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By P. M. Blair

This paper presents numerical solutions of the equations describing the imbibition of water and the countercurrent flow of oil in porous rocks. The imbibition process is of practical importance in recovering oil from heterogeneous formations and has been studied principally by experimental means. Calculations were made for imbibition of water into both linear and radial systems. Imbibition in the linear systems was allowed to take place through one open, or permeable, face of the porous medium studied. ln the radial system, water was imbibed inward from the outer radius. The effects on rate of imbibition of varying the capillary pressure and relative permeability curves, oil viscosity and the initial water saturation were computed. For each case studied, the rate of water imbibition and the saturation and pressure profiles were calculated as functions of time. The results of these calculations indicate that, for the porous medium studied, the time required to imbibe a fixed volume of water of a certain viscosity is approximately proportional to the square root of the viscosity of the reservoir oil whenever the oil viscosity is greater than the water viscosity. Results are also presented illustrating the effects on rate of imbibition of the other variables studied. INTRODUCTION The process of imbibition, or spontaneous flow of fluids in porous media under the influence of capillary pressure gradients, occurs wherever there exist in permeable rock capillary pressure gradients which are not exactly balanced by opposing pressure gradients (such as those resulting from the influence of gravity). The importance of such capillary movement in the displacement of oil by water or gas was recognized in early investigations and described by Leverett, Lewis and True in 1942.1 Methods advanced by these authors for studying the process using dynamically scaled models were rendered more general and flexible by the research of later workers.2"4 The influence of capillary forces in laboratory water floods has also been discussed by several authors.6 While imbibition plays a very important role in the recovery of oil from normal reservoirs, Brownscombe and Dyes7 pointed out that imbibition might be the dominant displacement process in water flooding reservoirs characterized by drastic variations in permeability, such as in fractured-matrix reservoirs. In water-wet, fractured-matrix reservoirs, water will be imbibed from fractures into the matrix with a countercurrent expulsion of oil into the fractures. If the imbibition occurs at a sufficiently rapid rate, a very successful water flood can result; if the imbibition proceeds slowly the project might not be economically attractive. Scaled-model studies have demonstrated the vital importance of imbibition in secondary recovery in fractured reservoirs. It is therefore important in the evaluation of waterflooding prospects to develop a thorough understanding of the quantitative relationships of the factors which control the rapidity of capillary imbibition. The imbibition process serves reservoir engineers in still another important way by providing a technique for studying the wettability of reservoir core samples. Such experiments are usually conducted by observing the rate of expulsion of oil or water from core samples submerged in the appropriate fluid. Several papers have been 'published on the experimental techniques involved?? Although Handy has recently published a method for calculating capillary pressures from experiments with gas-saturated cores, it has not yet been possible to deduce quantitative information regarding water-oil relative permeability and capillary pressure characteristics of the rock from the experimental results. Thus a technique is needed for studying the quantitative dependence of imbibition rate on oil and water viscosity, initial water saturation, relative permeability-saturation, and capillary pressure-saturation relations. The development of such information, including saturation and pressure profiles by laboratory experiments, would be very difficult. However, recent advances in the applica-

Jan 1, 1965

By P. S. Kotval, H. Hahell

PRECIPITATION of M23C6 carbides at grain boundaries in austenitic steels and nickel base superalloys has received considerable attention. Hatwell and Berghezan,1 in a study using carbon extraction replicas, observed that dendritic growth of the M23C6 carbide phase occurred at grain boundaries in austenitic steels. Merrick and Nicholson2 have observed that in thin foils of "Nimonic 75" alloy the precipitation of M23C6 carbide was discontinuous at grain boundaries. Lewis and Hattersley3 have suggested that the type of M23C6 precipitation observed in Ni-Cr austenites represented the early stages of discontinuous precipitation. In a more recent study, Singhal and Martin4 have concluded that grain boundary M23C6 precipitation involves the migration of an austenite grain boundary by a mechanism very similar to that proposed by Tu and Turnbull.5 Tu and Turnbull's suggestion essentially involves grain boundary migration under the driving force arising from the difference between the surface free energies of the opposite sides of the plate. Thus, Singhal and Martin's observation4 implies that the first stage of discontinuous precipitation has taken place and that the grain boundary has provided a diffusion short circuit for the sub-stitutional solute atoms (principally chromium) which assist the preferential growth of the M23C6 plate in contact with the grain boundary. However, no evidence of the characteristic cellular morphology typical of discontinuous precipitation was found in Singhal and Martin's studies. Presumably, this is due to the low volume fraction (i.e., low supersaturation of solute) of the precipitating carbide reported by Singhal and Martin.4 Recently, Raymond6 has studied precipitation of the M23C6 carbide in Incoloy alloy 825 and shown that the growth of this phase is perpendicular to grain boundaries at 1400°F and in the plane of the grain boundary at 1700°F. The former aging condition resulting in discontinuous or "cellular" precipitation. Raymond has suggested an explanation for this behavior based on the relative rates of chromium diffusion by volume and grain boundary diffusion at the two different aging temperatures. In the course of a recent investigation on precipitation behavior in several ' strengthened superalloys, precipitation of M23C6 carbide at grain boundaries was studied. Under conditions of a high degree of supersaturation, the M23C6 carbide precipitates in the discontinuous or cellular morphology in Waspalloy (Ni-18.51 Cr-2.0 Fe-3.53 Mo-1.16 Al-2.78 Ti-0.09 C). This note presents electron microscopy observations of this mode of precipitation and its effect on mechanical properties. Specimens of Waspalloy after "solution" heat treatment at 1950°F show essentially single phase matrix with a few residual particles of "primary" MC carbide. In normal commercial heat treatments, precipitation of Ni3(Al,Ti) ordered fcc r' phase occurs throughout the matrix and M23C6 precipitates as globular particles at the grain boundaries. In these commercial heat treatments the degree of supersaturation during precipitation is low. However, if specimens of Waspalloy are quenched from the solution heat treatment temperature of 1950°F and then aged at an aging temperature where the degree of supersaturation is high, discontinuous precipitation of M23C6 occurs. Figs. 1 and 2 show thin foil micrographs of Waspalloy, solution heat treated at 1950°F, water quenched, and aged at 1292° and 1598°F, respectively, for 500 Fig. 1—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 500 hr at 1292°F. Magnification 15,500 times. Fig. 2—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 114 hr at 1598° F. Magnification 13,000 times.

