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By A. B. Stevens, C. J. Coberly

The absolute porosity of a rock or sand may be defined as the volume of the interparticle space expressed as a percentage of the total rock volume. The effective porosity as contrasted with the absolute porosity is the volume of the interparticle spaces which intercommunicate with passages of sufficient size to permit the entrance or recovery of gas or oil, also expressed as a percentage of the total rock volume. A knowledge of effective porosity is of prime importance in estimating the ultimate recovery to be expected from oil and gas-bearing formations. The determination of the effective porosity of a rock includes the measurement of two values: (I) the volume of the rock as a whole, and (2) the volume of the grains and sealed pore space. This paper deals with a new apparatus which has been called a "hydrogen porosimeter" for determining the volume of the grains and the sealed pore space. This volume is determined by means of the pressure relations established in the instrument by the introduction of a known quantity of hydrogen. The Hydrogen Porosimeter The apparatus used in this work consists of an upper chamber for measuring the gas, a lower chamber for holding the sample to be tested, a gage for measuring the pressures, a tank of hydrogen, and the necessary connections. (Figs. 1 and 2.) Of the several gases that might be used for this work, hydrogen has been chosen for three reasons: (1) it deviates less from the gas laws than most gases; (2) it readily penetrates the sample; (3) it is absorbed less than most gases by the solids and liquids with which it may come in contact. Method of Operation After placing the sample to be tested in the lower chamber, the apparatus is thoroughly flushed with hydrogen to remove all air from the system, which is then brought to atmospheric pressure Po. The valve connecting the two chambers is next closed and the pressure in the upper chamber is brought up to a pressure PI by admitting gas from the tank.

Jan 1, 1933

By H. I. Aaronson, C. Laird

Although the past results of X-ray experiments indicate that the broad faces of 0' plates are coherent with their matrix, dislocations lying in arrays have frequently been observed at these boundaries by transmission electron microscopy. Critical experiments employing the latter technique have been carried out in order to determine the origin of these dislocations. It is concluded that 8' plates are essentially coherent with the matrix at their broad faces throughout the aging temperature/time envelope studied. Virtually all of the dislocation arrays observed are deduced to have been formed by plastic deformation accompanying transformation. The proportion of dislocations arising from convexity of the plates is shown to be negligible by comparison with that from plastic deformation. At the higher aging temperatures, a[001] dislocations appeared in moderate numbers. These dislocations were traced directly, however, to the ledgewise dissolution of 0' occasioned by the formation nearby of 0 crystals. On the other hand, since there is a parametric difference normal to the broad faces of the ?' plates, mismatch dislocations do form at their edges. A previous conclusion that these dislocations have Burgers vectors of type a[001] was confirmed directly. The edges of 0' plates were observed to develop octagonal shapes when growing, but circular shapes during dissolution. 1 HIS paper presents the results of an investigation of the interfacial structures of plates of the transitional phase, 8', formed in an A1-4 pct Cu alloy. In a companion paper, Part 11, the effects of these structures upon the migration kinetics of a:?f boundaries are reported. This work is pa.rt of a general program designed to establish the basis of precipitate morphology. The present authors in Al-Ag,1 and whitton2 previously in U-C alloys, have used transmission electron microscopy to examine directly the vander Merwe3-6 networks of dislocations anticipated7 to compensate the small amount of lattice misfit normally founda at the broad faces of Widmanstatten plates. Since the broad faces of 0' plates are considered to be perfectly coherent with the corresponding habit planes in the a matrix,' no dislocations should be present at these faces. Many reports have been published, however, giving evidence to the contrary.10-18 The primary objective of this investigation was therefore to ascertain the nature of these dislocation structures. An attempt to do this is described in the first three sections of this paper. Inspection of the matching of the a and 8 ' lattices at the orientations of the 0:0' boundary corresponding to the edges of 0' plates raises the possibility that these edges may be made up of rather closely spaced edge- type misfit dislocations oriented so as to be sessile with respect to the lengthening or shortening of the plates. Since this structure should severely inhibit migration of the plate edges (Ref. 7, Part II), a situation not originally anticipated,' an experimental determination of the interfacial structure of the edges of 8' plates was clearly in order, and is reported in Section III. Those aspects of the experimental procedure applicable to both Parts I and I1 are presented in the next section. Specific procedures applicable to individual aspects of each investigation, and also the relevant surveys of the literature, are then individually reported in the appropriate sections. I) GENERAL EXPERIMENTAL PROCEDURE The material used in both parts of these studies was the same as that of a previous investigation:" strips of A1-3.93 pct Cu, 0.009 in. thick, prepared as before, solution-annealed at 548°C for 6 hr, and quenched. Details of subsequent aging, and in some cases deformation treatments, are given in the Experimental Procedure sections of the individual parts of both papers. Specimens of the heat-treated strips were electro-thinned as beforeLg and examined in a Philips EM 200 microscope equipped with a goniometer stage. A commercial hot stage, of the grid-heater type and capable of * 30-deg tilt about one axis in the plane of the specimen, was also used for kinetic studies. The usual precaution of calibrating for the additional heat supplied by the electron beam was taken.19 A 16-mm cine cam-I era mounted outside the viewing window was frequently used to record the transformations. Conventional selected-area diffraction and dark-field viewing techniques were used to identify the precipitates in the foils. Normal bright-field images corresponding to two-beam diffracting conditions or dark-field images were employed to characterize the dislocations observed at the interfaces of the precipitates. The application of these techniques to the study of an interphase boundary, and the interpretation of the images,20'21 has been fully described in a previous paper.'

Jan 1, 1969

By James H. Gardner

It is a striking fact in the domestic oil statistics of 1926 that with an increase in production of 13,000,000 bbl., there was nevertheless a lowering of both crude and gasoline stocks. It was the first reduction in the last eight years. In 1918, the last year of the war, stocks of crude and refined products were lowered 16,000,000 bbl., but in the following seven years stocks were increased 350,000,000 bbl., due largely to the phenomenal crop of major pools discovered in 1923. The big pools of that year coming as they did through some curious coincidence unprecedented in the oil industry, not only piled up a sudden increase of stocks at a time of large imports but they continued to add their quota to an increase of storage until 1926. With an increase in crude production, according to the Oil and Gas Journal, from 760,000,000 bbl. in 1925 to 773,000,000 bbl. in 1926, and an increase in cracking facilities of about 30 per cent., there was a draft on storage of 22,300,000 bbl. of crude and 1,000,000 bbl. of refined. Crude and refined changed from a stock surplus of 29,130,000 bbl. in 1925, to a deficit of 23,300,000 bbl. in 1926, or a differential total of 52,430,000 bbl. With a stock reserve of 541,700,000 bbl. of crude and refined oil in 1925, the amount drawn from storage was not large in percentage but it marked an important contrast with previous years. It meant a year of stability in prices and a sound condition in the industry. The indicated domestic demand increased from 695,120,000 in 1925 to 743,360,000 in 1926, (7 per cent.), 1 per cent. of which was due to California fires. Most of the gain in consumption was due to the increased demand for gasoline. There was little comparative change in the combined imports of crude and refined oil. There was an increase in exports of 17,200,000 bbl. (1.5 per cent). A petroleum balance sheet for 1926 and a comparativl sheet for the last two years, production in the United States by major districts and pools, and a list of imports are given in Tables 1 to 5, inclusive.

