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By J. F. Smith, J. E. Davison

The heat capacity of CaMg2 was measured over the temperature interval, 4.8° to 287°K, by the technique of low-temperature adiabatic calorimetry. Heat content measurements were performed with a drop calorimeter over the temperature interval, 273" to 673°K. From these data the thermodynamic functions, (FT - H0)/T, ST - So, and & - Ho, were evaluated. A third-Law calculation of the standard entropy of formation of CaMg2 yields a value of -0.25 * 0.06 cal per (°K g-atom) , and the free-energy function derived from this study when combined with existing equilibria data yields a value for the standard enthalpy of formation which is in agreement with direct calorimetric enthalpy measurements. The accompanying paper' shows that the enthalpy of formation of CaMg2 has been determined with good precision by three different calorimetric techniques.'-= TWO independent determinations of the Gibbs free energy of formation of CaMg2 have also been made; both determinations were based on vapor pressure measurements, being in one case hydrogen vapor pressures over ternary Ca-Mg-H alloys4 and in the other case magnesium vapor pressures over binary Ca-Mg alloys.5 The present determination of heat capacity of CaMg2 below room temperature and of the heat content of CaMg2 above room temperature was undertaken to provide supplementary data. These data are useful in their own right but can in addition be used to evaluate an entropy of formation for CaMg2 which, because of the interrelation of free energy, enthalpy, and entropy, can be used as a check of the self-consistency of the composite of the presently available information. LOW-TEMPERATURE HEAT CAPACITY The heat capacity of CaMg2 was measured over the temperature interval 4.87° to 286.64°K in an adiabatic calorimeter. The physical details of the calorimeter and the experimental procedure for measuring the heat capacity of a specimen have been adequately described by Gerstein et a1.6 The source and purity of the calcium and magnesium are described together with the methods of sample preparation and chemical analyses in the accompanying paper.' Results of chemical analyses of the material which was used in the present investigation are shown in Table I. These analyses show that, on the basis of the published phase diagram,7 the heat capacity sample contained a slight excess of a calcium while the heat content sample contained a slight excess of magnesium. However, in both cases the excess was small, and X-ray diffraction patterns showed reflections which were without exception attributable to CaMg2. The sample which was used for heat capacity measurements weighed 69 g while the sample container and addenda weighed 132 g. The sample was in the form of annealed powder, 50 to 60 mesh, and was sealed into the sample container under 0.1 atm of helium. Copper fins inside the sample container facilitated thermal equilibrium of the powdered Sample. Time intervals of the order of 10 min were required for thermal equilibration, and such times are normal for this calorimeter regardless of the form of the sample. The observed heat capacities were corrected for the small excess of a calcium through use of the heat capacity values tabulated by Hultgren et a1.8 The corrected heat capacities are tabulated as a function of temperature in Table II. The free-energy function and the absolute entropy of CaMg2, which were calculated from the experimental heat capacity data, are listed in Table 111. A smooth curve was fitted to a plot of the experimental values of the heat capacity and in only two instances above 30°K did the plotted points deviate from the curve by more than 0.2 pct. Below 10°K the deviation of several of the points was as much as 50 pct. These large percentage deviations were attributed to the small value of the heat capacity and to the low sensitivity of the platinum resistance thermometer in this temperature range. The deviations in the region of 10°to 30°K were less than 5 pct. Although the percentage deviations of some of the low-temperature measurements are large, the actual value of these deviations is small since the magnitude of the heat capacity in that temperature range is small. The error in the value of the third-law entropy at 298.15°K was estimated to be less than 0.01 cal per (°K g-atom). A value of -0.25 ±0.06 cal per (°K g-atom) was obtained for the standard entropy of formation at 298.15°K from the relation:

Jan 1, 1969

By G. W. Binkley, G. K. Dumbauld, F. A. Brooks, B. E. Morgan

In recent years, oil well cementing compositions have been developed with low densities, controlled set strengths, and satisfactory thickening times. With the introduction of the permanent-type well completion method for cementing wells, another property—that of rate of filtration or water loss to permeable formations— has become important. Laboratory data show that cement slurries prepared with oil, water, bentonite, and calcium lignosulfonate possess satisfactory thickening times, strengths, and filtration properties for primary cementing of casing and for squeeze cementing with the permanent-type well completion technique. Cementing compositions have been prepared with oil-in-water emulsions varying in composition from 60 cc water and 20 cc oil per 100 gm cement to 90 cc water and 45 cc oil per 100 gm cement. These compositions have contained from 0.4 to 5.0 per cent calcium lignosulfonate by weight of dry cement. Slurries prepared from these compositions weigh 11.4 to 13.1 lb/ga1 and have filtration rates of from 10 cc to approximately 100 cc in 30-min API tests at room temperature. The unfiltered emulsion cements develop one-day tensile strengths of 60 to 220 psi; and the filtered mass sets to tensile strengths of 60 to 150 psi in 12 hours and develops strengths of 320 to 515 psi in seven days when cured at 125° F. Field experience gained from 13 field mixing jobs demonstrates the utility of the emulsion cement for permanent-type squeeze cementing operations. INTRODUCTION In recent years, research in oil well cementing composition has been directed toward the development of cements having low densities, controlled set strengths, satisfactory thickening times, and low rates of water loss by filtration. Two well cementing compositions that have been developed with these properties are the modified cements containing, respectively, 12 and 25 per cent bentonite clay and various concentrations of calcium lignosulfonate1,2 In a search for other ways to incorporate these characteristics in a cementing composition, consideration was given to the rheological properties of oil-emulsion drilling fluids. Many of the desirable properties observed in oil-emulsion drilling fluids are equally advantageous in a cementing composition. For example, low water loss by filtration and low density, which are inherent characteristics of these oil-in-water emulsions, are desirable for many oil well cementing operations. Furthermore, oil-emulsion slurries have lubricating properties similar to those of oil-emulsion muds, a factor which should provide ease of rotation of casing during primary cementing operations. The properties of lubrication and low filtration may be of special value in both primary and squeeze cementing operations encountered in slim-hole drilling. Studies in the preparation of oil emulsion systems have pointed out the need for violent agitation in order to disperse the oil into the water phase. It was thought, therefore,

