from r. Thus, this isothermal flow process for a pure substance would require that the heat of vaporization be supplied at r. over zero length of porous medium, at the precise rate necessary to maintain the constant temperature. This means that the solid matrix of the porous medium (reservoir rock) and the surroundings (impermeable strata confining the reservoir rock) would have to serve as infinite heat sources. Heat-transfer requirements would be somewhat less severe for the isothermal flow of a multicorn-ponent hydrocarbon as bubble and dew points at the same temperature correspond to different pressures. In this instance isothermal conditions would be sustained without complete vaporization of the fluid over zero length of porous medium. Nevertheless. as the flow is in the direction of decreasing

Jan 1, 1951

By W. F. Hosford, E. W. Kelley

By testing polycrystalline specimens from textured plates which had Previously been used to provide materials for growing single crystals, it has been possible to relate the plastic anisotropy of textured materials to the deformation behavior of single crystals. The deformation studies have been conducted at room temperature on textured polycrystalline magnesium and binary Mg-Th and Mg-Li alloys. Variously oriented specimens of the textured materials were deformed in plane-strain compression and in uniaxial tension and compression. The stress-strain curves are similar in their general jorm of anisotropy and stress levels to those obtained on single crystals of the same alloys. The degree of anisotropy is lower, however, in the polycrystalline materials and correlates with the intensity of the basal texture. Yield loci for the textured materials appear reasonable in terms of the deformation mechanisms, and deviate sharply from the form predicted by the Hill analysis for aniso-tropic material. A N earlier study1 of single crystals has shown that magnesium and magnesium alloys with thorium and with lithium deform at room temperature primarily by basal slip, {10i2) twinning, and (1011) banding. The (10i1) banding mode is a combination of {10ll) twinning followed by (1012) twinning and basal slip within the doubly twinned material.2, 3 Magnesium with lithium can also deform by {1010)(1210) prism slip.1&apos;4&apos;5 Still other deformation modes have been reported for magnesium6-11 but these are considered to play a minor role in room-temperature deformation. In a polycrystalline material, plastic deformation must occur in the individual grains through the operation of one or more of the various deformation modes. Because the critical shear stress for basal slip is very low compared to the activation stresses for the other deformation modes,&apos; basal slip accounts for much of the deformation in the polycrystalline aggregate. However, since there are only two mutually independent basal slip systems, and because five independent systems must be active for an arbitrary shape change in any material,&apos;&apos; modes other than basal slip must account for some of the strain. The deformation of textured magnesium, like that of other hcp metals, must be controlled by the same mechanisms observed in single crystals. In strongly textured material, the form of the anisotropy should be similar to that of single crystals, and the degree of anisotropy should depend on the intensity of the texture. EXPERIMENTAL PROCEDURE The anisotropy of deformation was investigated through the use of plane-strain compression tests, as well as uniaxial tension and compression tests. Materials. Test specimens were cut from the three textured plates of magnesium which had previously been used to provide material for single crystals.&apos; These plates, furnished by Dow Chemical Co., had been reduced about 80 pct during the process of being hot-rolled to their final 1/4-in. thicknesses. The plates had the three respective compositions, pure magnesium, Mg-0.5 wt pct Th (0.49 pct Th by spectro-graphic analysis), and Mg-4 wt pct Li (3.84 pct Li by chemical analysis). Impurities other than iron were less than 0.0005 pct Al, 0.01 pct Ca, 0.001 pct Cu, 0.0006 pct Mn, 0.001 pct Ni, 0.003 pct Pb, 0.001 pct Si, 0.001 pct Sn, and 0.01 pct Zn. Iron was 0.001 pct in the pure magnesium, 0.002 pct in the Mg-0.5 pct Th, and 0.014 pct in the Mg-4 pct Li. The textures of the three plates were determined by X-ray diffraction utilizing only the reflection technique out to an angle of 50 deg from the sheet normal. The resulting basal pole figures are presented in Figs. 1, 3, and 5. Grain sizes in the plates were ASTM number 4 in the pure magnesium and number 7 in each of the alloys. Plane-Strain Compression Tests. Plane-strain compression specimens approximately $ in. thick by 4 in. wide by $ in. long were prepared for each of the three compositions. These specimens were prepared in a manner similar to that used for the single-crystal specimens of the earlier study.&apos; All polycrystalline specimens were stress-relieved at 500°F for hr as the final step in their preparation for testing. The testing procedure was identical to that used for the single crystals, involving compression in a channel and using 2-mil Teflon film as a lubricant. The specimens were tested in six orientations of interest, these being the six combinations of the rolling, transverse, and thickness directions of the material serving as loading, extension, and constraint directions in the plane-strain compression test. Each of the six orientations was assigned a two-letter identifying code. These are combinations of the letters (thickness direction), R (rolling direction), and T (transverse direction) with the first letter signifying the loading direction and the second letter the extension direction. For example, ZR specimens were compressed in the thickness direction while extension was permitted to operate in the rolling direction of the textured material. To facilitate comparison of the present work with that of the single-crystal study1 the orientations used for single crystals are given in Table I along with the polycrystalline orientations that most nearly correspond. To insure reproducibility, at least three duplicate