Jan 1, 1927

By Leo Tarasov

MAGNETIC torque studies of ferromagnetic single crystals have been carried out in a number of laboratories during the last decade1,2 and some work has been reported on polycrystalline material showing preferred orientation. Goss3 used the method extensively in developing electrical sheet with desirable magnetic properties, but he used it as a control rather than as a means of studying the texture. Bozorth4 made a quantitative correlation of a torque curve he obtained from some cold-rolled iron with the texture as determined from X-rays, but did not extend his studies beyond the one specimen. Other studies, which have been reported from time to time 1.5 have also been incomplete in the sense that no effort was made to study a whole series of samples, differing only in degree of cold reduction, or in the annealing temperature, in order to ascertain the effect of such treatments on the texture as revealed by torque measurements. It is the purpose of this investigation to make such a study, mainly in order to see how useful the method can be made when used under favorable circumstances and to find what kind of a correlation can be expected between magnetic and X-ray studies of texture. Before proceeding further, it is desirable to say a little about single crystals, so as to make clear the concepts involved in magnetic torque measurements.

Jan 1, 1939

By H. Conrad, V. V. Damiano, G. J. London

The slip mode activated during the c axis compression of single crystals of commercial-purity ingot SR beryllium, high-purity (twelve-zone-pass) beryllium, and Be-4.4 wt pct Cu and Be-5.2 wt pct Ni alloys in the temperature range of 25° to 364°C was determined using two-surface slip trace analysis, slip-step height analysis, and electron transmission microscopy. All three techniques indicated the occurrence of copious pyramidal {1 122) (1123) slip in the alloys over the entire temperature range, the amount increasing with temperature. Pyramidal slip was also indicated in the high-purity beryllium by slip trace analysis and electron transmission microscopy, but the amount was somewhat less than in the alloys. For the commercial-purity ingot crystals, only a very small number of pyramidal slip lines were observed, and these were in the immediate vicinity of the fracture surface. No pyramidal dislocations could be detected by electron transmission microscopy in this material. Dislocatransmissiontions with Burgers vectors [0001] and +(ll20) were identified by electron transmission microscopy inthe (1122) slip bands, as well as those with the j (1123) vector. This was interpreted to indicate that the edge components of the 3(1123) vector dislocations activated during c axis compression dissociate upon unloading according to the reaction i (1123) — [0001] + 3(1120) THE microstrain c axis compression of single crystals of commercial-purity ingot SR beryllium (99.6 pct), high-purity twelve-zone-pass beryllium (99.98 pct), Be-5.24 pct Ni and Be-4.37 pct Cu alloys was described in a previous paper.1 This paper covers in detail the analysis of slip traces observed on two mutually perpendicular lateral surfaces of these specimens, and a detailed description of transmission electron microscopy studies performed on foils cut from the bulk crystals after they had been deformed to fracture in the c axis compression. Observation of slip traces on single surfaces of deformed single crystals are generally insufficient to positively identify slip or twinning modes. The use of two carefully cut and oriented perpendicular surfaces can greatly aid in the positive identification and index- ing of slip traces, although even this technique may be quite inadequate if more than one type of slip system operates and if an insufficient number of traces are observed on the surfaces. The problem is greatly simplified for symmetric cases like that for c axis compression of an hep crystal such as beryllium, in which the operating slip systems are all equally inclined to the direction of the applied stress, and each slip system of a given slip mode has an equal chance of operating. For such cases, the traces of any given slip mode observed on the surfaces cut parallel to the c axis are symmetrically tilted about the c axis. It is therefore possible to quickly determine whether one or more slip modes are operating. Confirmatory evidence in support of the observations made on the external surfaces can be obtained from foils cut from the deformed crystals and examined by transmission electron microscopy. This latter technique serves to identify not only the operating slip plane but also the Burgers vector of the dislocations which participate in the slip. For this purpose, a simplified technique based upon a double tetrahedron notation is used in the present paper. The planes and directions in the hep lattice are all designated by letters rather than indices and extinction conditions are easily determined if the Burgers vector lies in the plane contributing to the diffraction. RESULTS 1) Slip Trace Analysis. The standard (0001) stereo-graphic projection of beryllium is shown in Fig. 1. The two mutually perpendicular, lateral surfaces of the compression specimen are represented by the diametrical planes AA' and BB', also referred to as surface A and surface B. For the specific case represented (a Be-5.24 pct Ni specimen deformed by c axis compression at room temperature), the A surface is tilted 5 deg to the (10i0') plane and the B surface is tilted 5 deg to the (1120) plane. Two surface trace analyses may be facilitated by examining in turn the intersection of various great circle traces of specific pyramidal planes with two surfaces and comparing the angles made with the (0001) plane with those actually observed on the two surfaces. One then identifies the slip traces by trial and error on a best-fit basis. The (1122) type planes (it was found that slip occurred on these planes) are shown plotted on the stereographic projection in Fig. 1. One obtains directly the angles between the (0001) plane and the {1122) traces by measuring the angle from the periphery to the point of intersection along the lines