Jan 1, 1957

By E. S. Bartlett, D. N. Williams

QUANTITATIVE values for the oxidation rate of unalloyed molybdenum in air at temperatures above the melting point (1460°F) of the characteristic oxide are contained in the literature as a result of previous investigations. Lustman' reported values corresponding to 0.36 in. penetration per day (IPD) at 1500 and 1600°F in still air, noting essentially no variation in rate with temperature. Jones, Spretnak, and Speiser' reported values corresponding to 0.14 and 0.13 IPD at 1500 and 1800°F, respectively, in still air, attributing the decreased oxidation rate at higher temperatures to a lesser accumulation of the corrosive molten oxide on the surface at the higher temperature as a result of increased volatilization rate. Harwood3 ecently summarized work in the field, presenting generalized data corresponding to 0.48 to 0.96 IPD at 1800°F and 0.55 to 0.83 IPD at 1700°F in slowly flowing air. In a recent program at Battelle, it became desirable to know more about the characteristic oxidation behavior of molybdenum under varying conditions of temperature and atmosphere. Using oxidation-test apparatus designed for dynamic, continuous recording of weight change during testing,' values for the oxidation rate of molybdenum were obtained at temperatures from 1400 to 2150°F. In addition the effect of air flow on the oxidation rate was studied briefly at temperatures of 1600, 1800, and 2000°F. Exhaust of the contaminated atmosphere from the oxidation chamber was effected by an impeller pump attached to a 3/16-in.-diam opening in the oxidation chamber. The volumetric exhaust rate (cubic feet per hour) was normally maintained slightly in excess of the input rate to avoid condensation of MOO,,' on the sample suspension rod. The entering atmosphere was preheated prior to admission to the oxidation chamber by a 1 1/2-in.-diam cup packed with shredded asbestos. The experimental data are presented in Table I. Comparing conditions 2 and 3 (taking into account the temperature difference) and conditions 8 and 9. shows that in the absence of forced exhaust an atmosphere of moving air results in greater oxidation rate than a stagnant atmosphere. The use of forced exhaust, as shown by comparing conditions 3 and 4 and conditions 14 and 15: resulted in an even greater increase in oxidation rate. By virtue of the size of the atmosphere input and exhaust openings, it was calculated that the exhaust velocity was about 60 times that of the input velocity for essentially equal volumetric flow rates. Because of the proximity (about 3/4 in.) of the exhaust port to the specimen, it is logical to assume that cleansing of the atmosphere immediately surrounding the specimen was accomplished much more efficiently by the exhaust flow than by the input flow at a constant-volumetric flow rate. Also, it can be seen by comparing conditions 4 through 7 and conditions 11 through 13 that increasing the rate of atmosphere flow (by increasing input velocity with a proportional increase in exhaust velocity) above some optimum value has little, if any, further effect on the oxidation rate. These results suggest that there is a maximum oxidation rate for molydenum at a given temperature which is obtained when conditions are maintained such that the partial pressure of MOO3 in the atmosphere surrounding the specimen is at a low value. By controlling the partial pressure of MOO, surrounding the sample, it is possible to control the rate of volatilization of MOO:, from the surface. This, in turn, affects the rate of oxidation, since the thickness of the MOO3 layer determines the amount of oxygen which will be able to reach the reaction surface.' When the liquid oxide layer is less than some critical thickness, i.e., when the volatilization rate is high, enough oxygen is transported to the active surface to permit oxidation to proceed at the maximum rate allowed by the kinetics of the oxidation reaction. However, if the volatilization of MOO,, is suppressed, the thickness of the layer of MOO3 on the surface increases, and the diffusion of oxygen through the oxide layer becomes the rate-controlling step in the oxidation process. The lack of agreement between the present results and those of previous investigators is presumed to be due to differences in removal of the oxidation product (Moo,) from the immediate vicinity of the sample. By comparing conditions 1, 5, 10, 12 and 14, it is seen that when forced exhaust was used the oxidation rate of molybdenum increased with increasing temperature. A rapid increase was observed between 1400 and 1600°F, attributable to the effects

Jan 1, 1959

By P. K. Koh, H. A. Lewis, H. F. Graff

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 1'700°C for slags containing up to 20 pct A12O3. This paper presents the results of additional studies at 1600" and 1700° C which extend the silicon distribution data at these temperatures for CaO-A12O3-SiO, slags over a range from zero pct Al2O3 to saturation with Al2O3, or CaO.2Al2O3. The upper limit of SiO2 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 Recently4-7 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/Al203 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/Al,O3 = 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/Al0 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.2Al2O3 and of Al20,. 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: SiO2 (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 P. Greenfield, C. C. Smith, A. M. Taylor

The Mg-Zr alloy ZA and Mg-Mn alloy AM503(S) are shown to have a markedly improved resistance to creep deformation after suitable heat treatments. This improvement makes them suitable for certain stress-bearing fuel element components in nuclear reactors. The extent of strengthening is described and an explanation of the behavior of both materials is given, based on a combination of strain-aging and grain growth. The increase in operating temperatures of fuel element components in Calder Hall type nuclear reactors has necessitated the development of magnesium base alloys with a very high resistance to creep at temperatures up to 500°C. Such alloys are not required for fuel element cans, which require high-creep ductility rather than strength, but for can supporting and stabilizing components, which are needed to support the imposed loads without deforming more than about 1 pct in times of up to 40,000 hr. The amount and type of alloying addition made to magnesium for these parts is limited by the necessity of keeping the cross-section to thermal neutrons as low as possible. The alloys must also possess a high resistance to oxidation in CO2. Alloys which have been developed for this application include ZA, an alloy of magnesium with 0.5 to 0.7 pct Zr and AM503(S), an alloy of magnesium with 0.5 to 0.75 pct Mn. In the as-extruded condition these alloys are very weak and ductile in creep but it has been found that they can be strengthened to a significant extent by heat treatment. This paper describes the method of developing a high-creep resistance in ZA and AM503(S), the extent of the strengthening produced and discusses the probable mechanisms of strengthening. TEST MATERIALS Specimens were taken from typical casts of ZA and AM503(S) alloys extruded into 2 1/4-in.-diam bars, supplied by Magnesium Elektron Ltd. Typical analyses of the bars were as follows: The as-extruded mean grain diameter was 0.001 to 0.002 in. for the ZA alloy and 0.003 in. for the AM503(S) alloy. EXPERIMENTAL METHODS Extruded bars of ZA alloy, 2 1/4 in. in diameter and 9 in. long, were heat treated in electrical resistance furnaces in an atmosphere of flowing CO2 containing 50 to 300 ppm water, thereby reducing the extent of oxidation compared with that which would have occurred in air. Heat treatments were carried out at 600oc for times of 8, 24, 48, 72, and 96 hr and material was subsequently both furnace cooled and water quenched. In order to measure the effect of time of heat treatment, specimens were creep tested at 400°C and 336 psi for about 1000 hr. Subsequently, the behavior of material heat treated for 96 hr at 600°C and furnace cooled was tested at a variety of stresses from 200° to 500°C. Tests were also conducted at 200o and 400°C on material in the as-extruded condition for comparative purposes. With the AM503(S) alloy, only the effect of heat treatment at 565°C for 4 hr was examined. It has been shown1 that such a heat treatment produces marked strengthening in this alloy. Tests on this material were conducted at a variety of stresses at 200°, 300°, and 400oc with comparative tests on as-extruded material at 200o and 400°C. The creep tests were carried out on machines using dead-weight loading and direct micrometer strain measurements on specimens 5 in. long and 0.357 in. diameter. At temperatures of 400° C and below, the creep tests were conducted in air, but at higher temperatures an atmosphere of CO2 was used. Grain size measurements were made on ZA in the extruded and heat treated states and on each specimen after creep testing. This was done by a line count of a minimum of 20 grains in two or three random fields in the longitudinal and transverse directions. The same method was used for measuring the grain size of as-extruded AM503(S), but the grain size of the heat treated material was so large that this method could not be employed. For heat-treated AM503(S) the large grained characteristics (between 0.1 and 1 in.) were confirmed by the measurement of individual grains. In the case of the ZA alloy, specimens taken from various stages in the program were analysed for hydrogen by a combustion method. Material in various states was also analysed for the soluble and insoluble zirconium content by dissolving in dilute hydrochloric acid. This technique has been useda for the determination of amounts of zirconium present