Jan 1, 1970

By E. T. Hayes, A. H. Roberson, M. H. Davies

ZIRCONIUM has been produced on a pilot-plant scale for only a few years, but the potential uses have led a large number of research establishments to engage in a thorough study of the metal and its alloys. The work described in this paper is part of a cooperative project between the Bureau of Mines and the Air Materiel Command. The Zr-Cr system was one of the first investigated because of the possibilities of improving the properties at elevated temperatures, the chemical corrosion resistance, and the mechanical properties of zirconium in a manner similar to the enhancement of the properties of titanium by additions of chromium. There is no published work on the Zr-Cr system but from the similarity of the metals involved it was expected that it would be similar to the Zr-Fe' and Ti-Cr' systems. The materials used in this investigation were prepared in the Bureau of Mines laboratory at Albany, Ore. Zirconium was produced by magnesium reduction of zirconium tetrachloride, and a typical analysis is as follows: Fe, 0.06 pct; Ox, 0.08; N?, 0.01; C, 0.02; and other impurities such as Al, Pb, Ni, Ti, and Si less than 0.01 pct each. High purity chromium was prepared by treating crushed electrolytic chromium in a stream of dried and purified hydrogen." The resulting powder contained about 0.01 pct 0 and about 0.1 pct total metallic impurities. All alloys were prepared by arc-melting 50 g briquetted compacts of the desired composition in a Kroll-type" arc furnace using an inert atmosphere. The furnace was evacuated twice and backfilled with helium, which was gettered by melting a center zirconium button immediately before the alloys were melted. Alloys were remelted at least once to insure greater uniformity of composition and subsequently were annealed in vacuum at 1250°C for 48 hr. Fairly homogeneous alloys were obtained by this means; a slight loss of chromium from the surface by evaporation during the high temperature homogenization was noted. All alloys were analyzed for chromium and gave results in good agreement with the nominal composition. Spot checks on tungsten and nitrogen showed pick-up of these elements to be negligible. Over 70 alloys were prepared for use in this investigation; only the critical ones are shown in Table I. Alloys containing up to 10 pct Cr were amenable to hot working at 850°C and a number of these were sheath rolled to 1/16 in. thickness. Specimens were cut from the sheet for use as metallographic samples. For the thermal analysis a differential couple was used in conjunction with an X-Y recorder, the temperature of the specimen and the difference in ternperature between it and the standard nickel body were recorded simultaneously. Heating and cooling rates of 5°C per min were used. The sensitivity of the instrument was such that a difference in temperature between the specimen and standard equivalent to 0.1 mv produced a deflection of 1 in. on the recording chart. The chromel-alumel thermocouples were checked against a Bureau of Standards calibrated thermocouple. Melting-point determinations were made in a high vacuum induction furnace using an optical pyrometer. The pyrometer, calibrated against nickel, copper, and zirconium (iodide process) under near black body conditions, was focused on the base of a hole drilled in cylindrical samples. A North American Philips Geiger counter X-ray spectrometer was used for all diffraction studies. This instrument, in addition to supplying precise intensity measurements of planar reflections, has an added advantage in that metallographic specimens mounted in bakelite can be used directly, and this

Jan 1, 1953

By C. H. Li, S. H. Bendel, J. A. Sartell

Small additions of Mg to a 62 Cu-38 Ni alloy reduce the oxidation yates drastically between 500° and 850°C. Metallographic examination of the oxide scale disclosed a continuous network, identified by X-ray diffraction as (Ni, Mg)O solid solutions, located along the former alloy grain boundaries. This network acts as a barrier to diffusion. It is thought to result from the segregation of mg to the alloy grain boundaries. Oxidation occurs preferentially in these regions because of the presence of this more active element. To substantiate these ideas, homogenized alloys ulere oxidized. No oxide network was produced and oxidation rates were the same as for the parent 62 Cu-38 Ni alloy. An interesting aspect of the oxidation of the 62 Cu-38 Ni alloy previously described by the present authors, is the relationship between oxidation kinetics and changes in the microstructure of the oxide.' The oxide scale on these alloys consists of two layers: a thin layer of CuO outside a much thicker layer of Cu20 in which particles of NiO are dispersed. In addition, immediately beneath the oxide-metal interface there is an internally oxidized zone in which NiO particles are dispersed in a copper-rich alloy matrix. Experimental observations on the growth of the individual layers under isothermal conditions have led to the conclusion that the rate-determining step in the oxidation of this alloy is the diffusion of anions through the Cu20 layer. It has been found that this diffusion rate is increased by the recrystallization of the outer CuO layer. Willardson and Gorton have reported that the addition of magnesium to the 62 Cu-38 Ni alloy causes a decrease in the oxidation rate.2 The present investigation was undertaken in order to determine the mechanism by which magnesium additions improve the oxidation resistance of the 62 Cu-38 Ni alloy. EXPERIMENTAL PROCEDURE Fifty-gram ingots of Cu-Ni alloys were prepared by vacuum melting materials of 99.999+ pct purity. These ingots were then remelted in a He atmos- phere and magnesium added in the form of a previously prepared and analyzed Cu-Mg master alloy. This procedure was necessitated by the high reactivity of pure magnesium at high temperatures. The proportion of the alloying elements was adjusted so as to obtain alloys with the desired magnesium content while maintaining a Cu-Ni ratio of 62 :38 by weight. (All alloy compositions will be given in weight percent.) Since it was considered desirable to study the oxidation of only single-phase, solid-solution alloys, it was necessary first to determine the approximate limit of solid solubility of magnesium in the 62 Cu-38 Ni alloy. A series of melts with various magnesium contents was made, homogenized by annealing for 48 hr at 975OC, then cooled in the furnace. Metallographic samples were prepared, etched in a potassium dichromate solution and examined at XI500 for the presence of a second phase. The alloys were then chemically analyzed and it was found that the approximate limit of solid solubility of magnesium in the 62 Cu-38 Ni alloy was 1 pct Mg. The ingots containing less than 1 pct Mg (0.19, 0.29, 0.58, and 0.87 pct Mg) were cold-rolled down to thicknesses suitable for oxidation experiments and specimens for gravimetric studies were cut to dimensions of 3.0 by 1.5 by 0.05 cm, specimens for inert marker studies, 0.6 by 0.6 by 0.17 cm. These were heat-treated in a protective atmosphere at a temperature (975" C) well above the oxidation temperatures and furnace-cooled to insure structural stability of the alloy during oxidation. Immediately prior to oxidation, the specimens were chemically cleaned by immersion for 1 min in a solution of 2 parts nitric acid, 1 part acetic

Jan 1, 1961

By A. D. Schwope, L. R. Jackson, K. F. Smith

Burghoff and Blank1 have pointed out that the creep properties of hard-drawn coppers are closely associated with their individual softening characteristics and have further shown that the creep resistance of various types of copper is improved, under certain circumstances, by cold stretching. In the design of certain types of electrical machinery, it is important to have the creep resistance as high as possible; furthermore, short-time creep strength is important since in many cases stresses are large only during warming-up and cooling-down periods. In this paper, data are presented showing the effect of cold work on the short time creep strengths of various types of commercial copper under several conditions. It is shown that trends from short-time creep tests are evident at longer times. Materials Used in the Investigation The coppers used in this investigation were commercial grade and of two basic types, oxygen free high conductivity (OFHC) and tough pitch. Additions of silver in amounts of 15 and 25 oz per ton were added to each of the two coppers. The analyses of these six coppers are given in Table 1. Originally, they started as wire bars 4 X 4 X 54 in. A. square rod was made by hot rolling the wire bars to 9/16-in. rod in 8 passes. This rod was then cold drawn to 0.445-in.-diam rod and annealed for 3 1/2 hr at 1000°F. It was then cold drawn to 0.325-in. rod and again annealed at 1000°F for 3 1/2 hr. Hard square rods were then made by cold rolling to 0.257 X 0.257-in. rod. Soft wire was made from the hard- drawn material by annealing at 650°F for 3 hr. The final rolling was performed using a set of 9-in. grooved rolls revolving at 30 rpm, which produced square wires. Reductions of approximately 5, 20, 30, and 40 pct were obtained using several passes in the same direction for the large reductions. The 5 pct reduction by drawing was accomplished using a steel die having 2 parallel bearing surfaces. The die angle was 7 1/2 degrees and the wires were lubricated with a paste of ceresin wax dissolved in carbon tetrachloride. The speed of drawing was 13 fpm. Since work was done on only two sides of the wire simultaneously, it was necessary to rotate it 90 degrees each pass to insure uniform deformation. The room-temperature tensile properties of the various tempers are given in Table 2. The grain size of the an- nealed 0.257-in. wires was uniform and averaged about 0.035-0.045 mm. Experimental Procedures for Short-time Creep Tests Standard creep-test frames (Fig 1) were used for the testing. Special fixtures were designed to apply axial compressive and tensile loads to the copper wires. The compression specimens were 1 in. long and the ends were ground flat and parallel. The creep in compression was indicated by the movement of reference marks s-ratched on intersliding platinum strips attached to the moving heads of the fixture. The movement was measured with an optical micrometer fitted with a filar eyepiece on which the smallest division was 0.00005 in. The tensile creep specirriens were 4 in. long which provided ample gripping surface for the jaw-type grips. The platinum strips were attached to a one-inch gauge length of the wire and the creep measured as previously described. The single-specimen furnaces were connected to individual power and control sources. The controlling equipment consisted of Foxboro controllers