Jan 1, 1969

By M. M. Wong, D. E. Couch, G. M. Martinez

The Bureau of Mines electrowon hafnium metal with an average oxygen content of' 150 ppm at 700°C from an electrolyte containing 27 wt pct LiCl, 62 wt pct RbCl, and 11 wt pct HfC14. The average anode and cathode current efficiencies were 90 pct at anode and initial cathode current densities of 86 amp per sq ft. Haf-nium metal with an average oxygen content of 440 ppm was electrowon at 800oC from an electrolyte containing 90 wt pct KC1 and 10 wt pct HfCl4. The average anode and cathode current efficiencies were similar to those obtained in the LiCL-RbCl-HfCl, electrolyte. The chlorine gas given off at the graphite anode was vented through either a silica or a graphite tube to prevent cell corrosion. THE current method for the commercial production of high-purity hafnium is the thermal decomposition of Hfl4.1 The iodide method is not adaptable to continuous process techniques. Nettle, Hiegel, and Baker2 studied the electrorefining of hafnium from hafnium sponge containing 800 ppm oxygen. They failed to obtain hafnium with 600 ppm oxygen in their initial deposits and obtained AEC specification for oxygen only after 75 pct of the soluble hafnium had been removed from the electrolyte. Calculations using their data indicated this was approximately 4 lb of hafnium. The electrolyte was then used to produce approximately 3 lb of hafnium with a low oxygen content. However, no data are shown concerning the amount of anode material initially used or what percent of it was dissolved, therefore, results are not suitable for evaluation of a continuous operation. In general, it was not possible to consistently obtain low oxygen content metal with the electrolytes described by Nettle, Hiegel, and Baker. Wong, Hiegel, and Martinez3 investigated the electrorefining process for hafnium and showed that even by strict control of electrolyte composition only relatively low oxygen reduction could be obtained. The oxygen contained in the hafnium anode material tended to transfer to the cathode deposit and only a limited purification was possible. Both the "iodide" and the "electrorefining" processes depend upon hafnium sponge as a starting material. The sponge is normally produced by magnesium reduction of HfC14 ' and does not meet AEC specifications for hafnium metal. Since only 30 pct of the anode feed could be utilized3 in the electrorefining cells, the Bureau of Mines developed an electrowinning process. HfC14 was used as the feed material for the electro-winning process described in this report. Many of the electrolytes used in the electrorefining studies3 ap- peared to be suitable carrier-electrolytes for HfC14. However, in the initial studies on electrowinning, it was desirable to use electrolytes that had low solidus temperatures and could be operated over a wide temperature range to investigate parameters of the process. Therefore, electrolytes containing LiC1, NaC1, KC1, RbC1, CsC1, and HfC14, in various combinations were explored. EQUIPMENT Chlorinator. Hafnium carbide was chlorinated to produce HfC14 in the batch-type chlorination shown in Fig. 1. Chlorination temperatures were measured with a thermocouple placed in the center of the HfC charge. A flow meter was used to monitor the helium and chlorine. The exhaust side of the silica chlorina-tor tube was equipped with a flask for collecting organic material released during the initial heating of the HfC. The temperature of an internal heater, which extended from the HfC14 condensing flask to the hot end of the chlorinator, was adjusted to prevent the HfC14 from condensing before entering the collection flask. Helium and excess chlorine were exhausted through the lid of the collection flask to an aqueous NaOH solution. Sublimer. Initial studies were conducted using a sublimer, Fig. 2, made by placing a 13/8-in. OD nickel thimble 11 in. long, inside a 11/2-in. ID nickel bell 12 in. long, and locking it in place. This unit was loaded with HfC14 and partially immersed in the molten electrolyte for sublimation directly into the electrolyte. In another sublimer shown in Fig. 3, the HfC14 was contained in a "resin reaction flask". Quartz wool, previously heated to 600aC, secured between two nickel wire screens, was placed just above the HfC14 powder. The lid contained a vacuum outlet, a gage, an argon inlet, and an air-cooled pipe for condensing the HfC14. This sublimer was evacuated and heated. The sublimation temperature was not critical and the sublimer operated satisfactorily at all temperatures between 250" and 350°C. Electrolytic Cell. The electrolyte chamber, Fig. 4, was made of mild steel 8-in. schedule 20 pipe, 30 in. long. The exterior was metallized with a Ni-Cr alloy. The electrolytes were contained in a 16 gage nickel or iron liner with a nickel heat shield on top. The cell was heated by a resistance furnace. A 21/2-in. ID by 25 in. long air lock was connected to one port of a two-port cell cover assembly through a slide valve. The cover assembly of the air lock was electrically insulated from the cell and was equipped with a rubber sleeve that provided for the passage of the cathode lead. This allowed the cathode deposits to be removed and a new nickel cathode to be introduced without allowing air to enter the cell. A tube-rod assembly was bolted to the other port on the cell cover assembly and was sealed by a packing seal. The tube-rod assembly consists of a graphite

Jan 1, 1970

By P. D. Hunt, B. Tani, M. G. Chasanov, R. Schablaske

The Zn-Vphase diagram was studied by thermal. metallographic, X-ray, and sampling techniques. Three ternary phase equilibria were observed: Mutual solid solubilities in vanadium and zinc appear to be negligible. The liquidus line is retrograde from 670° to 756°C. 1 HE only information in the literature relating to the Zn-V system was a study of corrosion of vanadium by liquid zinc' and an examination of the effectiveness of zinc coatings in protecting vanadium-base alloys from oxidation at high temperatures.2 Establishment of the Zn-V phase diagram was undertaken as part of a study of transition metal solubilities in liquid metal solvents. Chemical, metallographic, thermal, and X-ray diffraction analyses were used to determine the diagram. MATERIALS AND EXPERIMENTAL PROCEDURES Vanadium (99.86 pct) in the form of powder and small chips was employed. Stick zinc (99.99 pct; major impurities: 10 to 15 ppm Pb and 20 ppm Cu) was used in the liquidus determinations and thermal analyses; zinc powder (98.80 pct) was used to prepare intermediate compositions. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The apparatus and sampling techniques were similar to those described by Martin, et al.3 The entire metal sample was dissolved to preclude analytical errors due to segregation on cooling. Vanadium was determined amperometrically, using iron (11) as the titrant,4 to an estimated accuracy of 1 pct. Standard techniques of thermal analysis were employed to examine alloy specimens contained in alumina crucibles under helium. Heating and cooling rates were about 1°C per min. At least five heating and cooling cycles over the range 420° to 700°C were performed for each of two Zn-15 pct V alloys. A Zn-0.2 pct V alloy was used in the determination of the eutectic temperature. The separation of intermediate phases from zinc-rich alloys was carried out by selective leaching with ammonium nitrate solutions. For further investigation of intermediate phases 1/4 in. diam powder compacts were prepared by pressing at 80,000 psi and were annealed in argon at 415" to 450°C for 10 days. Larger quantities of intermediate phases were prepared in sealed tantalum capsules heated in a rocking furnace. Temperatures were determined to an estimated accuracy of 0.5°C with a Pt/Pt-10 pct Rh thermo-

Jan 1, 1963

By Dol Duwez, R. H. Willens

A technique is described by which metastable alloy phases can be obtained by very rapid cooling from the liquid state. The results obtained so far have lead to; 1) extension of solubility limits beyond their equilibrium values, 2) new phases not found under equilibrium conditions, and 3) amorphous alloys. MANY new nonequilibrium phases have been found in alloys rapidly cooled from the liquid state. The technique used in these investigations essentially consisted of propelling a small molten globule of an alloy against the inside surface of a rotating copper cylinder. Since these original experiments were performed, the technique has been greatly improved. The purpose of this paper is to describe in detail, for the first time, a simple and efficient apparatus for producing foils of alloys which are rapidly cooled from the melt and to summarize some of the observations made on these alloys. I) FAST COOLING APPARATUS In the original fast cooling apparatus used by Duwez, Willens, and Klement,' the alloy was melted in a graphite container having the shape shown schematically in Fig. 1. A shock tube was attached to one end of the graphite part to supply the pressure for ejecting the molten globule. The globule was received on the inside of a rotating cylinder located about 0.5 in. from the exit of the graphite container. The globule trajectory made an angle of about 15 to 25 deg with the tangent to the cylinder at the point of