Jan 1, 1962

By R. E. Morgan, D. L. Douglass

The determination of phase relationships and solid-solubility limits can be performed by quantitative metallography in addition to the usual X-ray and metallographic techniques. For example, Beck and smith1 redetermined the ß/ß + ?, ß + ?/?, a/a + ß and a + ß/ß boundaries in the Cu-Zn system by measuring the volume fraction of second phase of several alloys and extrapolating the volume fraction-composition curves to 0 and 100 pct. A modification of this technique is suggested for certain alloy systems, in which it is not necessary to use several alloy compositions but merely one. A single two-phase alloy may be used to determine terminal solubilities in the following manner. The method consists of equilibrating samples of the alloy in a two-phase region adjacent to the desired solid solution, at three or more temperatures, quenching, measuring the volume fraction of second phase present, and applying an analytical treatment to calculate the unknown solid solution. However, two restrictions are inherent in this technique. They are: 1) only certain types of alloy systems are amenable to it, and 2) the general features of the system must be known. The first drawback to the new technique, i.e., that only certain types of systems may be studied, necessitates that the composition at one end of the tieline must either be constant with temperature or well established as a function of temperature. Either a pure metal or some intermetallic compounds fulfill the former. If it is assumed that the volume per gram-atom of a dilute solution is unchanged by the addition of element B to element A, the composition of the solid solution in equilibrium with the second phase may be determined by a material balance and is given by where X, = volume fraction of B in a solid solution Xc = volume fraction of B in compound c X = volume fraction of B in alloy f = volume fraction of second phase The composition by weight may then be determined by the use of tables in the Metals Handbook2 when the density ratio of the solid solution constituents is known. A possible alternative treatment involving the use of the lever rule is less precise than the above tech- nique. This may be used when the density of the solid solution is either known or may be calculated from X-ray data for several compositions. The following analysis is then made. The ratio of compound to solid solution (by weight) may be expressed as follows: x0 - x wc = xr-x = x0 - x r2i Xc -X where Wc = weight of compound w = weight of solid solution x, - alloy composition, weight percent x = unknown composition Xe = compound composition but where V, = volume of compound VA = volume of solid solution pc = density of compound p, = density of solid solution fc = volume fraction of compound fB = volume fraction of solid solution and fs = l -fc then If pc and xc are known, and f, is measured, then pB is the only unknown on the right side of Eq. [4]. The known densities of the solid solution can be plotted for various compositions and can then be expressed mathematically as a function of composition. The use of an expression of pB = f(x)reduces the equation to one unknown—the desired solubility. In the event that the densities are unknown, they may be calculated for various compositions from Vegard&apos;s law. The calculated values are then plotted and expressed analytically. The most accurate results are obtained for Eq. [4] when fc<< 1, i.c., when (x, -x,) - 0, &/l-f, - m; but as fc/l -fc - 0, (xl-x,)- (x, - x), and x - x,,. However, the accuracy with which fc can be measured decreases as f, decreases.3 Alloys for investigation must be selected by a compromise, which is based upon an error analysis of Eq. [4] and knowledge of the accuracy of volume fraction measurements. An examination of phase diagrams in the literature showed many which were amenable to the technique described here. The zirconium-copper system was selected in order to determine the solubility of copper in beta zirconium. Pieces of an alloy which was arc-melted three times were wrapped in tantalum foil and sealed under an argon atmosphere in Vycor tubes. The sealed samples were equilibrated at temperatures from 850" to 960°C for 3 weeks and quenched to room temperature by smashing the capsule in water. Several planes of polish were examined, and

Jan 1, 1960

By W. C. Hagel, H. J. Beattie

Seven austenitic alloys of varions base compositions and minor-alloy additions were solution-treated, aged systematically between 1200oand 1800oF, and examined by X-ray and electron metallography. Intragranular preczpitations of µ, Laves, s, ?&apos;, Ni3Ti, and x phases were observed as a function of composition and aging time and temperatwre. Phase solubility limits were detevtnitzed within 100Fo intervals. These inter metallic compounds fall into two distinct general classes, and whichever class predomznates depends on base composition. It has become increasingly evident that multicom-ponent austenitic alloys are well characterized by their precipitation processes. Since certain groups of elements act as one, the relationships among these processes are reasonably simple; complete identification of such processes is usually attainable by a systematic aging study with a combination of techniques centered on microscopy and diffraction. Several nickel- and cobalt-base alloys illustrating cellular precipitation and its interaction with general precipitation were reported previously.1 The group of alloys covered in the present paper demonstrates precipitation-hardening reactions involving two distinct classes of intermetallic compounds where the predominating class appears to depend on base composition. This dependency ties in with a crystal-chemistry regularity first observed some twenty years ago by Laves and Wallbaum but never amplified to our knowledge. Results of electron-microscope and X-ray diffraction studies on systematically aged hot-rolled alloys known commercially as S-816, S-590, Rene-41, Incoloy-901, M-308, and M-647 are reported here. Some of these alloys have previously undergone minor-phase analyses by other investiators. Alloy S-816 was investigated by Rosenbaum, Lane and Grant,3 and Weeton and Signorelli.4 Rosenbaum found only CbC in hot-rolled bars. Lane and Grant found CbC and a small amount of M6C in the cast structure and stated that both carbides form during aging, most of the precipitation being CbC. Weeton and Signorelli found CbC, M23C6 and a weak indication of a phase after a slow step-down cooling cycle from 2250°F. Rosenbaum also investigated hot-rolled samples of S-590 and identified CbC and M6C. Preliminary information on Rene-41, gained partly from the present work, was reported by Morris.5 Long-time precipitation phenomena in Incoloy-901 at 1350°Fwere investigated by Clark and Iwanski.B heir raw data re- semble those of our present heat with 0.1 pct B, while their interpretation of these data resembles our interpretation of data from another heat with only 0.001 pct B; they made no statement as to boron content. No previous minor-phase studies of alloys M-308 or M-647 have been reported. EXPERIMENTAL METHODS Table I gives alloy compositions in both weight and atomic percent. Specimens were solution-treated from 1700º to 2200ºF, aged at logarithmic-time intervals up to 1000 hours between 1200 and 1800 F, and examined in accordance with procedures previously described in detail. &apos; &apos; Phase extractions were carried out in electrolytic cells containing 800 ml of either 7 pct HC1 in denatured ethanol or 20 pct H3PO4 in water. After electrolysis for 48 hr at 0.1 to 0.2 amp per sq inch, residues were separated by filtration or centrifuging. X-ray powder patterns of residues were recorded on a diffractometer for accuracy and on film for sensitivity. Lattice parameters were calculated by least-squares analyses of indexed sin 8 values, and relative abundances were estimated from intensities of strongest lines of each phase. These phase abundances denote relative amounts with respect to each other rather than to the alloy. Mechanically polished specimens were etched in a freshly mixed solution of 92 pct HC1, 5 pct H2SO4, and 3 pct HNO3. Parlodion replicas for the electron microscope were chromium-shadowed in high vacuum at a glancing angle of 20deg. All electron micrographs are reproduced here with the shadowing source above. The correspondence betweenelectronmicrostructures and phases identified by X-rays was established by a high redundancy of correlation between relative amounts at different stages of aging and examination above and below critical transformation or solubility temperatures. EXPERIMENTAL RESULTS S-816 and S-590—The phases found in S-816 and S-590 after various aging and solutioning treatments are listed in Table 11. These data and the observed