Jan 1, 1950

By D. Harker, W. E. Seymour

CERTAIN alloys of iron and nickel, when rolled and annealed, possess a preferred crystal orientation: (001) in the rolling plane and [loo] in the rolling direction, when recrystallized at 850" to 1050°C after approximately 98 pct cold reduction. Since the preferred orientation makes a direction of easiest magnetization coincide with the rolling direction, these alloys, especially a 50 pct iron in nickel alloy, have found wide application in the electrical industry' for choke coils and special types of transformers. The rate of the recrystallization reaction was studied at temperatures ranging from 500° to 600°C. The heat of activation for the reaction was calculated from the observed rates, and crystal orientation determinations were made before and after re-crystallization. A vacuum melted iron-nickel alloy* analyzing 49.6 pct nickel, 0.018 pct carbon, and 0.30 pct manganese was used for the experiments. The alloy was cold-rolled 98 pct into strips 1/2 in. wide by 0.002 in. thick. Specimens 1 in. long were sealed under a vacuum (approximately 10-8 mm Hg) in 1/2 in. ID pyrex glass tubes. For heat treatment these tubes were fastened to Nicrohm wires and submerged in a molten salt bath controlled to ±2°C. (The maximum measurement error was within 3°C.) The time at temperature was varied logarithmically from one sample to another, and runs were made at 500°, 525", 550" and 575°C. A molten lead bath was used for a run at 600°C which was controlled to the same accuracy. To determine the extent of recrystallization after a particular time at a given temperature, a method was used suggested by the work of Decker, Asp, and Harker.3,4 This method employs an X-ray spectrometer whereby X rays are diffracted from crystallites whose diffracting atom planes are parallel to the rolling plane of the specimen. The intensities of the diffracted rays are measured by a Geiger counter. The counter can be rotated through a range of angle, and can be motor driven through this range at a speed of 2" per min. The measured intensities are plotted vs. angle by a potentiometer recorder. In a 50 pct iron-nickel alloy it was found that only (200) reflections were obtained from the rolling plane with recrystallized material, and that only (220) reflections were obtained from the rolling plane with unrecrystallized material. No other reflections were obtained under these conditions over a range of Bragg angle of 0 to 45" using either type of specimen. As a consequence, the intensity of the (200) reflections from the rolling plane was taken to indicate the amount of recrystallized ma-terial present in a specimen, and the corresponding intensity of the (220) reflections was taken to indicate the amount of unrecrystallized material present. To insure flatness and proper alignment of the reflecting specimen in the spectrometer, the sample was laid in a slot 1/2 in. wide x 0.001 in. deep which was machined in a 3/4x2x1/2 in. steel carrier. The specimen then was taped down with cellophane tape. This steel cradle was mounted vertically in the specimen holder of the spectrometer so that the bottom edge of the carrier rested against a horizontal shoulder. Intensity data used in plotting the percent of recrystallized material vs. time at temperature were obtained by directly counting the diffracted beam of nickel filtered copper Ka radiation used throughout the work. The X-ray spectrometer was employed also in obtaining pole figure data to be used for orientation determinations. At the beginning of this investigation a transmission pole figure holder was used." As a thickness of 0.002 in. of this alloy was found to be opaque to the copper Ka radiation, it was necessary to reduce the thickness of the pole figure specimen. A cold-worked sample was etched in a 50 pct HCl solution for 5 min and was found to transmit a

Jan 1, 1951

By B. B. Wood, M. J. Rzasa, E. W. Hough

An apparatus for the determination of fluid-fluid interfacial tension by the pendant drop method has been constructed. The apparatus is refined beyond those previously described in that the samples are introduced into an evacuated windowed cell without contacting air or mercury. Interfacial tension data are reported for the water-methane system between 74 and 280°F and 15 and 15,000 psi. The variation of wettability of the stainless-steel dropper tip with pressure and temperature was observed incidentally to the measurements. INTRODUCTION The most refined previous apparatus --for the determination of fluid-fluid interfacial tension at reservoir conditions was built by Hauser and Michaels.' These authors used the pendant drop method, previously investigated by Andreas, Hauser, and Tucker.' Recently, Fordham3 has made the pendant drop method an absolute one by numerical integration of the differential equation of drop shape. It is necessary to know the difference in density of the two fluids and the acceleration due to gravity in order to evaluate the interfacial tension from measurements of drop dimensions. Contact angle is not involved in the measurements by this method. Some precise tests of the method have been made at atmospheric pressure and 77°F by Douglas," who found agreement with established values to within about 0.1 per cent for water and air, cyclohexane and air, benzene and air, and benzene and water. No values of interfacial tension from the recent pendant drop apparatusJ have been published by Hauser and Michaels. However, values for the water-benzene and water-decane systems are given in Michaels' thesis5 or Dressures from 15 .to 10,000 psi and temperatures from 73 to 268ºF. Some determinations on gas-oil and gas-water systems in the range of 15 to 4,000 psi and 78 to 178°F have been made by Hozott,' by the drop-volume method. The capillary rise method has been used to investigate the interfacial tension in gas-oil systems at 88°F to several thousand psi by Swartz.7 Other determinations in gas-oil systems at pressures under 1,000 psia have been made by Jones: and Beecher and Parkhurst.9 The scarcity of data for pressures above 5.000 psi is apparent. APPARATUS An assembly drawing of the working section of the interfacial tenqion apparatus is given in Fig. 2. 'The endanant drop (A) is housed in a pressure chamber having glass windows (B). An agitator (6) is provided. The metal parts of the apparatus coming into contact with the sample are made of AISI: Type 316 steel. Drain grooves are provided around the whdows so that the sample in contact with the O-rings is not returned to the working section when the pressure is reduced. A schematic arrangement of the apparatus is given in Fig. 3. The working section containing the pendant drop (A) is filled by samples from bombs (B) with the aid of the vacuum system (C). The O-ring sealed pistons (D) used to separate the sample from the hydraulic fluid are shown together with the pressure production and measurement system (E). A front view of the apparatus is shown in Fig. 1. Most of the hydraulic system is at the top of the panel. The pump and displacement piston are at the lower right. The Variacs for the air bath heaters. the camera. and the vacuum gauge are a1so visible on the panel. The working section together with a window closure and a drop-forming tip closure are shown in Fig. 9. The carbon arc light source with filter is visible in the upper part of the picture. Two sides of the air bath with the impeller and a part of the convection shield can also be seen. The assembled air bath is shown in Fig. 10.