Jan 1, 1963

By B. A. Shaw

Historically, microwave tubes have been fabricated from massive metal and ceramic components. The current trend is to lighten tibes for airborne applications. The reqciiremenls of light weight and also reduced cost have created a novel approach to tube structure in which thin-film technology plays a major role. Although the electrical requirements of thin-film circuits in microwave tubes differ from those required or se,niconductor integrated circuits. the technology is basically similar. The stringent requirements of the micvowave tube have created sophisticaled thin-film techniques thut are of interest to the integrated-circuit industry in general. This paper describes a nunzber of thin-jilm techniques recently developed and discusses in detail the application of the technology in microwave tubes. The particular areas of interest are: 1) ceramic mounted thin-film slow-wave structures; 2) thin-film secondary emitters; 3) suppression of tube environnental multipactor by semiconducting' thin films; and 4) age-hardenable and dispersion-hardened thin metal films. SEVERAL thin-film techniques specifically applied to microwave power tubes are discussed in this report. There are two reasons for this work. One is the necessity of reducing weight and cost of microwave tubes and the other is related to overcoming problems in the tube operation by the use of applied thin-film technology. The major emphasis of this work has been on tube slow-wave structures. Other work in the area of secondary emission, either its suppression or its enhancement, is continuing; the most satisfactory results to date have been by utilization of thin-film technology. The requirements of high thermal and electrical conduction together with greater strength than normally obtained with elemental materials have led to the development of dispersion-hardened films. The paper will discuss: 1) ceramic-mounted delay-line microwave tubes; 2) multipactor and secondary emission; 3) hardened films. I) CERAMIC-MOUNTED THIN-FILM SLOW-WAVE STRUCTURES In a conventional crossed-field microwave tube, the slow-wave or delay-line structure is produced from two carefully machined components. One half of the structure is shown in Fig. 1. The other half is the mirror image of the first but is rotationally offset by a half a period. The combined structure now forms an interdigital type of slow-wave structure and is the anode of the tube as shown in Fig. 2. The period and finger length of an interdigital slow-wave structure are prescribed by the desired dispersion characteristics. The typical design is as shown in the first figure; it can be noticed that the finger width is several times greater than the finger thickness. Even assuming that it were mechanically possible to produce free-standing fingers of extremely small cross-sectional dimension, for example, 0.002 in. thick by 0.005 in. wide by 0.500 in. long, decreasing this finger width would increase the tube efficiency but would also decrease the thermal-conduction path, causing an increased temperature rise from intercepted rf current which in its extreme could easily cause finger melting. Hence, for free-standing lines of this type, the design is a compromise between mechanical capabilities, tube efficiency, and thermal dissipation. These structures are also expensive and tend to be heavier than purely electrical considerations would demand. In the present approach, we have transposed the three-dimensional structure previously shown into an essentially two-dimensional structure as shown in Fig. 3. The linear structure is used here for clarity of detail. The support member is a ceramic material and the line is deposited copper. The final tube design is shown in Fig. 4. Because of the backwall sup-

Jan 1, 1967

By R. L. Perrine

This paper presents results obtained by consider ation of unstable miscible displacement within a porous medium as a quasi-turbulent displacement process, that is, a process characterized by fluctuations around a simpler, mean flow behavior. The instability usually results from the miscible displacing fluid having a viscosity lower than that of the displaced fluid. Such instability is evidenced in suitable experiments by the presence of viscous fingering. A unified theoretical relationship applicable to both stable and unstable displacement is derived. Parameters in the theory are obtained by empirical means. Although the theory describes an idealized conceptual model, agreement with experiment is quite reasonable up to moderately adverse viscosity ratios, such as 17:1. INTRODUCTION Many experimental studies of miscible displacement in porous media have been conducted with prediction of reservoir displacement efficiency as the ultimate objective. Most such studies have utilized lower displacing than displaced fluid viscosity, scaled to potential reservoir fluid pairs. Theoretical approaches have been largely limited to unit viscosity ratios, however, in spite of the necessity for an understanding of the mechanism of the unstable, adverse viscosity ratio displacement process. An obvious reason is the difficulty of describing in mathematical form the viscous fingering characteristic of these conditions. Observation of experiments conducted with dyed fluids in transparent systems suggests an analogy between unstable miscible displacement and turbulent flow in a pipe. In both cases there are fluctuations around a simpler, mean flow behavior. An important difference is that flow behavior of interest in the porous medium is entirely transient, contained within a transition zone between displacing and displaced fluids. Transient behavior complicates description in that coefficients in the equations become variables rather than constants. In the study reported here, the analogy with turbulent flow has been used in treating unstable miscible displacement as a quasi-turbulent displacement process. The purpose has been to derive, even if restricted to an idealized conceptual model, a unified theoretical relationship applicable to both stable and unstable displacement. A relationship meeting these specifications up to moderately adverse viscosity ratios, such as 17:1, is presented. One fluctuation parameter in the theory and dispersion coefficients are obtained by empirical means. The idealized theory is compared with experimental results. UNSTABLE MISCIBLE DISPLACEMENT AS QUASI-TURBULENT DARCY FLOW The miscible displacement of one fluid by another within a porous medium is considered in this study. Flow conditions are such that Darcy's law is applicable. It is further assumed that, by the stability criterion proposed by perrine,1 initial flow conditions lie well within the regime of instability. Thus substantial viscous fingering is assured. We wish to show how this flow regime can be represented as quasi-turbulent. That is, the Reynolds number for the established flow conditions is below that for inertial or turbulent flow within a porous medium, and lies within the regime for which Darcy's law is valid. Yet flow behavior can be described as the combination of some relatively simple average result, and characteristic fluctuations that are superimposed on the simpler behavior. Stated another way, flow behavior includes the movement of layers of fluids with different velocities past or over one another. Such descriptions are characteristic of turbulent pipe flow. The fluctuations in the present case are a direct consequence of the local viscous fingering which accompanies the unstable displacement process. Should displacement become stable, fluctuations would die out. It is of particular importance to note that fluctuations such as these can interact in a way that contributes to material transport by the basic flow. The basic transport equations required for engineering calculations must be modified to reflect this fact.

By G. W. Elger, H. E. Bell, J. E. Tress, J. B. Wright

This paper describes laboratory techniques and subsequent results of US Bureau of Mines (USBM) research to produce chlorination-grade feed- stock from an abundant, low-grade, domestic, rock ilmenite ore. The research is part of the Bureau effort to devise technology that may help decrease US dependence on imported raw materials. A rock ilmenite containing about 46 wt % TiO2 was smelted in an electric arc furnace with coke, wood-chips, and Na2CO3 to separate most of the iron as pig iron and to form a low-iron, titanium-enriched slug. The slug was ground, pelletized, oxidized, and then sulfated with mixtures of SO2 and air in a continuous 4.5- to 9.1-kg/h (10- to 20-lb per hour) apparatus at 1023° to 122J0 K (1380° to 1740° F). The sulfated slug, containing 60% to 65% TiOb, was reground and leached in water at ambient temperature to decrease the combined levels of the troublesome calcium, magnesium, and manganese impurities from 7.0 to 1.7 wt 70. The final product was upgraded to about 8.4 wt % TiO2. This material is potentially suitable for chlorination in a fluidized bed reactor. The most favorable results were achieved with leached slug sulfated at a feed rate of 4.5 kg/h (10 lb per hour) and at temperatures of 1073° to 1123° K (1470° to 1560' F).