Jan 1, 1962

By Robert H. Richards

IT will hardly be worth while to spend time over the discovery of this mine, how lumps of galena, were picked up and brought to town, and how legends were told of an old mine from which Revolutionary bullets were made. This is an entirely new mine, with no evidences of former or ancient workings in its immediate vicinity to guide or attract the prospector. The first pit was opened in May, 1874. In August I made a visit to this pit, which was 6 feet wide in the northwest direction, 12 feet long north 80° east, and 6 feet deep. About 4 tons of a galena carrying gray copper, siderite, and quartz, had been taken fron this pit. The lumps were all of them evidently float specimens, and varied from 8 to 12 inches thick, and showed very distinct indica- * An abstract of this paper was kindly presented by Dr. T. Sterry Hunt at the February meeting of the Institute, but as it was not fully written out until the following December, it will describe the mine in a little more advanced stage than when the paper was originally presented.

Jan 1, 1875

By A. W. Schlechten, R. F. Doelling

Parkes&apos; process crusts were vacuum distilled using a shortened Pidgeon retort. Zinc was effectively removed below 800°C and recovered as a zinc sheet easily stripped from the furnace liner. Lead dasdistillationazinc required about 950°C and the resulting lead condensate tillationtended to stick to the thin metal liner. Final purity of residue is limited only by nonvolatile metals such as copper. THE successful commercial application of vacuum distillation for the removal of zinc from lead, as described by W. T. Isbell,&apos; raises the question of whether or not a similar method can be used for other metal separations. Preliminary laboratory experiments on the vacuum distillation of Parkes&apos; crusts by one of the authors&apos; gave such encouraging results that it was decided to make a series of tests with large scale equipment to determine the results that might be expected in plant operation. The pilot-plant test results are reported in this paper. The great advantages of vacuum dezincing are its simplicity, the relatively low temperature of operation, and the fact that the zinc is recovered in the metallic state ready for use again in the desilveriza-tion of lead bullion. These same advantages and others would be realized from the vacuum distillation of the zinc-lead-silver crusts made in the Parkes&apos; process. Zinc readily will distill over at temperatures of 800" to 900 °C as contrasted with the 1200°C or more used in the Faber du Faur furnace. Furthermore, the recovery of zinc as metal is practically perfect since there is no loss by oxidation or fuming. If the vacuum distillation is continued and hastened by raising the temperature to around 1000°C, the lead will distill over at an appreciable rate and deposit in a warmer zone of the condenser. This lead will contain a small amount of silver, but it can be returned to the desilverizing kettles and there is not the chance of loss that there is in disposing of the rich litharge from cupelling. The lower temperatures required will mean a saving of fuel and less wear on the equipment. One further point is that the vacuum distillation could be run on a small scale practically continuously, so as to avoid the accumulation of large amounts of silver-rich material and the need of assembling a large crew for special cupellation runs. It should be pointed out here that the final purity of the silver residue will depend on the copper or iron content of the crusts, as these and other metals with low vapor pressure will not be eliminated. The idea of treating the silver-zinc-lead crusts from the desilverization of lead bullion by vacuum distillation is not a new one, but such experiments have not been reported, as far as can be determined. In 1912, T. Turner presented a paper3 before the Institute of Metals on the vacuum distillation of brass, and a member of the audience suggested that he try his method on Parkes&apos; crusts. In 1935, W. J. Kroll, noted for his discovery of debismuthiz-ing lead by calcium additions, published a paper&apos; on vacuum distillation of metals and pointed out possible applications in the lead industry. Principles of Separation The successful separation of two or more metals by distillation depends upon an appreciable difference in the effective vapor pressures of the metals in the alloy to be treated. The vapor pressures of the common metals have been determined with considerable accuracy; for example, at 800°C the vapor pressures of the individual metals which are of particular interest in this paper are about .as follows: Zn, 241 mm; Pb, 0.0553 mm; and Ag, 0.0000276 mm. Unfortunately,, data are not available on the activities of the components in the ternary system Zn-Pb-Ag, but it can be estimated that on the basis of the vapor pressures of the individual metals a good separation can be made by distillation. The preliminary laboratory tests previously mentioned&apos; supported this assumption. The pilot-plant size vacuum distilling furnace is shown in Fig. 1. It consisted of an abbreviated Pidgeon retort, 5 ft long with an ID of 8 in., heated by six silicon carbide elements placed symmetrically

Jan 1, 1952

C. M. Bishop (Aircraft Div., A. V. Roe Cnnada Ltd., Toronto)—Reference is made to the coherency hardening of ß due to ß&apos; and also to the hardening of ß due to a coherent precipitation of the a phase. What is meant by the term "ß&apos;?" Would not the coherency hardening of ß during cooling be due to precipitation of a sub-microscopic dispersion of a, as is the case during reheating a ß-quenched alloy? I feel that these two phenomena are essentially the same mechanism, i.e., precipitation of a from unstable or supersaturated ß. From the text, it would appear that Tables III and IV are intended to show the effect of the martensite transformation on the properties of Ti-Mn alloys. Referring to Table 111, the ß-quenched alloys would contain a greater proportion of retained ß than would the equilibrated alloy. Could not the increase in properties be attributed to this, along with possible coherency hardening of the ß? In the same way, the structures referred to in Table IV contain ß from which they could derive their hardness. It would appear to be difficult, if not impossible, to assess the role of the martensite transformation from the data contained in these tables. F. C. Holden, H. R. Ogden, and R. I. Jaffee (authors&apos; reply)—In reply to the first question raised by Mr. Bishop, the term "ß"&apos; designates an apparent retained-p structure which is harder than it is after the most rapid cooling from the ß field. It is thought to be the result of a coherent precipitation of a. The mechanism by which hardening takes place is undoubtedly the same as that involved in the early stages of aging of a re-tained-p structure, and we are in agreement with Mr. Bishop on this point. The term "ß&apos;" to designate the anomalously hard retained-ß structure was agreed upon at a symposium in 1953." The authors do not agree that the quantity of retained ß and/or ß&apos; in the ß-quenched specimens of Table III is necessarily greater than that of the 600°C equilibrated specimens. The ß-quenched specimen has a structure which appears to be completely a&apos; formed by the martensite reaction. It is recognized that there could be some retained ß (or ß&apos;) between the a plates if the M, temperature is below room temperature. This is unlikely for the 3.4 pct Mn alloy where the M, is known to be at about 640°C. Therefore, the increase in strength cannot be attributed to the presence of a greater quantity of coherency-hardened ß, but, rather, the increase in strength must be attributed to the transformation products formed, e.g., a&apos; (martensiti-cally formed a). Concerning the data in Table IV, we agree that it is difficult to estimate the role of the martensite reaction, since the 6.4 pct Mn alloy was retained ß in the quenched condition.