Jan 1, 1951

By Robert D. Pehlke, Weldon L. Daines

The reduction of manganese oxide from a basic slag by silicon dissolved in liquid iron at steelmaking temperatures was studied to determine the rate-controlling step for the process. The experiments were carried out under an argon atmosphere in a resistance-heated vertical-tube furnace. The two liquid phases, slag and metal, were held in zirconia crucibles. Sampling and chemical analysis of the slag phase led to time-concentration curves for the system. Results obtained by varying parameters such as temperature, stirring rate, concentration, and melt geometry defined the limiting reaction mechanism. The reduction of manganese oxide by silicon is a fast reaction and reached equilibrium within 90 min. The rate of stirring has a marked effect on the reaction rate, while, on the other hand, the effect of temperature is very small. This identifies the rate-controlling step as diffusion rather than interfaciul chemical reaction. The variation of other parameters revealed that a) diffusion of manganese in the iron phase is the slow step, b) the value of D/6 for manganese in iron at 1550°C is 7x 10-4 cm per sec, c) the energy of activation for the apparent rate constant is 7 kcal per mole, and d) increasing the amount of silicon in the iron decreases the diffusion coefficient of manganese. THE equilibrium relations pertinent to the reduction of manganese oxide from a steelmaking slag by silicon dissolved in liquid iron have been studied, but little is known about the mechanisms that control the rate of the process. The purpose of the present investigation was to study the rate of reduction by silicon and to determine the rate-limiting step. The effects of stirring rate, temperature, composition, and melt geometry were investigated as a means of identifying the controlling step. On the laboratory scale, relatively little work has been done in the area of slag-metal kinetics, primarily because of the problems confronted in attempting to contain liquid slags and metals in laboratory crucibles at steelmaking temperatures. Since graphite is an ideal material for a crucible, several investigations have been carried out on the reduction of various oxides from a slag by carbon in graphite-saturated iron and on the transfer of sulfur between a slag and graphite-saturated iron. Most of this work has been performed in induction furnaces. Studies where the container was not graphite are extremely limited. A single kinetic study of manganese transfer between molten iron and basic slags was carried out by Sano, Shiomi, and Matsushita.' These investigators prepared calcium oxide and titanium oxide crucibles to contain the two-phase system. Only a few experiments were carried out and the results had to be treated qualitatively. Despite the paucity of kinetic data, a large quantity of information is available in the literature concerning the thermodynamics2-12 and physical properties'3-21 of the slags containing manganese oxide and the dilute liquid iron alloys containing manganese and silicon which were involved in this research program. EXPERIMENTAL METHOD A vertical-tube resistance-heated furnace was used in this investigation to study the slag-metal reaction Although most previous slag-metal studies were carried out in induction furnaces, a resistance furnace has several advantages including better control of temperature and stirring rate. Hence, a resistance furnace was selected for this study, and its design is shown schematically in Fig. 1. Slip-cast, fine-grained, low-porosity, lime-stabilized cubic zirconia crucibles were used for the kinetic experiments. The crucibles were 4 1/2 in. high and 2 1/8 in. OD with a 1/16-in. wall. The crucibles were only slightly

Jan 1, 1969

By Tasuku Fuwa, John Chipman, David H. Kirkwood

Fe-C-Si alloys in silica crucibles were held at 1600°C in a controlled atmosphere of CO and Co2 and the approach to equilibrium was obsertsed. Results were not of sufficient precision to establish the activity and interaction coefficients. Observations 012 the equilibrium provided an average value for the standard free-energy change which differed by + 1.1 kcal from the earlier accepted value. The C-SL relation at other temperatures is calculated and shown graphically. IN the refining of steel in an acid-lined furnace, it is well known that, unlike in basic refining, a very significant amount of silicon may remain dissolved in the metal even when the carbon content approaches a final endpoint. Further, it is known that the residual silicon increases with increasing temperature. The quantitative relation between silicon and carbon can be calculated for equilibrium conditions from data already available on the Fe-C-O and the Fe-Si-O systems. Such equilibrium calculations could show us approximately the limitations within which the reaction would be expected to operate in practice. In the oxidation of a bath containing both carbon and silicon it is well known that at low temperatures silicon is preferentially oxidized first. It can be shown by calculation that at high temperatures carbon will be oxidized preferentially. It is the purpose of this paper to record direct observations on the Si-C relation by means of experiments carried out in an atmosphere of carbon monoxide for Fe-C-Si alloys contained in silica crucibles. When such a system is brought into equilibrium, at a fixed temperature, the composition of the liquid metal is governed by the following equations: Both K1 and K2 are known with a fair degree of accuracy, and may be calculated from the tabulated In general the percentage of CO2 is extremely small compared to that of CO and in the experiments to be described the partial pressure of the latter was generally only slightly below 1 atm. EXPERIMENTAL METHOD The induction furnace employed was the same as that described by Rist and chipman' and by Fuwa and chipman.2 It was modified slightly in view of the change from alumina to silica crucibles. The small silica crucible was surrounded by a thin susceptor of molybdenum sheet which in turn rested inside a zirconia crucible. Since the zirconia was subject to breakage, it was supported inside an alumina crucible. The charge consisted of 30 to 35 g of electrolytic iron along with the required amounts of refined silicon and graphite to produce a melt of required composition. Purified carbon monoxide and carbon dioxide were passed into the furnace through carefully calibrated flow meters. Two separate and independent series of experiments were carried out. In Series I (D.H.K.) the melt was held in the furnace at 1600°C for periods of time up to 6 hr. Samples were taken at intervals in silica tubes and were analyzed for carbon and silicon. The results of the last one or two samples taken from each experiment and the direction in which equilibrium appeared to be approached are shown in Table I. In Series II (T.F.) the silica crucibles were of less satisfactory strength and the melts were held at 1600° C for periods of only 2 to 4 hr. In heats number 29 to 45 inclusive, the metal was cooled in the furnace and the ingot itself served as a sample for analysis. In heat 46 and all subsequent heats, samples were withdrawn in silica tubes at the termination of the heat, and these samples were analyzed. The results of all of these experiments in which equilibrium appeared to be approached are listed in Table II.

Jan 1, 1965

By Pol Duwez

The effect of the rate of cooling on titanium, zirconium, and thallium has been measured. For titanium-molybdenum alloys, it has been shown that for molybdenum concentration up to 8 pct the rate of cooling has no effect on the transformation temperature, but this temperature decreases progressively with increasing molybdenum content. HIGH strength to weight ratio and remarkable corrosion resistance have often been advanced as the main reasons for the present widespread interest in titanium. For the physical metallurgist, the existence of an allotropic transformation in titanium is another important factor. As in the case of iron, an allotropic transformation may be the fundamental property upon which the response of Ti-base alloys to heat treatment will depend. It is therefore important to study the mechanism of the allotropic transformation in pure titanium and the effect of alloying elements on this transformation. The existence of an allotropic transformation in titanium was reported in 1931 by Schulze.' Later, De Boer et al.' determined the transformation temperature from a discontinuity in the electrical resistivity at 882"42O°C. According to recent work," the transformation temperature is 882.5"&1°C. The crystal structure of the room temperature a phase is hexagonal close-packed and the high temperature fi phase is body-centered cubic.' It is well known that the high temperature /3 phase of pure titanium cannot be retained by quenching to room temperature. Several investigators'-' have shown that in alloys of titanium with metals which are soluble in the @ phase (for example, nickel, molybdenum, chromium, or manganese), the /3 structure can be retained, providing the concentration of the alloying element is greater than a certain critical value. Below this critical value, the alloys transform during quenching, at least partially, into a supersaturated solid solution having the a. structure. This behavior is very similar to that found in some iron binary alloys (Fe-Ni and Fe-Mh, for example) and is an indication that the transformation might occur by means of a shear mechanism analogous to that observed in the austenite-martensite reaction. The present investigation is mostly concerned with the effect of the rate of cooling on the /3 to a transformation. In the first portion of this paper, the results obtained on pure titanium are described. Two other pure metals, zirconium and thallium, were also investigated, because they both have an allotropic transformation like titanium, from an hexagonal close-packed to a body-centered cubic structure. For purposes of comparison, the effect of rate of cooling of the y to a transformation of iron was included in the experimental program. The second part of this paper deals with Ti-Mo alloys. The equilibrium phase boundaries involving the solid state reactions on the Ti-rich side of the system were determined and a study was made of the effect of the rate of cooling on the transformation of the high temperature /3 solid solution. Experimental Procedure Since the main object of the present investigation was the determination of the effect of the rate of cooling on a transformation temperature, the best technique available was that used by Greninger" in his study of the martensite arrest in carbon steels. This method consists of heating a very small sample of metal to which fine thermocouple wires are .attached, cooling the sample rapidly by means of a blast of helium, and recording the temperature vs. time curve on an oscillograph. The apparatus used in the present experiments was very similar to that described by Greninger, except that the heating coil was made of molybdenum wire (0.040 in. in diam) and the assembly was placed in a bell jar under vacuum of 10" mm Hg or less. The specimen con-