Jan 1, 1986

By R. F. Campell, W. L. Jensen

IT is not uncommon for martensitic high carbon steels having a coarse austenite grain size to exhibit microcracks when polished and etched and examined with a microscope, as described by Davenport, Roff, and Bain.' Whether such cracks exist before etching or are the result of acid attack during etching has been debated from time to time. Fig. 1 illustrates the effect of electrolytic polishing, mechanical polishing and etching subsequent to each polish on microcracks produced by oil quenching from 1800°F a steel containing 1.14 pct C, 0.23 pct Mn, 0.33 pct Si, and 0.45 pct Mo. The austenite grain size was 3-4 on the ASTM scale. Grinding on lead laps followed by either electrolytic polishing with acetic anhydride-perchloric acid solution' or mechanical polishing with Linde "B" alumina on "microcloth" (sometimes referred to as Gamal cloth) revealed microcracks without conventional etching, as shown in Fig. la and b, respectively. These same fields, after subsequent etching with saturated picral, are shown in Fig. lc and d, and the cracks are seen to be typical microcracks; moreover, the cracks appear to be broader and longer than before etching. Although the microcracks were revealed by electrolytic polishing alone, the possibility of acid attack was present; however, the mechanical polish was accomplished without any intermediate etching to remove disturbed metal, hence this is regarded as definite evidence that microcracks are present before etching.

Jan 1, 1954

By Dean Goodermote, Carla S. Stone

I Introduction Coal fuels China. Roughly 70 percent of all commercial energy demand is supplied by domestic coal production and with the recent Chinese opening to the West, the Chinese Coal Industry may figure prominently in the export market as well. Because of the importance of China's coal industry to the future of China and the Pacific Rim energy balance, this paper reviews the industry and offers some cautious projections for its outlook. II Energy's Position in the Current Political and Economic Climate Traditionally, Chinese society has been dominated by the policies of its most important government leaders. Deng Xiaoping, Vice Chairman of the Communist Party is the current leader of China. Deng and his proteges are pragmatists. Although China's government structure is based on Marxist/Leninist tradition, Deng and his followers are promoting experiments with market economics and expanded relationships with Western Countries, which have encouraged foreign investment in China. Energy companies represent just one type of industry that is interested in helping the Chinese to develop their abundant natural resources. Although China's leadership is committed to a program of economic modernization, that program currently is experiencing what the Chinese government terms "readjustment". Readjustment cuts back in imports due to deficient foreign exchange and deemphasizes heavy industry, while it encourages agricultural and consumer goods output and, most imporant, energy production. Increased Chinese coal and oil production is essential both to fuel industry and, equally important, to provide foreign exchange. If sufficient energy production is not forthcoming, then economic growth will be severely retarded. China's 1979 per capita GNP of $260 is only slightly better than the weighted average achieved by low income countries of $230. (1) Delays in growth could lead to social unrest, threatening the position of the current leadership. Since there is no institutionalized mechanism for leadership succession and policy continuation, it is reasonable to assume that leadership changes could result in energy policy changes. III Energy Consumption Energy production is important to China's future economic health as highlighted by the World Bank. If China's economy grows rapidly, 5 percent to 6 percent during this decade, the Bank noted, a significant energy shortfall could occur as early as 1985. This state of affairs contrasts sharply with China's current position as a net hydrocarbon exporter. (2) To assure a healthy economic future, China's leadership is attempting to reduce its rate of increase in energy demand through conservation as well as to boost energy output. A massive conservation promotion program has been underway since 1979 and there is much room for improvement. China's industrial sector is only about half as energy efficient as is U.S. industry. (3) During the last two decades, each percent of increase in GNP has been accompanied by a 1.8 percent of increase in energy consumption. (4) This compares rather poorly with the United States where a less than one-to-one relationship exists. IV Energy Supply The short term prospects for oil production are uncertain. Production increases were rapid in the 1960's and early 1970's, averaging 20 percent annually, but most of this increase came from one field, Daquing. Now that Daquing's production has peaked and the offshore potential has yet to be developed, petroleum production has maintained a plateau of 2.1 million b/d, at least temporarily, of which approximately 15 percent is exported. (5) Output

Jan 1, 1982

By J. Richard Kyle

On page 1617, the author's box was incorrect. It should have read: J. R. Kyle, member SME, is an assistant professor of geology. Dept. of Geological Sciences, The University of Texas at Austin. Austin, TX. On page 1616, the italic line 22, beginning "Murray, R.C. ... " should have been deleted. On the same page, the first two lines (27 and 28) referring to Norris, A.W., 1965 . . . should have been deleted. Column 2 should have preceded column 1.