Jan 1, 1969

By J. Paces, E. Miller, K. L. Komarek

The resistivity was determined as a function of temperature over the composition range from pure cadmium to 40 at. pct Cd. Melts with cadmium contents less than 85 at. pct had negative temperature coefficients of resistinity. On cooling below a transition temperature close to the liquidus temperature, the slope of the resistivity-temperature curve changed sharply. The activation energy calculated from the slope was 0.07 ev above the transition temperature and 0.14 ev below. The resistivity vs composition curve shows two maxima corresponding in composition approximately to CdSb and Cd3Sb2. THE relationship between the structure of a liquid and that of the crystal formed on solidification is at present not well-under stood. Various experimental determinations of the properties of liquids indicate that deviations from random atomic arrangements in liquids occur and that the properties of a solid and of its melt are closely related. Thermody-namic activities of liquids usually show negative deviations in systems where compound formation occurs in the solid,&apos; and X-ray data indicate that close-packed solids and their melts frequently have nearly the same coordination number. Electrical resistivities and viscosities of liquids frequently exhibit maxima at compositions corresponding to compounds in the solid state. It should be of interest to study systems which have both stable and metastable compounds in the solid, and to determine if the short-range order in the liquid is affected by the existence of the metastable solid phase. The Cd-Sb system exhibits such a metastable phase. The phase diagram is shown in Fig. 1.3 The stable system has one intermetallic compound, CdSb, crystallizing in the orthorhombic crystal structure, with a melting point of 456°C. The metastable system also has one compound, Cd3Sb2, melting at 420°C and crystallizing in the monoclinic structure. Metastable alloys transform to the stable crystal structure in the temperature range from 250o to 350°C. Several distinct indications of very strong short-range order in the liquid phase have been reported in this system, with a close relation between the ordering in the liquid and the existence of both the stable and metastable solid phases. Scheil and Baach4 have observed distinctly different vapor pressures for liquid Cd-Sb alloys depending on whether the liquid solidified to the metastable- or stable-phase configuration. They observed an unusually sharp increase of the activity in a limited temperature interval immediately above the liquidus temperature of stable alloys, followed by a sudden decrease in slope to what they considered normal values. On cooling, the activity data reproduced the values in the normal range but then deviated from the values obtained on heating. They also observed that specimens of the stable phase upon melting and resolidifying always crystallized in the stable crystal structure as long as the melt was not heated to more than 485° to 525°C; otherwise solidification to the metastable phase occurred. However, in a later investigation, these results were not reproduced (13). The resistivity of liquid Cd-Sb alloys has been investigated by Matuyama 5, Oleari and Fioram, 8 and Belaschenko (141, but only above 500°C, the temperature region where Scheil and Baach observed no vapor-pressure anomalies. The data of Matuyama and of Oleari and Fiorani are reproduced in Fig. 5 and show a maximum in resistivity at 50 at. pct Cd. The data of Oleari and Fiorani, however, show the maximum as being rounded, and their values in general are slightly higher than those of Matuyama.

Jan 1, 1964

By J. P. Boisseau, C. N. J. Wagner, E. N. Aqua

An analysis ulas made of powder-paltern peaks from cold-rolled polycrystalline copper and from copper powders, compacted into briquets (1 in. diameter) with pressures up to about 106 psi. Powder-pattern peaks from both contact faces were measured with a diffractometer and CuKa radiation. Laltice-parameter measurements indicate the presence of residual stresses in the bulk specimen of the order of a - -10 kg per sq mm after 93 pct reduction in thickness, and give some evidence for the occurrence of deformation stacking faults (probability a - 0.003) in both bulk and powder samples. Fourier analyses of the line profiles were carried out on the (111) - (222) and (200) - (400) Pairs of reflections. The particle sizes decrease rapidly with increasing deformation and reach asymptotic values of De (111) = 550A and D, (200) = 350A at about 25 pct reduction in thickness or 80,000 psi pressure for compaction. The anisotropy of the particle sizes indicates the presence of microtwins and stacking faults on (111) planes. The rms strains increase also with deformation and reach limiting values of 2 x 10-3 in the [100] direction and 1 x 10-3 in the [Ill] direction at a distance L = 100A normal to the reflecting planes. THE diffraction of X-rays in cold-worked, polycrystalline, fcc metals and alloys yields Debye-Scherrer patterns in which the individual (hkl) lines may show a broadening, a shift, and an asymmetric shape.&apos; These effects can be explained by the fragmentation of the small, coherently diffracting domains, the presence of residual elastic strains in the lattice, and the formation of stacking faults. X-ray studies of stacking faults in fcc metals and alloys have been methodically performed during the last few years, but so far most of the investigators dealt with cold-worked powder specimens obtained by filing.2-8,10-19 In such specimens, the crystals are randomly oriented and the average elastic strains are assumed to be zero, so that the observed peak shifts are due to stacking faults only. The agreement between X-ray diffraction theory1,20 and experiment is generally good. On the contrary, cold-worked, polycrystalline bulk specimens (after wire drawing, rolling, plastic deformation by tension or compression, etc.) contain residual elastic strains, which may not average to zero in the surface of the specimen and show very strong preferred orientation of certain lattice planes (texture) parallel to the specimen surface. Nonzero elastic strains also produce peak shifts, the magnitudes of which depend upon the crystallographic orientation of the reflecting lattice planes in elastically anisotropic materials as well as on the type of plastic deformation and which have to be taken into account when measuring stacking-fault probabilities in deformed bulk specimens.21-23 The purpose of the present investigations was to perform a detailed X-ray analysis on a bulk specimen of a fcc metal deformed by rolling at room temperature and on powder of the same material deformed by compaction, and to compare these results with those previously obtained on cold-worked filings.18 Pure copper was chosen for this study since it is known to produce only a small quantity of stacking faults by filing at room temperature.3,16,17,19 The residual elastic strain in the surface of the bulk copper should be the predominant factor determining

Jan 1, 1965