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By L. H. Reiss, J. Groult, L. Montadert

Many fields, where the reservoir is composed of sandy layers, show great complexity because of the lack of continuity which results from a particular type of seditnentation. This complexity may be a factor of prime importance in studying reservoir drainage, especially in the displacement of oil by water or gas. This paper describes work done to study this heterogeneity and its influence in the exploitation of the fields of the lower Devonian sandy shale in the Fort Polignac Basin in Algeria. Two lines of research were followed. 1. On the border of the hasin, a detailed sedimentological study established rules for the distribution of the sandy zones, which furnished hypotheses necessary for devising a geologic model of the reservoir. A certain number of sandy zones were recognized and characterized by their sedimentation. 2. In the interior of the basin, production logs deterrnined the productivity profile. Study of these point data led to a description of the distribution of oil and gas phases in the reservoir so that the continuity of different zones between the wells could be deduced. These techniques were applied to the study of the lower Devonian sandy shale reservoir of Zarzaitine. The sedimentological study guiding the correlation work, with the aid of the conventional static data (logs and cores), led to the establishment of a useful geologic model of the reservoir. Production logs, thanks to the contribution of dynamic elements, permitted corrobora-tion of the model. In particular, the logs confirmed separation, as proposed by the sedimenfological study, of two comparable sandy groups by revealing the continuity of a thin impermeable layer, invisible on conventional logs. INTRODUCTION The heterogeneity of sandstone reservoirs considerably influences the distribution of fluids, as well as their displacement in the reservoir. Rational development of a field and maximum recovery of hydrocarbons are closely tied to an exact and precise knowledge of the intern architecture. We will try to show how it is possible I refine the knowledge of the reservoir by seeking qui different and varied sources of information. Productic geology, the group of techniques which leads to idei concerning reservoir architecture and its geometric descris tion, furnishes the framework of this undertaking. Of these techniques. those used so far are qui varied. Descriptive as well as quantitative, the technique partake as much of classical geology as of reservo science. They include (1) geologic studies of the enti basin, especially a stratigraphic and sedimentologic study of the reservoir member at its outcrop, detail1 observations of cores taken from wells and, finall oriented cores; (2) interpretation of geophysical dat (3) interpretation of electric logs, nuclear and sonic lo and dipmeters: (4) petrophysical study of the reserve on samples taken from wells; (5) reservoir dynamics (stu of the production history and, in particular, interpretati of production logs); and (6) analysis of the fluids a thermodynamic studies. This incomplete list could also include (1) study the migration of the fluids, (2) geochemistry (chemi characterization of the oils), (3) regional hydrodynamii and (4) injection and detection of tracers. If most of these techniques are classic, attention i nevertheless be called to applying two of the techniql in conjunction: the study of the reservoir member its outcrop and the study of dynamic distribution fluid phases in the reservoir through use of product logs, used in the study of the sandy shale reservoirs the lower Devonian of the Fort Polignac Basin, Alge in particular, their application to the study of the 2 zaitine field where they have led to a new and satisfact model of the reservoir will be described. THE ZARZAITlNE FIELD Situated in the interior of the Fort Polignac 8 about 150 kilometers (km) north of the lower Devol outcrop, the Zarzaitine Devonian oil field was discovc On Ian. 28, 19'' (Figs. 1 and l8). It is in the fern a monocline truncated by two perpendicular fault: great throw, with a downthrown section to the north\: Erosion at the top of the structure has caused one of it to disappear. It is a reservoir with a gas cap an m coefficient on the order of 1:5, open to the aql On the northeast, with the oil zone covering an Of 106 sq km and with initial oil reserves of 222 mi