Jan 1, 1981

By G. M. Schwartz, J. N. Gundersen

Utilization of magnetite-bearing taconite from the great Mesabi range of Minnesota is fast becoming a major industry in the state. The planning and early development stages of taconite processing projects have been de-scribed1-3 and an excellent discussion has appeared recently4 concerning the current mining, crushing, concentrating, and pelletizing techniques of the Reserve Mining Co., whose operations lie entirely within the Eastern Mesabi district. The present paper will deal only with some of the geological aspects of taconite utilization in the district, with emphasis placed upon some of the common mineralogical and textural features of the tacon-ites currently being mined or stripped and how these factors generally affect the potential recovery of the iron from the metamorphosed Biwabik iron-formation. The generalized geologic setting of the Eastern Mesabi district is presented in Fig. 1. The small circles on the geologic map, adapted from Grout and Broderick,3 mark the location of drill holes that were available for inspection during this study through the courtesy of Reserve Mining and Erie Mining Cos. The cores from these holes were divided into stratigraphic units and examined for their mineral content. Typical mineral associations and grain fabrics were also determined from hundreds of thin and polished sections. Available metallurgical tests made it possible to determine the probable response of a given variety of taconite to magnetic concentration. The longitudinal section of Fig. 1, projected along the strike of the iron formation, presents the simple stratigraphy of the area. It also shows the uniformly thick nature of the iron formation members in the district as well as a somewhat abrupt thickening of the formation to the west of the probable fault. The stratigraphy of these precambrian rocks has been described5-' elsewhere and need only be briefly reviewed. Historically, the oldest rocks unit, the Giants Range granite (Algoman) was covered by the Animikie group of sediments (Middle Huronian?), consisting of the Pokegama, Biwabik, and Virginia formations. Outcrops of the Pokegama quartzite are locally distributed along the northern limit of the Biwabik iron formation, but they are too limited to depict on the geologic map of Fig. 1. The effects of the intrusion of several small diabase sills within the Virginia and Biwabik formations are obscure because all of these rocks have been subsequently highly metamorphosed, mainly by the Duluth gabbro. The emplacement of the transgressing Duluth gabbro (Middle Keweenawan) and that of numerous peg-matitic veins in the iron formation8 has resulted in extensive contact and metasomatic metamorphism which has locally reconstituted the previously existing minerals of the Biwabik formation, in large part quartz and magnetite, into a wide variety of silicate mineral assemblages9 that have a profound effect upon the re coverability of the remaining magnetite. The entire region has subsequently been eroded and largely buried beneath Pleistocene glacial deposits. Structurally, the strike of the gently dipping Animikie group generally parallels the elongate outcrop pattern of the Biwabik iron formation on the map of Fig. 1. The Animikie group most commonly dips from 5" to 15" to the south-southeast. In this area, the Duluth gabbro pluton is somewhat sill-like, dipping about 30" to the southeast. Projecting these present structures upward, it seems probable that the gabbro once extended over the underlying Animikie group in the Eastern Mesabi district. SELECTION AND PRESENTATION OF DATA Because of the locally intense metamorphic activity in the district, mineralogical variations within the magnetite-bearing taconites are commonly abrupt, both vertically and laterally. Consequently it is difficult to select a single hole or small group of holes whose cores will be entirely representative of all of the district. Two holes have been selected, however, that in a general way represent mineralogical and textural variations that are likely to be encountered in both the eastern and western parts of the district. These recently drilled holes were chosen for discussion because it was possible to log the core and then to place the sample intervals at stratigraphic boundaries prior to preparation of the core for magnetic tube tests.

Jan 1, 1961

By Peter Soo

Pvestrained Ferrovac E iron has been neutron-irradiated at approximately 90°C to an integrated flux of 1020 nut (E > 0.82 mev]. The irradiation was found to produce an incveased temperature dependence of the flow stress in addition to a greatly increased athemal stress. Measurements of the flow stress and stress relaxation, from which the activation volume and activation energy for slip were deduced, show that neutron irradiation changes the rate -controlling slip process to one based on dislocation interactions with tetragonal distortions which are Produced around submicroscopic interstitial loops in the lattice. The study indicates that without prestraining prior to irradiation the chances of detecting a change in the rate -controlling slip process are greatly reduced because in the initial stages of slip a substantial fraction of the radiation defects are swept out of the slip plane by gliding dislocations. Thus, activation parameters which are subsequently measured are representative of a greatly reduced defect density and would not differ appreciably from those for unirradi-ated material. The large increase in the athermal component of the flow stress is probably connected with the presence of depleted zones in the lattice which are introduced by irradiation. ALTHOUGH fast neutron-irradiation has not been observed to markedly alter the activation parameters for slip in bcc metals,' small but significant changes do occur. Most experimenters agree that irradiation predominantly increases the athermal component of the yield stress.'-= In addition to this, Laidler and smidt7 have shown that in iron irradiated to 5 X 10" nvt and molybdenum irradiated to 10" nvt, changes occur in the activation volumes for slip. A similar conclusion has been reached by Milasin and Malkin8 for irradiated iron. Work by Ohr et a1.5 shows that for Ferrovac E iron, irradiated to 1.2 X 1016 nvt, small increases in the activation energy for slip also occur. So far these changes in the activation parameters have not been explained on a firm theoretical basis. One important factor which would minimize the chances of detecting a change in the slip mechanism upon irradiation is the presence of "channeling" which has been observed in molybdenum,9 niobium,10 and iron.11These channels are formed by gliding dislocations which sweep irradiation defects out of the active slip planes and thereby create zones in which continued dislocation motion is encouraged. The activation parameters for the dislocations gliding in the defect-free channels would, therefore, be similar to those for unirradiated iron and a change in the rate-controlling slip process would be difficult to detect. In the present work, an attempt has been made to reduce the effect of uneven deformation on the measured activation parameters for slip in neutron-irradiated Ferrovac E iron polycrystals, so that a more realistic assessment of the effects of neutron-irradiation could be made. Primarily, the experiments involve the irradiation of specimens which had been prestrained to 9 pct elongation at room temperature prior to insertion into the reactor. It was hoped that the introduction of a large number of evenly distributed dislocations would substantially decrease any channeling effect which might otherwise occur. MATERIAL AND EXPERIMENTAL PROCEDURE The starting material was vacuum-melted Ferrovac E iron, an analysis of which is given in Table I. The standard tensile specimen had a gage length of 1.125 in., a cross-sectional diameter of 0.120 in., and a re-crystallized grain size of 1.2 x 10-3 in. All tensile tests were conducted on a floor model "Instron" tensile machine at a strain rate of 3 x 10-4 per sec. The irradiation of the prestrained specimens was performed in the Brookhaven High Flux Beam Reactor to an integrated flux of 1020 nvt (E > 0.82 mev) at a temperature of about 90°C. All specimens were excap-sulated in high-purity aluminum sheaths which were lightly swaged around the samples to ensure good thermal contact. Subsequent measurements on the irradiated specimens showed that within experimental accuracy the swaging had not deformed them. EXPERIMENTAL RESULTS Fig. 1 shows the flow stresses for a series of unirradiated control samples. In order to produce a comparable dislocation substructure throughout the test sm range, all specimens were prestrained