Jan 1, 1952

By J. L. Lytton, T. E. Tietz

The recovery of flour stress of recrylstallized are-cast molyhdenum after 10 pet prestrain at 150°C was studied for recovery temperatures of 725o 801o and 901oC. The yield phenomenon observed after recovery was such that the yield drop diminished and disappeared as recovery proceeded. A fractional flow-stress recovery parameter fr, was developed and it was shown that, independent of recovery ternperatzwe, equal f, values of about 0.16 produced superposition of stress-strain curves except for the initial yield phenomenon. The activation energy for low degrees oj recovery was found to he 32,600 cal per mole, in close agreement with a reported valzie for difjzdsion of carbon in molybdenum. For values of fr greater than about 0.15 where recovery was thought to predominate over strain aging, the activation energy varied from 43,600 to 82,500 cal per mole and increased with increasing recovery and recovery temperature. A 10 pet pre-strain shifted the ductile-brittle transition temperature, as indicated by tensile elongation, from 10°C. to about -22"C. A 100-hr recovery anneal at 801oC was shown to shift the transition temperature to about —5oC, the major shift occurring during the first hour of recovery. ThE recovery of cold-worked metals is accompanied by changes in the arrangement of the dislocations generated during cold work. In recent years, the use of transmission electron microscopy has allowed direct observation of some of the dislocation configurations formed, such as "tangles", networks, cells, subboundaries, and loops. These observations have recently been reviewed by Keh and Weissmann.' Accordingly, some understanding has been gained concerning the nature of the dislocation rearrangements involved. The relationship between recovery and the decrease of mechanical strength, however, has only recently been explored. Previous efforts of the authors were directed toward investigating the decrease of tensile flow stress of aluminum and Al-1 pet Mg during recovery2 and the effects of concurrent elastic and plastic strain on the flow-stress recovery of aluminum.3 In addition, an investigation of the effect of four different solute additions on the tensile flow-stress recovery of aluminum has been made.4 Many important metals, however, have the bee crystal structure, e.g., iron, molybdenum, tungsten, vanadium, columbium, tantalum, and chromium. These metals might be expected to behave differently during recovery from those with other crystal structures for two reasons. First, the previous and present investigations of aluminum and its alloys have shown that tensile flow-stress recovery is strongly affected by foreign atoms in the lattice. In the bee metals, interstitial impurities are usually present and might be expected to have various effects upon both flow behavior and recovery. For example, heterogeneous yielding might occur during prestraining. The diffusion of these interstitials can also relock dislocations during recovery so that a yield point might be obtained upon restraining (strain aging). Second, some of the bee metals (e.g., iron, molybdenum, and tungsten) undergo the familiar structure-sensitive ductility transition and exhibit brittle fracture at suitably low temperatures. It is of considerable interest to determine the effects of recovery on the transition temperature of such metals. The purpose of the present investigation was to extend our knowledge of flow-stress recovery to the bee metals and to study the effects of recovery on the ductile-brittle transition temperature. Unalloyed recrystallized are-cast molybdenum was chosen as a test material, since it exhibits a well-defined ductility transition near room temperature. As in the previous studies, the degree of recovery was measured in terms of the decrease of tensile flow stress. Prestraining and restraining were carried out at 150°C to avoid the possibility of brittle fracture. EXPERIMENTAL PROCEDURE The are-cast molybdenum sheet used in this investigation was obtained from the Climax Molybdenum Co. of Michigan. It was 0.060 in. thick by 10

Jan 1, 1964

By J. H. Scaff, H. C. Theurer, E. E. Schumacher

The microwave region of the radio spectrum was effectively utilized in radar designs during the recent war and it has become of increasing interest in the field of communications. Work in this field has led to an important use for silicon—that of the point contact rectifiers†1 in the frequency converter of microwave (radar or radio) receivers—and has stimulated considerable interest in the electrical properties and preparation of silicon and its alloys. Silicon is an electronic semiconductor. Its conductivity at room temperature results principally from the presence of certain impurities. While for metals an increase in impurity content increases the resistivity, for semiconductors such as silicon the opposite occurs and, in general, the addition of impurities lowers the resistivity. Silicon materials may be classified into one of two groups depending upon the manner in which the impurities contribute to electrical properties. These have been termed for convenience p-type or n-type. P-type silicon develops a very large positive thermal emf against metals, has a Hall coefficient of positive sign and a low resistance direction in point contact rectification with the silicon positive with respect to the point. N-type silicon, on the other hand, develops a negative thermal emf against metals, has a Hall coefficient of negative sign and a low resistance direction in rectification with the silicon negative with respect to the point. Impurities which produce n-type silicon are called donors inasmuch as these elements contribute to electrical conductivity by donating electrons to an unfilled energy band in the silicon. On the other hand, elements which produce p-type silicon are known as acceptors as these impurities contribute to the electrical conductivity by accepting electrons from a filled energy band permitting what is known as conductivity by "holes" in which the sign of the carriers appears to be positive. A general treatment of the mechanism of conduction in semiconductors from the viewpoint of modern band theory has been given recently by Pearson,2 by Becker, Green and Pearson,3 and by Torrey and Whitmer.4 In this investigation boron and aluminum have been found to be acceptors, and phosphorus, arsenic, and antimony to be donors in silicon. Data on the effect of boron and phosphorus on the electrical properties, when present singly and in combination, have been acquired. These data are discussed in the present paper. Raw Materials Used and Methods for Adding Seeond Constituents Silicon from two sources was used in this work and these will be referred to as A and B respectively. Silicon A is a material of high purity supplied by the Electro Metallurgical Co. It is prepared by chemical purification of "commercial" silicon obtained from the arc furnace reduction of SiO2. It contains 99.8 pct silicon, minimum, with small amounts of calcium, iron, aluminum, boron, and phosphorus as the principal impurities. This material was extensively employed in these studies as well as in the commercial preparation of rectifier materials. Silicon B is a material of high purity from the du-Pont Co. It is prepared by a pyrolytic reduction of Sicl4 and is free of analytically detectable amounts of boron and phosphorus. Its use permitted study of the effect of boron and phosphorus individually on the properties. This material contains, however, spec-troscopic traees of a number of metals, some of which affect electrical and rectification properties. Typical analyses for the two grades of silicon are given in Table 1. To make controlled additions of boron to the charge it was necessary to employ a low boron content master alloy since the quantity of boron to be added was usually only a few thousandths of one percent. The alloy containing nominally one percent boron was prepared by melting chemically pure boron with silicon A using the melting techniques for 320 g silicon