Jan 1, 1967

By J. D. Verhoeven

The effectiue distriblltion coefficient has been Measured in a series of vertical, normal freezing experirtzents with large current densities passing through the solid-liquid interface. The results indicate that the effect of the current on solute redistribution is due to electvotransport in the liquid. The high currents produced extensive mixing in the liquid which was considerably reduced by solidifying in small lubing. Analysis of the convection indicates that it probably vesulls from a horizontal temperature gradient produced by the Joule heating- of the electvic crirver~t. Due to the strong dependence of this convection upon the specimen radius, it is conclnded that only for specit~ens with radii of less than somewhere between 1 and 2 mm wilt electric field freezing be getlerally effec-tire at enhancing the purification of zone-melting experittierats in loe-melting alloys. Experiments on 0.8-mm lubes illustrate some interesting potential applications of this techniqne as a means of solute control on smcrll specimens. In a number of papers published within the last few years'-4 it has been found that passage of large dc currents through the solid-liquid interface of a freezing alloy produces a change in the solute redistribution accompanying the solidification. It had been predicted theoretically by Hucke et al.s and by Pfann and Wagner that such an effect would occur as the result of electrotransport within the liquid boundary layer at the solid-liquid interface. These authors independently derived the following relation between the effective distribution coefficient and the variables of the process: Where k0 is the equilibrium distribution coefficient, V is the mobility of the solute relative to the solvent, E is the electric field intensity, D is the solute diffusion coefficient, R is the rate of interface motion, and 6 is the boundary layer thickness. Both groups of authors show that this equation predicts the possibility of extending the purification ability of zone-melting experiments by the addition of an electric current. However, there are other effects in addition to electro-transport which could be produced by the high dc current and might, perhaps, invalidate the applicability of Eq. [I]. For example, high electric current might affect the interface reaction or perhaps the equilibrium distribution which was assumed to exist at the interface. It was the purpose of this work to determine the applicability of Eq. [I] by systematically investigating a simple system for which all of the necessary parameters were known. It was of particular interest for speculating on the potential usefulness of this technique to determine the maximum practical field intensities obtainable, and the effect of these high fields upon convective mixing in the liquid. The initial work in this study was published in a previous paper3 which will be referred to as I. In that work, a current density of 2000 amps per sq cm was used with specimen diameters of 5 mm. The results gave a qualitative confirmation of Eq. [I.], and also showed that a large amount of convective mixing was produced in the liquid by the current. The present study is an extension of that work to smaller specimen diameters and higher current densities. Two points were overlooked in I and will be emphasized here: a) the value of ko has not been well-established in the Sn-Bi system and b) the observed convection could be due to thermal convection produced from the Joule heating. EVALUATION OF k0 To evaluate Eq. [ I.] it is necessary to know the value of the equilibrium distribution coefficient, k,. Tn I the value of k, was taken as 0.3 from a published phase diagram.7 According to ansen' the best data on the phase boundaries of the Sn-Bi system are those of Davidson.5 The data of Davidson give a k, value ranging from 0.21 to 0.25 for the compositions studied in this work, or an average value of around 0.23. In a recent publication, Rigaud and Tougas'10 determined ko by means of a solidification technique. For an alloy of approximately the same composition as that used in this work they obtained a ko value of 0.39. Hence, there is considerable uncertainty in the value of ko and, consequently, a series of experiments were made to determine k, more accurately.