Jan 1, 1955

By Huey-Lin Luo, T. R. Anantharaman, William Klement

Two new metastable phases have been obtained in Au-Ge alloys by rapid cooling from the melt. One is of the hep structure with near-ideal axial ratio and may be considered a Hume-Rothery phase. The other has a complex tetragonal structure (a = 11.627Å and c = 22.191Å for the Au60Ge40 alloy) and may be looked upon as a superlattice made up of forty-four fee unit cells. Alloys with the tetragonal phase are charactevized by marked preferred orientation. The metastable constitution of the Au-Ge alloys is discussed with reference to the rate of cooling from the melt. THE Au-Ge equilibrium diagram features a rather deep eutectic near 27 at. pet Ge with a maximum solid solubility of 3.2 at. pet Ge in gold and is similar to the Ag-Ge, Ag-Si, and Au-Si diagrams.&apos; The present study of the effects of rapid cooling from the melt on the structure of Au-Ge alloys constitutes an extension of similar investigations2-8 in this laboratory on alloys of noble metals with germanium and silicon. Nonequilibrium hep structures have so far been obtained by quenching Ag-Ge2, 3 and Ag-Si4, 5 alloys from the melt; an Au-Si alloy of approximately eutectic composition has been found6 to solidify in a noncrystalline state. EXPERIMENTAL PROCEDURES Twenty-nine alloys prepared from gold of 99.9+ pet and germaium of 99.999 + pet purity were investigated. The method of alloy preparation, the technique of rapid quenching from the melt, and the X-ray diffraction procedures were similar to those described previously.3, 4 Essentially, small sections (-20 mg) of thin alloy rods (-1 mm diam) were rapidly heated up to 1200°C in a graphite crucible under argon and the liquid alloy ejected by a helium blast onto a polished copper strip held on the inner periphery of a rotating wheel. The resulting thin foils were examined with or without the copper substrate in a G.E. X-ray Diffractometer or in a 114.6-cm-diam Debye-Scherrer camera. RESULTS Table I gives the constitution of liquid-quenched Au-Ge alloys, as estimated from intensities of X-ray reflections from the corresponding phases, viz., a (fee solid solution), ß (hep phase), ? (tetragonal phase), and diamond-cubic (dc) germanium. Despite unavoidable variations in the quenching rates, the proportions of the phases in different alloys were generally reproducible and stable at room temperature. There was no evidence of quenching strain, since the a doublets were well-resolved in high-angle Debye-Scherrer reflections in all cases except where stacking faults in the a fee and ß hep structures contributed to X-ray line broadening. The ß and ? metastable phases showed signs of decomposition to the equilibrium a phase and germanium only after a few hours annealing above 100°C. A few alloys around the eutectic composi-

Jan 1, 1965

By D. A. Kraai, S. Floreen

The effect of 1 to 50 ppm S on the ductility of nickel at 800° to 1400°F was studied. Results at each temperature showed a decrease in the reduction of area from approximately 95 to 5 pet over the sulfur range studied. Ductility varied with grain size, but only to a minor extent relative to the sulfiw effect. The effects of sulfur were completely offset by the addition of small amounts of magnesium. The results indicate that the "hot-short" loss in ductility is not an inherent property of nickel. Some possible mechanisms which cause the loss in ductility are described. MANY metals or alloys that normally possess high ductility exhibit a ductility loss at intermediate temperatures. This loss in ductility is often called "hot-shortness". Numerous examples of this phenomenon have been reported in the literature. Much of this work has been reviewed by McLean1 and by Rhines and Wray.2 To date there is no fully satisfactory explanation of the cause of this intermediate-temperature hot-shortness. It is generally recognized that impurities, and particularly impurities that form low-melting phases, can cause embrittlement. Examples of hot-shortness have been reported, however, where there were no obvious impurities present which would lower the ductility. Thus there has been some basis for believing that hot-shortness is an inherent property, and that even the purest metal would display a hot-short loss in ductility. This latter hypothesis was recently put forward by Rhines and wray2 based on studies of nickel and nickel alloys. In the discussion of this paper, however, Guard noted that high-purity nickel showed no hot-shortness.3 Thus there is reason to doubt whether pure nickel, or by inference any other pure metal, will inherently exhibit hot-shortness. The present work was initiated to determine the extent to which hot ductility was sensitive to very small amounts of an impurity element. If it could be demonstrated that hot-shortness could be induced by only minor amounts of an impurity, then it might be argued that hot-shortness in general is an impurity effect, and not a fundamental property of pure metals. The particular impurity studied was sulfur in nickel. The deleterious effects of sulfur are well- known. It is also well-known, and will be shown below, that additions of magnesium will render sulfur innocuous. When no such refining agents are added, however, the Ni-S system is a very useful one for studying the influence of small amounts of impurities. EXPERIMENTAL PROCEDURE Two heats containing -24 ppm S were vacuum-melted and small amounts of magnesium were then added under an argon atmosphere. These alloys were used to show the effectiveness of the normal magnesium treatment in overcoming the influence of sulfur. A second series of alloys with a sulfur range of 1 to 50 ppm was then prepared by vacuum melting nickel in alumina crucibles. No elements, such as magnesium, which tend to combine with sulfur were added. The higher sulfur contents were attained by adding nickel sulfide. Lower sulfur contents were prepared using a method in which the melt was oxidized under vacuum to produce the reaction S + 2O = SO2 These heats were subsequently deoxidized with carbon. Ten- to twenty-pound ingots were cast of all of the alloys studied. The compositions are given in Table I. The ingots were forged and hot-rolled to 3/4-in. bar. They were then annealed at either 2000" or 1600°F to produce different grain sizes. One-quarter-in.-diam tensile specimens were machined from the bars. These were tested at 800°, 1000o, 1200°, and 1400°F. The specimens were held at temperature approximately 45 min before testing. The strain rates were 0.005 min-1 to yielding, and 0.05 min-&apos; after yielding. No extensometers or gage marks were placed on the specimens because the higher sulfur heats tended to fracture at the knife-edge indentations or gage marks. The properties measured were ultimate tensile strength and reduction of area. The analytical technique for determining sulfur at low levels was that developed by Burke and Davis.4 They reported a standard deviation of 1 ppm at an average sulfur level of 4 ppm in NBS standards. A standard deviation of 3 ppm is probably more realistic for the alloys used in this investigation considering the possibility of some segregation in the ingots. RESULTS A summary of the tensile results is given in Table I. As shown in the table, both heats to which