Jan 1, 1950

By P. Chiotti, J. T. Mason

Thermal, X-ray, metallographic, and resistivity data were obtained to establish the phase diagram for the Yb-Zn system. Six intermetallic compounds and five eutectics have been identified. The compounds position at 695°C. No evidence for the compound YbZn,, was observed. Whether this compound is stabilized or inhibited by small amounts of impurities is uncertain. SEVERAL aspects of the Yb-Zn system have been reported in the literature. Much of this work deals with the crystallographic identification of some of the compounds. The YbZn compound has been reported by Iandelli and palenzonal and the YbZn, structure and thermal data for the composition range between YbZn and Yb3Znll have been reported by Michel et al. A compound of uncertain stoichiometry in the range 60 to 68 wt pct Zn with a cubic structure has been reported by Kuz'ma et aL4 The YbzZn17, YbZn,,, and YbZn13 compounds have been reported by both Kuz'ma et a1 and Iandelli and Palenzona.' YbnZn17 has also been identified by Laube. This investigation was undertaken to establish the phase diagram of this system. Ytterbium in many respects behaves as an alkaline earth rather than a rare earth metal6 and it is of interest to note the resemblance between the Yb-Zn system, the Ca-Zn,' and typical rare earth-zinc systems.g'10 MATERIALS AND EXPERIMENTAL PROCEDURES The materials used in this investigation were Ames Laboratory ytterbium and Bunker-Hill slab zinc, 99.99 pct pure. Analyses of the ytterbium showed 38 ppm Ta, 82 ppm 0, and 15 ppm N with Ca, Cu, C, Mg, Al, Si, Cr, Fe, Ni, Sc, Y, Er, Tm, and Lu all less than 50 ppm. The ytterbium was dehydrogenated by heating in tantalum under vacuum for 8 hr at 900°C. The metal was kept under argon except when being cut with shears and when being weighed. Tantalum was found to be a suitable container for alloys in the composition range between ytterbium and Yb2Zn17. With higher zinc concentrations the tantalum was penetrated by the alloy and failed after several days at temperatures of 600" to 700°C. Approximately 20 g of zinc and ytterbium metal were sealed under argon in *-in.-diam tantalum cruci- bles equipped with thermocouple wells. The crucibles were in turn sealed in stainless-steel jackets. The alloys were equilibrated in an oscillating furnace and given various heat treatments in a soaking furnace. The steel jackets were removed and differential thermal analysis data were obtained under an atmosphere of argon. The thermal analysis apparatus was calibrated against the melting points of pure zinc, aluminum, silver, and copper and found to give thermal arrests within 1°C of the accepted melting temperatures for these elements. The thermal analysis apparatus has been described in an earlier paper.g Alloys were further heat-treated as necessary and subjected to metallographic examination and X-ray diffraction analysis. Most alloys were etched with Nital (0.5 to 10 pct nitric acid in alcohol). EXPERIMENTAL RESULTS The results of the thermal analysis are summarized by the points on the phase diagram, Fig. 1. Six compounds and five eutectics were observed. The eutectic temperature and compositions in weight percent zinc are 491°C and 12 pct, 645°C and 32 pct, 687°C and 54 pct, 742°C and 67 pct, and 750°C and 77 pct. The compounds YbZn, YbZn2, Yb2Zng, Yb2Zn17, and YbZnll melt congruently at 650°, 751°, 75Z°, 754", and 755"C, respectively. The compound Yb3Znll undergoes a peritectic decomposition at 695°C. The transformation and melting temperatures for the ytterbium were observed to be 797" and 817°C. re-

Jan 1, 1969

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-' to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6'9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3'5'7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5'7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f '([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1' Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962

By S. F. Frederick, W. A. Bailey

The relationship between microstructure and mechanical properties of cast 356-type aluminum alloys was studied to determine the cause of the variations in properties resulting from differences in solidification rate. It was found that variations in strength are a consequence of variations in ductility and that ductility is inversely proportional to the dendrite cell size. A mechanism is proposed to account for this correlation based on the fracture strain of the inter-dendritic silicon particles and the differential strain across dendrite cell boundaries. IT has long been assumed that permanent mold castings of aluminum are superior to sand castings because of their finer grain structure and reduced porosity.' A systematic variation of static properties was noted during unpublished studies of fatigue-strength variations with solidification rate of A356-T6. Of particular interest was the observation that for a given composition and heat-treatment, both ductility and the ultimate strength increased with higher solidification rate. Because the A1-Si system forms the basis of many alloys used for castings and welding wire, a study was initiated to determine the details of how higher cooling rates improved mechanical properties of these alloys. The results of this study are presented here. EXPERIMENTAL PROCEDURE Specimens were prepared from 356-T6 to supplement the A365-T6 alloy data from earlier studies. This allowed a comparison of behavior of alloys with substantially different strengths but with only small differences in alloy composition. The composition and heat treatment of both alloys are given in Table I. The specimens were cut from a chill plate casting,' which is a 6 by 9-in. plate, 1 in. thick, which has one end heavily chilled, and a large riser at the other so that solidification is essentially unidirectional from the chill end to the riser. Although not measured here, solidification times measured on similar specimens by embedded thermocouples are a few seconds at the chill end and up to 5 min near the riser. Specimens were obtained by cutting slabs from the plate, parallel to the chill; these represented different cooling rates, with essentially the same composition. For the tests, either 0.125 or 0.250-in. thick slabs were cut for standard 2-in. gage length specimens. The thicker specimens were tested to failure at 2000 lb per min while the thinner specimens were tested in an Instron machine at a constant cross-head speed of 0.02 in. per min. These thin specimens were intended for trans- mission electron microscopy. Some thin specimens were tested to failure while the remainder were given various amounts of prestrain. Dendrite cell sizes were measured by the linear intercept method on photomicrographs at either X100 or X50, depending on the cell size. It was assumed that the dendrite cells were outlined by the silicon particles. Determinations were made on two mutually perpendicular planes and an rms average taken. Electron fractographs of representative tensile specimens were made in the conventional manner using the two-stage replica technique.3 Samples for transmission electron microscopy were prepared by chemical milling followed by electropolishing. RESULTS AND DISCUSSION The results of the tensile tests and the dendrite cell-size determinations are given in Figs. 1 and 2. All data show the same trends, namely, a decrease in ultimate strength and elongation with increasing distance from the chill (and solidification time), and a corresponding increase in dendrite cell size. The yield strength remains essentially constant. The constancy of the yield strength was particularly significant since it indicated that variation in the solidification rate does not affect the stress required to initiate plastic flow. By plotting true stress-true strain curves as in Fig. 3, it can be seen that both