Jan 1, 1968

By H. W. Schull

The Alligator Ridge gold deposits are located in northwest White Pine County at the southwest end of Alligator Ridge. Alligator Ridge is on the west side of Long Valley in the range of hills that separates Long and Newark valleys. The nearest population center is Ely, about 113 km (70 miles) to the southeast. Access to the Alligator Ridge gold mine from Ely is via US Highway 50 and the Long Valley Ruby Marsh Road. The latitude and longitude is approximately 39° 45' north and 116° 30' west. The Alligator Ridge gold deposits occur in the lower 61 m (200 ft) of the Mississippian-Devonian Pilot Shale formation, a laminated calcareous carbonaceous siltstone. The gold deposits contain carbonaceous, oxide, and jasperoid type gold ore. For more details on the geologic features of the deposits, see Schull, Sutherland, and Ilchik (in press). The discovery story of Alligator Ridge began in the spring of 1976 when the areas mapped as jasperoid on the 1:250,000 scale geologic map of White Pine County (Hose and Blake, 1976) were examined and sampled. Seventeen samples, about 23 kg (50 lb), were collected from an area about 0.65 km2 (0.25 sq mile). Of these 17 samples 10 reported atomic absorption values of less than 0. 1 ppm Au and 7 reported values in the 0.1 to 1.0 ppm Au range. In June of 1976 20 lode claims were staked to claim the area of the rock chip sampling. The claims' end and side center lines were used as a grid for soil sampling. Sample stations were 91 m (300 ft) apart and sample lines were 229 m (750 ft) apart. The samples were sieved to - 180 µm (- 80 mesh). Out of 99 soil samples, seven samples reported Au values in the 0.1 to 1.0 ppm range. Of the seven auriferous samples, five were located over the jasperoid outcrops previously sampled; one over unmineralized Pilot Shale a few hundred m (ft) downslope from some Au-bearing jasperoid; and one from a 15 x 15 m (50 x 50 ft) talus outcrop area of hitherto unnoticed mineralized Pilot Shale. Subsequent sampling, mapping and drilling would show that this 15 X 15 m (50 x 50 ft) outcrop area was the top of the Vantage 1 ore body, about 1.27 Mt (1,400,000 st) of over 3 g/0.9 t (0.11 oz/st) Au. Late in the summer of 1976 about 30 more 1.4 to 2.2 kg (3 to 5 lb) rock chip samples were collected in the course of preliminary geologic mapping. This mapping and sampling showed that the gold-bearing jasperoids occurred at the contact between the Pilot Shale and the underlying Devils Gate Limestone. Rock chip samples of 0.1 ppm Au or greater were restricted to the jasperoids and the mineralized outcrop area of Pilot Shale located by the soil sample survey. Rock chip samples from the area of mineralized Pilot Shale were in the 3 to 5 ppm Au range. Activity resumed in the summer of 1977 with a more detailed soil geochemical survey. The jasperoid areas were defined as large geochemical gold anomalies of values greater than 0.1 ppm and locally greater than 0.2 ppm Au. Soil samples from the area of mineralized Pilot Shale outlined a greater than 0.1 ppm gold anomaly 61 x 152 m (200 x 500 ft) in size. Further geologic mapping showed that elsewhere, even where bleached and silicified, the Pilot Shale areas were geochemically very low in gold (less than 0.1 ppm Au). In November, 1977 twelve rotary percussion drill holes were drilled to test the gold-bearing jasperoid areas and the mineralized Pilot Shale area. Drilling of the jasperoid areas showed that the jasperoids gave way at shallow depths [less than 24 m (80 ft)] to unmineralized unaltered Devils Gate Limestone. A five hole cross pattern was drilled to test the area of mineralized Pilot Shale. Four of the five holes re-

Jan 1, 1985

By H. L. Gilbert, W. W. Stephens

Production of anhydrous zirconium tetrachloride by direct chlor- ination of a zirconium oxide carbon mixture in a silica-brick-lined chlorinator is described. Theory and thermodynamics of reactions are discussed. A pilot-model chlorinator and full-scale production equipment are described and operating data are included. ANHYDROUS zirconium tetrachloride required as a starting material in the Kroll process for production of ductile zirconium has been produced in this country principally by chlorination of the carbide or "carbonitride" made by reduction of zircon sand concentrates with carbon in the arc furnace. This process and the equipment used have been fully described.'.' It is well known that zircon or badde-leyite ores may be chlorinated directly with chlorine in the presence of carbon, and this one-step approach would seem at first glance to be preferable to the two steps involved in the carbide-chloride operation. As previously discussed1 considerations leading to adoption of the longer process were: 1—Chlorination of the carbide proceeds rapidly at temperatures below 500°C, whereas temperatures above 900°C were considered necessary for chlorination of zircon-carbon mixtures. 2—The highly exothermic nature of the carbide-chlorine reaction makes it self-sustaining, while heat must be supplied continuously in direct chlorination of the ore. 3—Silicon was thought to be chlorinated along with zirconium in the direct chlorination of zircon, leading to high chlorine consumption. In production of carbide in the arc furnace, silicon is driven off as silicon monoxide and does not enter the chlorinator. 4—For efficient direct chlorination, the ore must be finely ground and intimately mixed with carbon, and the mixture briquetted. 5—Direct chlorination requires a much larger chlorinator for a given production capacity than chlorination of carbide. Recently it has become necessary to produce large quantities of zirconium metal from a chemically purified zirconium oxide. Since the cost of the latter is high, the relatively high losses encountered in production of carbide in the arc furnace could not be tolerated, and a graphite resistor furnace5 was developed for production of carbide, which was then chlorinated in equipment previously used for chlorinating arc-furnace carbide. This method of operation was quite satisfactory, and losses in the carbid-ing step were minimized. However, operating costs were relatively high, and the process did not lend itself particularly well to large-scale operation because of the multiplicity of small units required and the hand labor needed to load, unload, and maintain the furnaces. To chlorinate the carbide, a vertical-shaft chlorinator was used in which the charge was heated with a central split graphite-rod resistor.' Operation of this chlorinator was somewhat less satisfactory with the resistor furnace carbide than it had been with the arc-furnace carbide due, principally, to the differences in physical properties of the carbide. The arc-furnace carbide is obtained as a fused metallic-appearing mass which can be crushed to -1/4 in. with production of a minimum of fines, whereas the resistor-furnace product is lightly sintered and produces a large proportion of fines in crushing and handling. These fines tend to pack in the chlorinator and promote channeling. which results in poor chlorine efficiency and low capacity. Data based on production of 22,000 lb of chloride from resistor-furnace carbide in this equipment are shown in Table I. Necessity for increasing production of chloride from about 2,000 to 15,000 lb per week led to further investigation of possible methods for direct chlorination of the oxide or oxide-carbon mixtures. Direct chlorination of the pure oxide presents much less difficulty than chlorination of zircon sand or oxide ores. The oxide is easily ground to —200 mesh, and no silica is present to cause excessive consumption of chlorine or contamination of the product. Theoretical Considerations The principal chemical reactions involved in chlorination of mixtures of zirconium oxide and carbon may be written as follows: ½ ZrO2 (c) + C(c) + Cl2(g) = ½ ZrCl,(g) + CO(g) [I] 1/2 ZrO, (c) + CO(g) + Cl2(g) = ½ ZrCl,(g) + CO2(g) 121 ½ ZrO2 (c) + ½ C(C) + Cl2(g) = 1/2 ZrCl4(g) + ½ CO2(g) [3]