Jan 1, 1964

By Ben Gumpertz

The important factors in any study of the screening of sand with a gravel envelope, as applied to use in oil wells, are: (I) sand size and shape, (z) gravel size and shape, (3) ratio of gravel size to sand size, (4) flow velocity, (5) viscosity of the fluid. Perhaps the first extensive investigation of the function of gravel in screening sand was performed by Coberly and Wagner,&apos; from which the following conclusion was drawn: "The diameter of the largest grains in a single classified sand suitable for gravel packing is approximately 13 times the grain size at the ten-percentile analysis of the formation sample." ?;his applies to sands classified by Tyler screens and is for gravel grains of the maximum size that could be used to form a stable bridge. Field practice has shown that the screening effect of a given gravel for a given sand apparently varies with the flow velocity." Also, it has been assumed by some operators that the thickness of the walls of the gravel envelope surrounding the well has little effect upon the screening process. It is thought by others that a narrow envelope of gravel might form an ineffective screen. Thus the purposes of this work are: 1. To investigate the effect of gravel-sand size ratio upon screening action under the condition of varying flow velocities. 2. To investigate the effect upon screening action of varying the thickness of the gravel screen. 3. To investigate sand migration in the gravel screen and the effect of flow velocity and gravel size upon sand migration. Description of Apparatus In an attempt to reproduce field conditions for the purposes of this investigation, a flow tube was constructed, according to the manner of Urenj3 to represent a radial drainage segment of an oil sand. To arrive at the dimensions of the flow tube, a radial drainage segment of rectangular cross section was assumed to define an area of z sq. in. on the face of a well 6 in. in diameter. From this the dimensions of the segment were calculated out to a distance of 5 ft. from the face of the well. By computing cross-sectional areas at a number of sections along the rectangular segment and transforming these areas into the circular form, a drainage cone was obtained having everywhere the same cross-sectional area as the drainage element of rectangular cross section. To construct the apparatus, two sections of pipe of 7%-in. inside diameter, one 13 in. and the other 4 ft. long, were joined by a bolted flange. A mandrel having the dimensions of the drainage cone was centered in the pipe and a neat cement mixture was cast around it. A protective gasket was placed between the two sections of pipe so that the cement body could be separated at that point. When the mandrel was withdrawn a drainage cone was obtained (Fig. I).

Jan 1, 1941

By Ben Gumpertz

The important factors in any study of the screening of sand with a gravel envelope, as applied to use in oil wells, are: (I) sand size and shape, (z) gravel size and shape, (3) ratio of gravel size to sand size, (4) flow velocity, (5) viscosity of the fluid. Perhaps the first extensive investigation of the function of gravel in screening sand was performed by Coberly and Wagner,&apos; from which the following conclusion was drawn: "The diameter of the largest grains in a single classified sand suitable for gravel packing is approximately 13 times the grain size at the ten-percentile analysis of the formation sample." ?;his applies to sands classified by Tyler screens and is for gravel grains of the maximum size that could be used to form a stable bridge. Field practice has shown that the screening effect of a given gravel for a given sand apparently varies with the flow velocity." Also, it has been assumed by some operators that the thickness of the walls of the gravel envelope surrounding the well has little effect upon the screening process. It is thought by others that a narrow envelope of gravel might form an ineffective screen. Thus the purposes of this work are: 1. To investigate the effect of gravel-sand size ratio upon screening action under the condition of varying flow velocities. 2. To investigate the effect upon screening action of varying the thickness of the gravel screen. 3. To investigate sand migration in the gravel screen and the effect of flow velocity and gravel size upon sand migration. Description of Apparatus In an attempt to reproduce field conditions for the purposes of this investigation, a flow tube was constructed, according to the manner of Urenj3 to represent a radial drainage segment of an oil sand. To arrive at the dimensions of the flow tube, a radial drainage segment of rectangular cross section was assumed to define an area of z sq. in. on the face of a well 6 in. in diameter. From this the dimensions of the segment were calculated out to a distance of 5 ft. from the face of the well. By computing cross-sectional areas at a number of sections along the rectangular segment and transforming these areas into the circular form, a drainage cone was obtained having everywhere the same cross-sectional area as the drainage element of rectangular cross section. To construct the apparatus, two sections of pipe of 7%-in. inside diameter, one 13 in. and the other 4 ft. long, were joined by a bolted flange. A mandrel having the dimensions of the drainage cone was centered in the pipe and a neat cement mixture was cast around it. A protective gasket was placed between the two sections of pipe so that the cement body could be separated at that point. When the mandrel was withdrawn a drainage cone was obtained (Fig. I).

Jan 1, 1941

By Potts N. L., Eilerts C. K., Summer E. F.

The second-order, nonlinear, partial- dillerential equation representing the transient radial flow of gas - condensate fluids in reservoirs has been integmted by using finite -dillerence equations and electronic computers. Effect was given to pressure -dependent permeability, viscosity, and compressibility and to distance-dependent permeability. The influence of a second-degree velocity term in the Darcy equation was investigated. Implicit methods were used and practical, convergent solutions were obtained with material balance to less than 6 x 10-4 for recovery of one- hall the reserve at constant flow rate. Integration results provide the productive period of a reservoir for a given constant rate and the fraction of the fluid initially in place that can be recovered in that period. The properties of a lean and a rich fluid are represented in a set of integrations designed to demonstrate the effect of different constant-recovery rates and significant variables emphasized one at a time. INTRODUCTION A method is needed for computing the availability or reserve of a gas in a formation, making use of all technical and engineering information that is pertinent. As a step in this direction, a program for computing transient linear flow1 was developed that utilizes principles of earlier finite-difference computing for a similar purpose2-4 and gives effect to significant pressure- and distance-dependent properties of reservoirs and their contents. The present paper pertains to transient, radial flow of gas-condensate fluids. In the partial-differential equation of flow, effect is given to the variables viscosity and compressibility,5 and also to permeability. Included in the study is the quadratic form of the Darcy equation of flow that has been the subject of field tests6 and that has been applied to a gas with constant properties in transient flow computing. 7 Inclusion in the differential equation of variable coefficients to represent properties greatly complicates the higher derivatives of the equation. Because it was impractical to make a required improvement in certain of the finite-difference derivatives by Taylor-series expansion, five-term derivatives were used in the implicit computing. Related methods were developed that can improve general facility in manipulating finite-difference equations. BASIC EQUATIONS PARTIAL DIFFERENTIAL EQUATION The basic partial differential equation for transient radial flow in the direction of decreasing radius is l_ a(vpr) _? .......(1) r gr at where r = radius, L v = apparent velocity aIong radius, L/t p = density, M/L3 t = time, t Ø = porosity, dimensionless. In this equation, only the porosity is regarded constant. The density is where p = pressure, m/Lt2 M = molecular weight of fluid, m T = constant temperature of fluid, T z(p) = pressure-dependent compressibility factor, dimensionless R = gas Constant, mL2/t2t. The physical boundary of the reservoir is at re, and the producing boundary is defined to be at tq with rq = re /200. By definition,