Jan 1, 1970

By R. Q. Shotts

Nitric acid oxidation rate analyses of three coals, previously studied microscopically by the Bureau of Mines, revealed three components. Relative quantities agree with those found for the four components given by the Bureau and results are consistent with current ideas of coal constitution. Possible multi-component composition for bright coal and a reactivity-rank relation are suggested. THE physically dissimilar components of bituminous coals often are easily recognized mega-scopically. Under the microscope, reflected light or light transmitted through thin sections reveals the presence of the different components, even when these are intimately mixed. Optical methods for the quantitative estimation of the relative abundance of the various components, both by means of thin sections and by particle count, have been fully described.'. ' It has long been recognized that there are chemical and physical differences between the various petro-graphic components of bituminous coals, although analytical differences usually are small.:'. ' Only in the case of fusain have chemical differences been used for quantitative determination of a component. C. C. Hsiao and associates, at the Mineral Industries Experiment Station of the Pennsylvania State College, have described a method of analysis which is based upon the differences in the rate of nitric acid (8N) oxidation, fusain, and the other components of coal."," The reproducibility of their method and its applicability in checking microscopic determinations of fusain content have been supported by several independent investigations.'. " The writer has proposed the use of differences in oxidizability for the estimation of other components." "' The results of the oxidation of whole coals and of float-and-sink fractions of coals were reported. In most cases the plots of the logarithms of the percent dry, non-fusain, organic residue from oxidation, against time, revealed the presence of at least two distinct components. Both components appeared to oxidize according to a first order law, but the reaction constants for the components were distinctly different. One or more of the dull density fractions were found to contain but one component, and some of the lower rank coals oxidized in such a way as to suggest the presence of three components. A suitable way to check the identity and significance of the components delineated by oxidation would be to analyze a sample of coal both by the nitric acid oxidation procedure and by a microscopic method. The writer was wholly unfamiliar with either of the microscopic techniques commonly used, and to make such a comparison it was necessary to rely upon microscopic analyses made by someone else. It is hoped that some laboratory which is equipped to make both types of analyses will some day make them upon identical samples. During the past 20 years, four Alabama coals have been analyzed petrographically and the results published by the United States Bureau of Mines. They are: 1—Flat Top mine, Mary Lee bed; 2—Empire mine, Black Creek bed; 3—Wylam No. 8 mine, Pratt bed, all in the Warrior field; and 4—Soot Creek mine, Fairview bed, in the Coosa field."-" Of these, only the Flat Top mine is still operating. Because of the closing of these mines, it first appeared necessary to rely upon the indirect and unsatisfactory procedure of sampling the beds in other mines located as near to the closed mines as possible. Upon investigation, however, it was found that the Bureau of Mines still had, in storage, the very same samples which had been used in the published petrographic studies. The Bureau very generously furnished about 2000 g each of the Pratt, Mary Lee, and Fairview bed coals, largely lumps but with some fines. The blocks of coal, when received, still were covered by the paraffin coating which had been placed on the polished surface, in the case of the Mary Lee coal almost twenty years ago. Procedure The procedure for oxidizing the coal sample and removing the alkali-soluble humic acid has been described. In the present study, oxidation periods of 1/6, 1/3, 1/2, 3/4, 1, 2, 3, and 4 hr were used. All oxidations were made in triplicate. After the paraffin had been removed in boiling water and the coal washed carefully with cold benzene, the entire sample of approximately 2000 g, obtained from the Bureau of Mines, was crushed to pass a No. 4 sieve. About 200 g of this material was pulverized to pass

Jan 1, 1954

By J. M. Tobin, L. H. Cadoff, L. M. Adelsberg

The reaction between liquid zirconium and graphite at temperatures above 2000 °C has been investigated. The reaction products were found to be carbon-saturated zirconium metal and ZrC which formed between the graphite and the metal. Parabolic growth behavior was observed for the ZrC Phase at all temperatures of this investigation. The parabolic growth constant at temperatures between 2000° and 2860°C was measured to be 1.83 exp 84,300/RT) sq cm per sec. The reaclion mechanism was proposed to be the rapid carbon saturation of the liquid metal and the formation of ZrC at the metal-carbide interface with diffusion of carbon through the ZrC, the "rate - determining step" of the reaction. The concentration-independent diffusion coefficient of carbon in ZrC, (DZrC), was expressed as 0.95 exp? 78,700/RT) sq cm per sec. This value mas calculated using the temperature-invariant ZrC phase fields proposed in the literature. The [ZrQiq)] — [ZYQiq) + ZrC] phase boundary over the temperature range 2000° to 2800°C was determined and the ZrC + C eutectic temperature was found to be 2890° ± 50°C. ThE Group IV and VB transition-metal refractory carbides are of interest because of their high melting points, high temperature strength properties, and relative inertness in certain corrosive environments. The present-day understanding of these materials, however, is limited by the general unavailability of accurate and reliable physical and chemical property data. This is due primarily to the difficulties associated with the preparation of suitable, high-density, high-purity carbide samples, and the achievement and control of uniform high-temperature environments. Accurate measurement of temperature is also an important factor limiting the reliability of reported data. The Zr-C reaction was selected for investigation because of the high melting point (>34000C) and favorable nuclear properties of the reaction product, ZrC. The direct reaction method afforded an opportunity to obtain kinetic data on the fully dense carbide. In this paper, layer-growth techniques were used to estimate the diffusivity of carbon in ZrC and to investigate the phase equilibria in the Zr-C system at temperatures above 2000°C. EXPERIMENTAL PROCEDURES AND DATA Crystal bar zirconium (99.9 pct Zr), purchased from the Nuclear Materials and Engineering Corp., and ZTA graphite (99.9+ pct) were used in this study. The analyses of the materials are listed in Table I. A schematic of the high-temperature carburization apparatus is shown in Fig. 1. The sample was a zirconium metal charge in a 1/2 -in.-ID graphite crucible which was capped with a tightly fitting graphite stern. The crucible and stem were designed to closely approximate black-body conditions. The graphite crucible was packed in lampblack (outgassed 1 hr at 2100°C) which provided insulation and thermal stability to the system. The inert atmosphere was maintained by a constant flow of high-purity argon or helium gas. The nozzle-diffuser section on the top flange was sufficient to prevent back-diffusion of air into the system. Chemical analysis of the carburized samples revealed oxygen and nitrogen concentrations of less than 44 and 20 ppm, respectively. The sample was heated by induction with a Westing-house 5 kw-450 kc power source. Temperature was measured with a Milletron two-color pyrometer which was sighted into the crucible by reflection from an overhead front surface mirror. Optical losses due to glass absorption and light reflection at air-glass interfaces were minimized by the employment of the dynamic-gas seal. It was found that no correction was required for the front surface reflector. The pyrometer was calibrated periodically against a U.S. Bureau of Standards tungsten ribbon secondary standard. Temperatures inside the crucible were also calibrated against the Zr-ZrC eutectic (1850°C)1 and the Nb-Nb2C eutectic (2335°C)2,3 temperatures and agreed to within ±10°C of these values. The temperature was controlled by manually adjusting the power input; variations of