Jan 1, 1969

By E. W. Hough, B. B. Wood, M. J. Rzasa

An apparatus for the determination of fluid-fluid interfacial tension by the pendant drop method has been constructed. The apparatus is refined beyond those previously described in that the samples are introduced into an evacuated windowed cell without contacting air or mercury. Interfacial tension data are reported for the water-methane system between 74 and 280°F and 15 and 15,000 psi. The variation of wettability of the stainless-steel dropper tip with pressure and temperature was observed incidentally to the measurements. INTRODUCTION The most refined previous apparatus --for the determination of fluid-fluid interfacial tension at reservoir conditions was built by Hauser and Michaels.' These authors used the pendant drop method, previously investigated by Andreas, Hauser, and Tucker.' Recently, Fordham3 has made the pendant drop method an absolute one by numerical integration of the differential equation of drop shape. It is necessary to know the difference in density of the two fluids and the acceleration due to gravity in order to evaluate the interfacial tension from measurements of drop dimensions. Contact angle is not involved in the measurements by this method. Some precise tests of the method have been made at atmospheric pressure and 77°F by Douglas," who found agreement with established values to within about 0.1 per cent for water and air, cyclohexane and air, benzene and air, and benzene and water. No values of interfacial tension from the recent pendant drop apparatusJ have been published by Hauser and Michaels. However, values for the water-benzene and water-decane systems are given in Michaels' thesis5 or Dressures from 15 .to 10,000 psi and temperatures from 73 to 268ºF. Some determinations on gas-oil and gas-water systems in the range of 15 to 4,000 psi and 78 to 178°F have been made by Hozott,' by the drop-volume method. The capillary rise method has been used to investigate the interfacial tension in gas-oil systems at 88°F to several thousand psi by Swartz.7 Other determinations in gas-oil systems at pressures under 1,000 psia have been made by Jones: and Beecher and Parkhurst.9 The scarcity of data for pressures above 5.000 psi is apparent. APPARATUS An assembly drawing of the working section of the interfacial tenqion apparatus is given in Fig. 2. 'The endanant drop (A) is housed in a pressure chamber having glass windows (B). An agitator (6) is provided. The metal parts of the apparatus coming into contact with the sample are made of AISI: Type 316 steel. Drain grooves are provided around the whdows so that the sample in contact with the O-rings is not returned to the working section when the pressure is reduced. A schematic arrangement of the apparatus is given in Fig. 3. The working section containing the pendant drop (A) is filled by samples from bombs (B) with the aid of the vacuum system (C). The O-ring sealed pistons (D) used to separate the sample from the hydraulic fluid are shown together with the pressure production and measurement system (E). A front view of the apparatus is shown in Fig. 1. Most of the hydraulic system is at the top of the panel. The pump and displacement piston are at the lower right. The Variacs for the air bath heaters. the camera. and the vacuum gauge are a1so visible on the panel. The working section together with a window closure and a drop-forming tip closure are shown in Fig. 9. The carbon arc light source with filter is visible in the upper part of the picture. Two sides of the air bath with the impeller and a part of the convection shield can also be seen. The assembled air bath is shown in Fig. 10.

Jan 1, 1951

By H. Biloni, B. Chalmers

Metallographic studies of the segregation of solute in and near the surfaces of chill-cast alloys have shown that, under sufficiently severe conditions, nucleation on the cold mold surface is followed by the formation of a disc of solid of the same composition as the liquid. This disc is surrounded by two concentric rings in which the concentration first decreases and then increases. The discs and rings are surrounded by a region in which arms of low solute concentration separate regions of high concentration. These arms start at the periphery of the outer ring and are initially radial; they make a gradual curved transition from the radial direction to a crystallographic direction. A normal dendritic substrcture is established beyond the position at which the arms have become crystallographically aligned. When the cooling is less severe, the disc becomes less irregular in shape and has a concentration minimum at the center. The term "Predendritic" is proposed for these transitions. A qualitative explanation is outlined for the phenomena observed at the surface and in the equiaxed region of the ingots. It is well-established1-' that the normal mode of solidification for alloys under most conditions is dendritic. A characteristic of dendritic solidification is the growth of rods or plates in specific crys-tallographic directions. The remaining liquid solidifies later, usually with a higher concentration of solute than the original liquid. Very little is known, however, about the transition from a crystal nucleus until the dendritic pattern is established. It is clear that there must be a transition because the nucleus is much smaller than the characteristic spacings found in the "steady-state" structure. And it also seems clear that the initial conditions must be important since the undercooling existing during the nucleation of the grains has a remarkable influence upon the grain size4 and the segregation pattern. The present paper reports a study of the micro-segregation in regions where crystals have nucleated, and the conclusions that can be drawn regarding the early stages of growth, in connection with the details of the solidification process. Aluminum of 99.993 purity, A1-Cu alloys containing 0.5 to 20 wt pct Cu, and Pb-Sn alloys with 5 wt pct Sn were cast and examined metallographically at the as-cast surface, close to the surface, and in the interior after casting. The alloys were cast from controlled temperatures against surfaces at different temperatures ranging from room temperature to approximately the liquidus temperature of the alloy. The surfaces were, in various experiments, graphite, stainless steel, copper, and aluminum. The methods used for metallographic examination were as follows. 1) The Nomarski phase contrast interferometer6 was used to obtain information on the topography of the as-cast surface. 2) The distribution of any solute present in A1 99.993 pct and copper in the A1-Cu alloys was studied by the anodic film technique originated by Lacombe and Mouflard7 and previously applied in the study of the solidification of aluminum by Biloni.8 The electropolished surface of the specimen is anodized under controlled conditions so that the thickness of the oxide film and therefore the interference colors under white light are sensitive to the local composition. This technique was applied to the as-cast surfaces and to metallographically prepared surfaces from the interior. 3) If in Al-Cu alloys, the surface is anodically oxidized for several minutes, instead of seconds as in the color-film technique, the copper segregation is outlined by a different level with respect to the matrix. This method is less sensitive but complementary to that for the color films. 4) The distribution of copper revealed and mapped by the metallographic techniques was confirmed by electron probe. 5) In samples with high concentration of copper, evidence for the copper distribution could be seen optically after electropolishing.

Jan 1, 1965

By T. G. R. Rawlins, L. E. Brosselard

Direct platinum carbon replicas have been used to study substrates prior to growth and after initial nu-cleation of the layer. Replicas have been directly stripped and correlations have been made with other replica techniques. Mechanically polished substrates are very flat with occasional areas of "dirt", which is apparently silicon. When such substrates are etched in hydrochloric acid gas, scratches and hexagonal defects (thought to be polishing compound) are revealed, together with areas of apparent redeposition. Chemically polished substrates are much less flat although much more homogeneous in appearance. Heat treat)nents have no effect. Nuclei deposited on these surfaces, using a normal silicon tetrachloride system, have been examined. Nuclei on mechanically polished subsrates occur in random areas only, whereas on chemically polished surfaces they are more uniformly distributed. THE interest in the study of thin films and now their rapidly expanding use in many fields has increased over a period of years. Much of this current interest, particularly in the field of single-crystal or epitaxial thin films, has derived its stimulus not only from possibilities for application but also from fundamental electron-microscope studies which have indicated the manner of growth of such layers from the initial nuclei.1-5 Previous work involving study of growth processes may be divided into three categories. First, vacuum deposition, primarily of metals, on a variety of substrates has been studied by electron microscopy and electron-diffraction techniques. These have shown the three-dimensional aspect of nucleation and the remarkable liquidlike behavior of the growing nuclei which coalesce to form a complete layer. More recently this work has been expanded in two ways: by growth inside the electron microscope this has obvious advantages for kinetic studies; and by growth in ultrahigh vacuum—much of this work has been done on semiconductors.8-11 It is of interest to note that metals, specifically gold deposited on rock salt, will form only polycrystalline layers in ultrahigh vacuum unless the substrate surface is contaminated.12 In general the mode of growth for vacuum-deposited semiconductor films is the same as that for metal films. The second method of growth that has been studied is that of electrodeposition.13,14 The little that has been published suggests that the mode of growth is similar to the vacuum case, except that irregularities may perturb the electric field and disturb the growth process. The third and last primary method of growing epitaxial layers is by use of chemical methods. These techniques have generated much interest and much has been published on them. Considerable electron-microscope work has been done on the defects in the layers; however comparatively little work has been undertaken on the initial nucleation and early stages of growth. Confining ourselves now exclusively to the case of silicon, Charig et a1.15 have considered the growth of silicon on silicon substrates by hydrogen reduction of trichlorosilane, and studied the films by means of replica and transmission techniques. Subsequently they have studied the same system for growth on quartz,16 and with the addition of pyrolysis of silane on quartz and alumina.17 Also Manasevit el al. have studied deposits using silane and silicon tetrachloride on sapphire.18-14 Finally, in this volume studies of deposition on beryllia and sapphire are reported. Although Revesz and Evans20 have examined complete layers, grown by means of the widely used silicon tetrachloride reaction, no detailed examination similar to that published by Charig and Joyce21 for the trichlorosilane system has been given. Therefore this investigation has examined substrate surfaces prior to growth and then nucleation on these surfaces for the silicon tetrachloride system. EXPERIMENTAL In this work the surfaces have been studied by means of standard replica techniques. Because of the very real problems associated with artifacts introduced,22 different replicas and different cleaning