Jan 1, 1966

By E. M. Porbansky

DURING the investigation of the electrical transport properties of copper, it became necessary to prepare large single crystals of the highest obtainable purity. In an effort to meet these demands, single crystals of copper have been grown by the conventional pulling technique—as has been used for the growth of germanium and silicon crystals.&apos; Low-temperature resistance measurements made on these crystals show that, as far as their electrical properties are concerned, they are generally of significantly higher purity than the original high-purity material. The use of these pure single crystals with very high resistance ratios has made possible the acquisition of detailed information regarding the electron energy band structure of copper2-&apos; and has stimulated widespread effort on Fermi surface studies of a number of other pure metals. It is the purpose of this note to describe our method of preparing very pure copper crystals by the Czochralski technique. Precautions were taken to prevent contamination of the melt from the crystal growing apparatus. A new fused silica growing chamber was used to prevent possible contamination from previous groqths of other materials such as germanium, silicon, and so forth. A new high-purity graphite crucible was used to contain the melt. This crucible was baked out in a hydrogen atmosphere at -1200°C for an hour, prior to its use in crystal growth. Commercial tank helium, containing uncontrolled traces of oxygen, was used as the protective atmosphere. A trace of oxygen in the atmosphere appears to be necessary for obtaining high-purity copper single crystals. A 3/8-in-diam polycrystalline copper rod of the same purity as the melt was used as a seed. The copper rod was allowed to come in contact with the melt while rotating at 57 rpm. When an equilibrium was observed between the melt and the seed (that is, the seed neither grew nor melted), the seed was pulled away from the melt at a rate of 0.5 mils per sec. As the seed was raised, the melt temperature was slowly increased, so that the grown material diminished in diameter with increasing length. When this portion of the grown crystal was -1 in. long and the diameter reduced to less than 1/8 in., the melt was slowly cooled and the crystal was allowed to increase to - 1-1/4 in. diam as it was grown. By reducing the diameter of the crystal in this manner, the number of crystals at the liquid-solid interface was decreased until only one crystal remained. Fig. 1 shows a typical pulled copper single crystal. The purity of the starting material and the crystals was determined by the resistance ratio method: where the ratio is taken as R273ok/R4.2ok. The starting material, obtained from American Smelting and Refining Co., was the purest copper available. Most of the pulled copper crystals had much higher resistance ratios than the starting material. The highest ratio obtained to data is 8000. Table I is an example of the data obtained from some of the copper crystals. Note that Crystal No. 126 had a lower resistance ratio than its starting material and this might be due to carbon in the melt. The melt of this crystal was heated 250" to 300°C above the melting point of copper. At this temperature it was observed that copper dissolved appreciable amounts of carbon. The possible presence of carbon at the interface between the liquid and the crystal will result in reducing conditions and negate the slight oxidizing condition required for high purity as discussed below. The possible explanations of the improvement in the copper purity compared to the starting material are: improvement in crystal perfection, segregation, and oxidation of impurities. Of these, the latter seems to be most probable. A study of the etch pits in the pulled crystals showed them to have between 107 and 108 pits per sq cm. The etch procedure used was developed by Love11 and Wernick.10 The resistivity of the purest copper crystal grown was 2 x 10-10 ohm-cm at 4.2oK; from the work of H. G. vanBuren,11 the resistivity due to the dislocations would be approximately 10-l3 ohm-cm, which indicates that. the dislocations in the copper crystals would contribute relatively little to the resistivity of the crystals at this purity level. Segregation does not seem likely as the reason for purification of the material, since the resistivity of the first-to-freeze and the last-to-freeze portions are approximately the same, as was observed on Crystal No. 124. On most of the crystals that were examined, the entire melt was grown into a single crystal. If the

Jan 1, 1964

By T. L. Chu, G. A. Gruber

Silica films hare been rleposited 011 silicon substmtes at 400° to 600°C by a chemical-transport technique using hydrogen fluoride as the transport agent ill a closed system. This transport takes place from a source materia1 1071: temperature to substrates at higher temperatures, as indicated by the thermochemistry of the transport reaction. The experimental variables of- the transport process, such as the substrate temperature, the pressure pi the transport agent, and so forth, have been studied. The rate -determining step of the transport process appears to he the ),ale of chemical reaction in the source region. The transported films are similar to thermally grown silica films in physical proper-ties with the exception of &apos;some what higher dissolrrtion rates. SILICA films deposited on suitable substrates serve many purposes in electronic devices. They are used for the fabrication of tunneling devices, the surface passivation of devices, and the shielding of devices from nuclear radiation: and as selective masks against the diffusion of specific impurities into semiconductors. Doped silica films can also be used as sources for the diffusion of impurities into semiconductors. Several oxidation and deposition techniques for the preparation of silica films have been developed to meet the requirements of these applications. The therma1 oxidation of silicon by oxygen or steam at temperatures above 900 C is commonly used in silicon technology. The deposition techniques are perhaps more advantageous since they usually require lower temperatures and are not limited to silicon substrates. Silica films have been deposited on silicon and other substrates by reactive sputtering and chemical reactions. The sputtering of silicon in an oxygen atmosphere is capable of depositing good-quality silica films on silicon&apos; and gallium arenide. Many chemical reactions are known to yield silica at room temperature or higher. These reactions may involve intermediate steps. However, the final step yielding silica should take place predominately on the substrate surface in order to produce adherent films. When silica is formed in the gas phase by volume reactions, no adherent deposit can be obtained. Generally, the experimental conditions of a reaction can be varied so that the surface reaction predominates over the volume reaction. The chemical reactions which have been used successfully for the deposition of silica films are briefly as follows. The pyrolysis of alkoxysilanes in an inert atmosphere or under reduced pressure has been employed to deposit silica films on germanium3 and silicon4 at 650" to 750°C in a flow system. The deposition of silica films from alkoxysilanes has also been achieved at nearly room temperature by a low-pressure plasma. Device quality silica films have been deposited on germanium and gallium arsenide by the deposition of an amorphous thin silicon film followed by oxidation at 600" to 700" . Silica films for high-temperature capacitors have been produced by the hydrolysis of silicon tetrabromide at 950°C in argon and hydrogen atmospheres.7 We have developed a chemical-transport technique for the deposition of silica films on semiconductor substrates at relatively low temperatures. The thermochemistry of the transport reaction, the experimental variables of the transport process, and the properties of the transported silica films are described in this paper. THERMOCHEMICAL CONSDERATIONS The transport of solid substances by chemical reactions in the presence of a temperature gradient has been used for the preparation of films and crystals of many electronic materials. In this technique, a gaseous reagent is chosen so that it reacts reversibly with the solid substance under consideration to form volatile products. Since the equilibrium constants of most reactions are temperature-dependent, the transport of these products to regions of suitable temperature in the reaction system would cause the reverse reaction to take place. depositing the original solid. When the equilibrium is shifted toward the formation of the solid as the temperature is decreased, the solid is transported from a high-temperature zone to a lower-temperature region, and vice versa. This chemical-transport technique can be carried out in a closed or gas-flow system. In a closed system, chemical equilibrium is presumably established in the different temperature regions of the system, and the transport agent regenerated in the deposition region repeats the transport process in a cyclic manner. The local chemical equilibrium may not be approached in a flow system: however, this system offers a greater degree of flexibility. Silica reacts reversibly with hydrogen fluoride and this reaction was chosen for the transport process. The over-all reaction between silica and hydrogen fluoride may be written as: SiO2(s) + 4HF(g-) = SiF4Ur) + 2H2O(^)