Jan 1, 1967

By Ravindra M. Nadkarni, Milton E. Wadsworth

The kinetics of cetnentation of copper with iron were observed to follow first-order kinetics and increase with speed of agitation to a limiting value. Maximum rates agree closely with theoretical values based upon a model of aqueous solution diffusion through a litniting boundary film. Back reaction kinetics are shown both theoretically and experimentally to be independent of ferrous iron concentration in solution. The inlportance of attnospheres of air, oxygen, nitrogen, and hydrogen was studied and the results have been correlated with several impovtant oxidation processes involving metallic iron and copper. The kinetics of the reaction of ferric ion with metallic iron were found to be slow in the absence of metallic copper and essentially proportional to the surface area of metallic copper present in the system. THE precipitation of copper on iron is classic as an example of a relatively ancient art applied successfully for centuries with little fundamental understanding of the important parameters involved. There is some indication that the process has been a commercial means to produce copper since the sixteenth century.' The amount of fundamental work on the cementation of copper with iron is not great. Wartman and Roberson2 carried out a series of detailed copper cementation experiments using natural and synthetic mine water. The following were presented as the three principal reactions: Reaction [I] is the desired cementation reaction and accordingly 0.88 lb of iron would produce 1 lb of copper. In actual practice iron consumption would more normally fall in the range of 1.5 to 2.5 lb per lb of copper. Wartman and Roberson attributed the excess consumption of iron to Reactions [2] and [3]. They found that Reactions [I] and [2] proceeded at approximately the same velocity while Reaction [3] was much slower and would be diminished by controlling the contact time. It was also pointed out that increased agitation is beneficial in removing hydrogen bubbles and barren layers of solution at the iron surface as well as removing contaminants resulting from the hydrolysis of iron. Episkoposyan3 and Episkoposyan and Kakovskii4 studied copper and silver cementation on rotating iron disks in chloride solutions. The kinetics based upon a diffusion model were first order and varied linearly with surface area and with angular velocity raised to the one-half power according to the Levich equation. The experimental activation energy for both copper and silver was approximately 3 kcal per per mole. Excess iron consumption was found to increase with temperature. The rate of cementation first increased with increasing acidity and then diminished at high acid concentrations. sutolov5 has presented an excellent review of the Leach-Precipitation-Flotation (LPF) process including a discussion of copper cementation from an electrochemical point of view although few experimental results were presented. From voltage considerations he predicted that cementation should not be influenced by the concentration of ferrous iron in solution. He considered several secondary reactions including Reactions [2] and [3] and pointed out the importance of oxidation of ferrous iron to ferric with oxygen. In addition it was suggested that Reaction [2] was enhanced by the dissolution of metallic copper by ferric iron which in turn consumed excess iron by the cementation reaction, Eq.[1]. Cementation of copper on metals other than iron has been studied by several investigators but, as in the case of iron, the amount of fundamental work is not extensive. Bashkova and kovalenko6 and Bashkova7 studied the cementation of copper on indium from copper and indium sulfate solutions. The rate was found to be first order and to increase with acidity. This was associated with a decrease in potential (EIn — ECu) and the simultaneous reduction of hydrogen ions at low pH. The rate of cementation also decreased with increasing indium concentrations which was postulated to be due to the decrease in the rate of diffusion of the ions in solution. Below 97°C the experimental activation energy was found to have the unusually low value of 2 kcal per mole and was attributed to diffusional control. Above 97°C the rate increased suddenly and was explained as a change in the rate-controlling step to a chemical reaction. In Part I of this study Nadkarni et a1 .1 have reported on preliminary results obtained in a laboratory study of the kinetics of the cementation process. The rate was found to be first order, proportional to the surface area of the iron, and to increase with speed of stirring until a maximum rate was observed. At low stirring speeds the deposit was spongy and adherent. At medium speeds the copper peeled off in bright strips and at high speeds finely divided copper was produced and continually removed from the surface. The amount of excess iron consumed increased with speed of stirring and with temperature. The average experimental activation energy combining results from several types of iron was 5.8 + 1.6 kcal per mole suggesting diffusional control through a limiting boundary film. Traditionally copper cementation has been carried out over the centuries in gravity-fed launders of various design containing scrap iron. More recently rotating drum precipitators and activated launders8'10 have been used. In the latter, copper-bearing solutions are

Jan 1, 1968

By W. C. Winegard, J. R. Carruthers, A. Plumtree, L. R. Morris

The unidirectional solidification of dendrites containing central twin planes was studied in A1-Ti alloys. Once nucleated, the twinned dendrites are a Twore ejficient form for solute redistribution and therefore grow in preference to the normal columnar dendvites. Comparison of these twinned dendrites to adjacent colunmar dendrites by means of decanting experinzents and electron-probe rnicvoarmlysis indicates that these special dendrites grow with less undercooling than normal dendrites. These findings are further supported by the effect of forced convection on the dendrite morphologies. COMMERCIAL semicontinuous cast ingots of most aluminum alloys frequently exhibit large grains which appear to be composed of hundreds of parallel, continuous, thin lamellae. This structure has been termed "basaltic",' "fiederkristall", or, commonly, "feathery grain". The lamellae are 'about 100 p thick, several inches long, and each lamella contains a central (111) coherent twin boundary. The feathery grain has been reported to have a (112) direction2 and a (110) direction4 in the twin plane parallel to the casting direction, in contrast with the usual columnar structure where a (100) direction predominates. Aust et uZ.~ proposed that the twin boundaries were growth twins nucleated by stacking faults on the octahedral planes. chalmers6 has suggested that feathery grain may grow by a re-entrant edge mechanism, as proposed by wagner7 for twinned dendritic growth in germanium. Cahn et ~1.~ have concluded that the occurrence of feathery grain is evidence of some form of lateral layer growth rather than the atomically continuous growth normally observed in metals. The postulates by Chalmers and Cahn would seem to be contradicted by the work of Nakao~"' who showed that feathery grain only occurs when growth rates are high and the aluminum contains some solute. Specifically, Nakao found that in order to obtain feathery grain, in small castings solidified unidirec-tionally upward, the rate of growth must be above 2.4 cm per min and a critical solute concentration must be present. Below this solute concentration the grain structure was totally columnar. The critical solute concentration was found to be approximately: 0.04 wt pct Ti, 2 wt pct Cu or Mg, and 8 wt pct Zn. As pointed out by Chalmers it is not obvious why a twin-plane re-entrant edge mechanism would occur in aluminum which is thought to have a diffuse solid-liquid interface. The present experiments were undertaken to determine the growth mechanisms in- volved and to study the solute segregation in more detail. EXPERIMENTAL PROCEDURES Alloys ranging in composition from 0.05 to 0.23 wt pct Ti* were prepared from 99.9 pct pure Ti and 99.993 pct pure Al. Two-hundred-gram samples of A1-Ti binary alloys were solidified unidirectionally and vertically upward from a water-cooled copper base, in a heated insulated mold. The 1-in.-diam, 6-in.-length mold was made of Marinite (manufactured by Johns-Manville Co.). The mold was attached to a 24-in. pivoted arm such that by dropping a weight the mold was rotated 180 deg, throwing the liquid metal from the solid. In this way, the solid-liquid interface was revealed by decanting. A sketch of the decanting mold is shown in Fig. 1. The alloy was poured into the mold at temperatures ranging from 680" to 750°C, partially solidified by water cooling from the base, and decanted after a measured time interval. Growth rates for each metal-pouring temperature were calculated from solidification-time vs length solidified curves. Temperature gradients in the melt were measured using four No. 34 gage thermocouples which protruded into the mold cavity. Grain orientations were determined by X-ray diffraction using Laue back-reflection techniques. Grain substructures were examined metallographically, using polarized light, by applying a thin epitaxial anodic film to polished sections after the method of Hone and pearson." Titanium micro segregation was measured by electron-probe microanalysis using a NORELCO AMR/~ with a mica crystal and proportional-flow counter. Several of the cast samples exhibited feathery and columnar dendrites growing in the same direction and

Jan 1, 1967