Jan 1, 1967

By J. Geertsma

The relationship between porosity and the speed of propagation of acoustic waves in fluid-saturated porous rocks as measured by the Sonic log and by ultrasonic tecbniques is analyzed. Biot's continuum theory 1 is used to explain the difference in acoustic wave propagation between a dry and a liquid-saturated porous material. The porosity is a variable in this theory. However, the acoustic wave propagation in the dry rock depends too on porosity, and this dependence is not predicted by the theory. Frequently in dry sandstones, a nearly linear relationship between reciprocal acoustic wave velocity and porosity is observed in the low-porosity range. The physics behind this behavior is outlined. An empirical relationship of the form, 1/v = A + F, applies accordingly for many porous dry rocks, provided the porosity is the only variable. The presence of a liquid in the pores changes the value of B, and this change is found to be in agreement with the Biot theory. The time-average relation introduced some years ago2 results in an equation of the same type — 1/V = F/Vf + (1 - F)/Vr — but is not based on a sound physical picture. Still, this relation sometimes predicts approximately correct A and B values. Carbonate rocks with their complicated pore structures sometimes show a different relationship between wave velocity and porosity, unfavorable for log interpretation. Examples are presented. The simultaneous presence of calcite, dolomite and anhydrite, with their different grain densities and matrix compressibilities, complicates acoustic-log interpretation in carbonate rocks still further. Other complicating effects of acoustic-log interpretation are discussed. They are related to the influence of shale streaks and natural fractures on the average wave velocity observed by the logging tool and to the effect of adsorption phenomena on wave propagation in unstressed rocks particularly in sandstones. INTRODUCTION The velocity of propagation of sound waves in porous sediments as a function of depth is a quantity frequently measured. Velocity loggers of various d-sign may be used, for which velocity is defined as the. distance between a wave generator and a wave detector (one-receiver system) or the distance between two wave detectors (two-receiver system), divided by the shortest time required for a vibrational pulse to cross this distance. Velocity loggers ale used to assist in seismic prospecting, to differentiate between the various types of sedimentary rock layers, and also to determine rock porosity and pore fluid content. This paper is especially concerned with the relation between velocity and porosity and the effect of the pore fluid. Most velocity-log interpretation in terms of porosity is based on a formula advocated by Wyllie, et al,2 suggested earlier by Hughes and Jones,3 and known as the "time-average relation". This formula app1ies for a model consisting of a layered system of parallel alternating slices of a solid and a liquid, crossed by the wave path perpendicular to the interfacrbs. This must be an unsuitable model for the derivation of wave propagation properties of liquid-saturated porous media. It suggests that only rock matrix and fluid properties influence the wave velocity. The surprising fact, nevertheless, is that applications of this formula to clean sandstones under specific conditions (sufficient effective stress) results in porosity predictions which are close to reality. Other authors, such as Gassmann,4 White and Sengbush,5 Brandt,6 and Hicks and Berry,7 make use of more realistic models to arrive at a wave velocity formula for porous sediments. Their models consist of various liquid-saturated packings of frictionless spherical grains and are, therefore, also highly idealized. A number of experimental results obtained in the laboratory can be better explained with these model theories than by the time-average relation. A study of a general character, not depending a priori on a special model of the porous structure, was still lacking.

By M. E. Nicholson

The effect of boron on the austenitic transformation rate of iron is smaller than on low carbon steels. The influence of austenitizing temperature on B-Fe is the reverse of its influence on steels. THERE have been many studies made of the influence of boron on the hardenability of steel, but apparently none has been made of its influence on the y-a transformation of pure iron. There are several facts suggesting that boron should have a pronounced effect on the transformation rate of iron. First, Simcoe et a1.l indicated that boron reduces the nucleation rate of ferrite and bainite. Second, they showed, along with others,', " that the lower the carbon content of steel the greater the influence of boron on hardenability. If this trend extends to pure iron, the influence on rate of ferrite formation should be considerably greater for iron than for medium carbon steels. According to Rahrer and Armstrong," the multiplying factor for boron in pure iron should be about 2.40, compared with 1.50 in a 0.35 pet C steel. According to an extrapolation made by Grange and Mitchell,' the effect should be even greater, and the multiplying factor should be about 3.5 in iron. Many investigations of the boron influence'.7, 2, 5 indicated that boron is effective only when in solid solution. On the other hand, Chandler and Bredig" suggested that boron increases hardenability by combining with nitrogen, thereby preventing formation of AlN, which catalyzes the decomposition of austenite. If their hypothesis is valid, boron should have no effect on an alloy free from nitrogen. Digges et al." showed that so far as low nitrogen high purity Fe-C alloys are concerned this is not the case. No experiments, however, have been made on low nitrogen iron. To determine whether or not boron has an effect on low nitrogen iron and, if an effect exists, to determine whether it is as large as predicted from the investigations of boron treated steels, the following work was performed. Because of the rapidity with which iron transforms from austenite to ferrite at even a moderate degree of supercooling, it was decided to study the influence of boron on the transformation rate of iron by determining the effect of quenching rate on the temperature of the beginning of transformation. The technique, essentially that used by Greninger' and Duwez,H consisted of heating small specimens, 0.1 in. sq and 0.010 in. thick, in an atmosphere of purified helium with a resistance heater coil, and then quenching the sample in a jet of helium gas. At the time the jet was applied, the heating coil was removed from around the sample. The sample was suspended in the furnace on 30 gage chrome1 and alumel wires, one welded to each side of the specimen, which also served as a thermocouple for measuring the specimen temperature. Specimens were prepared from vacuum-melted iron obtained from the National Research Corp. which was rolled to a thickness of 0.060 in. and then decarburized in wet hydrogen for 51/2 hr at 700°C. This treatment also removed any boron present in the iron. The resulting iron contained 0.001 pet C. 0.0002 pet N, and 0.005 pet 0. One half of the piece was then boronized by surrounding it with 325 mesh boron powder and heating it for about 2 hr at 900°C in H,. The boronized iron was then homogenized at 1100°C for 24 hr. The iron boride case formed by boronizing was removed by grinding 0.010 in. from each side of the plate, and the piece was finally rolled to a thickness of 0.010 in. The resulting alloy contained

Jan 1, 1957