Jan 1, 1965

By Frank Firmstone

IN the early decades of the past century the method of starting iron blast-furnaces by "scaffolding-down" seems to have been in universal use for coke-furnaces and, at least in this country, for charcoal-furnaces also. It was likewise used at some of the early anthracite-furnaces, as is stated in the important "Reminiscences" printed by the late Samuel Thomas. I It had been generally superseded in Great Britain as early as 1850, by some variations of the plan now used, and was rarely used when Percy wrote.&apos; On the Continent it was still followed in the 60&apos;s,3 and was elaborately described by Valerius in 1852. I have never read any statement as to when and by whom &apos;4 scaffolding" was first dispensed with, but the following extracts from journals of my father seem to fix an authentic date for an instance in this country:

Mar 1, 1907

By John C. Calhoun, J. E. Warren

A study of waterflood efficiency, given in terms of oil recovery at water breakthrough and u1timate recovery, has been made on short, consolidated Pyrex glass cores rendered oil-wet by chemical treatment. Contact angle. interfacial tension, permeability and porosity were the variables considered. Oil and water viscosities, core length and velocity of flooding were held constant. The data permit interfacial tension, contact angle, porosity, and permeability to be grouped into a scaling coefficient along with viscosity, velocity of flooding and length of core. Correlation of the .scaling coefficient with recovery at water breeakthrough is found to follow prediction; correlations of ultimate recovery demand a scaling coefficient different from that which correlates breakthrough recovery. The work indicates that, with proper control, a group of similar natural cores, of permeability plug size, call he correlated 10 indicate basic flooding performance. INTRODUCTION The fraction of oil recovered from a porous medium is related to both reservoir conditions and production techniques. An investigation of all factors that enter into this relationship is necessary in order to arrive at the optimum method of exploitation for oil reservoirs. To define this relationship, laboratory studies have been made by a great many investigators. However. an important obstacle arises if the results of these experiments on water flooding are to be applied to practice. Ditferences in behavior are to be expected between reservoirs of the dimensions encountered underground and those used in laboratory work. Factors which play an important role under laboratory conditions may be of no consequence in reservoirs. Laboratory operating practices generally differ from field operating practices. Thus. a mere understanding of the mechanism of the displacement of oil by water is not enough. It is just as necessary that the process be analyzed dimensionally to give continuity and validity to the conversion from laboratory to field. The theory of oil displacement that has come to be accepted by the majority of those who are associated with reservoir mechanics had its beginning in the work of Leverett¹ and Buckley and Leverett2. The banking of oil, observed by many previous workers, was described by the "fractional flow" and the "frontal advance&apos;&apos; equations. The validity of the Buckley-Leverett theory was substantiated by the experimental and theoretical work of Terwilliger et al³; moroever, the theory was extended by the introduction of the idea of a "stabilized zone" to describe the banking of oil. Levine5 showed that the Buckley-Leverett equations gave reasonable agreement between calculated and experimental breakthrough recoveries only if the capillary pressure and gravity terms were included. Rapoport and Leas1 investigated the properties of linear floods and showed that both breakthrough and maximum recovery are related to a "scaling coefficient&apos;&apos; derived from the Buckley-Leverctt equations. Jones-Par-ra and Calhoun6 presented another scaling coefficient which included both viscous and capillary variables. Such scaling coefficients should suffice to predicl waterflood efficiency. However, some experimenters report data which does not appear consistent with the healing coefficient approach. For example, Engelberts and Klinkenberg7 conducted an extensive series of experiments on a dimensional model which contained a

Jan 1, 1956

By Edward A. Loria

Vanadium is one of the materials being considered for use in fast-breeder nuclear reactors. It is a good heat conductor and nearly transparent to radiation, properties regarded as ideal for nuclear fuel containers. The problem has been the metal lacks ductility needed for forming. In our program at Reno Laboratory the effects of the U.S. Bureau of Mines (previous affiliation) the effects of oxygen, nitrogen, and carbon have been reported21,22 nd most recently the effects of boron and boron with carbon.23 The continuing study by the Ames Laboratory of the effects of hydrogen, the most subtle and fugitive element in its relationship to structure and properties, is commendable. The solubility of oxygen, nitrogen, and hydrogen in vanadium (and other bcc metals as well) is related to material purity. With the available limit on metal purity and the interaction (clustering) of hydrogen with the other interstitial and substitutional elements present in their base metal, would the authors comment on the tolerance of hydrogen in relation to oxy- gen that will avoid intergranular fracture and above what content or how seriously harmful in oxygen at various carbon levels? Understanding the true effects of hydrogen (and other interstitial impurities) in vanadium depends on knowledge of the amount present under various conditions and its distribution between various possible positions. Significant amounts of hydrogen may be in "thermo-dynamic" solution, but not as individual atoms in interstitial positions. It may be in grain boundaries, in subgrain boundaries, in vacancies, or in dislocations. Some of the hydrogen may be paired or in complexes with impurities in substitutional solid solution in vanadium. This makes the analysis of the effect of hydrogen vastly more difficult. It should not be expected that hydrogen in grain boundaries will affect slip in the same manner as hydrogen in interstitial positions, nor will the complexes react to heat treatment the same way as hydrogen in dislocations. It is gratifying that the authors have quoted results from two of our inestiations,&apos; but neglected one2&apos; which applied the Petch theory to electrorefined vanadium of high purity and analyzed the effects of oxygen, nitrogen, and carbon on the ai and ky values obtained by the extrapolation and grain size methods. Details can be found in the paper. Briefly, we obtained a ui value of 10,300 psi (t = 5150 psi) at 273°K. The metal also exhibited profuse twinning with high ductility at 123" and 77°K. Nitrogen was more effective than oxygen in increasing ui, the increase being about twice as much for the same impurity level. Carbon additions resulted in only minimal changes in Ui. The corresponding ky increased as oxygen and nitrogen increased, with nitrogen being more effective. Carbon additions resulted in little change. Although the difference in yield strength of vanadium was explained on the basis of the Cottrell-Bilby model of the tearing away of dislocations from the impurity atoms,

Jan 1, 1970