Jan 1, 1953

By D. H. Yardley

GEOCHEMICAL investigation of trace elements in surface materials was begun near Ely, Minn., in 1953 along the basal contact of Duluth gabbro with Giants Range granite (Fig. 1). This article presents data on the distribution of copper and nickel in till and in stream sediments in the area and proposes an explanation for the types of distribution found. The Duluth gabbro, one of the world's largest basic intrusives, intrudes rocks which range in age from Keewatin to middle Keweenawan. Within the test area the gabbro is in contact with granite except for short sections where it is in contact with remnants of iron formation. Sulfide mineralization occurs within the gabbro, near and parallel to the basal contact for a distance of several miles. Schwartz and Davidson' have described the geologic setting of the mineralization. The sulfides, believed to be syngenetic, include chalcopyrite, cubanite, pentlandite, pyrrhotite, and minor amounts of bornite. They occur disseminated in the silicates and as small interstitial masses. The ratio of copper to nickel is about 3.8:1, based on 66 chemical analyses of rock samples from various outcrops (Ref. 1, p. 702, and Ref. 2). Test Procedures: With specified exceptions, all nickel and copper tests were made by the chromo-graph method,:' which measures the intensity of a colored spot formed by a reaction between the metal being determined and special reagent paper. The intensity is then compared to the intensity of spots prepared from samples of known metal content. Details of the test procedure are outlined in another article (Ref. 4, pp. 77,78). All soil samples tested in this investigation to date have been weighed on an analytical balance. However, a volumetric scoop designed to provide about 0.1 g of soil adds to the speed and ease of testing and has been found to give satisfactory results (Ref. 5, p. 531, and Ref. 19). The size of the samples used for the tests was 0.1 g. Whenever such small samples are used there is some question as to whether they are representative of the several grams in the field sample. Many repeat tests of the samples used in this investigation demonstrated that results can be reproduced within the limits of accuracy of the method without formal mixing beyond that inherent in screening the soil fractions. Furthermore, the 0.1 g is probably as representative of the field sample as the field sample is of its area of influence. Hawkes and Lakin (Ref. 6, p. 291), who considered the general problem, compared ground and quartered bulk samples of 500 g with 5-g grab samples. They concluded that "there is no significant loss in accuracy of data by substituting grab samples for bulk samples." The term soil implies somewhat different things to the geologist, engineer, and soil scientist.' For convenience the term as used in this article refers to unconsolidated material (the mantle) overlying bed rock. Sampling Procedure: Samples were taken at 100-ft intervals along north-south traverse lines across the gabbro-granite contact. The soil (till) samples were taken at an average depth of 1 ft, which was below the high-humus surface layer and into clean till. Samples taken at 1-ft intervals down to ledge showed as high a metal content at 1 ft below the air-surface as at greater depths and in two instances were slightly higher. The till at 1-ft depth did not appear to differ from material at greater depths. Total depth to bedrock has been tested at only a few points and where measured varied from 1 to 10 ft. Aerial Distribution Contours and Profiles: Plotting of copper, nickel, and cobalt content in contour form (Fig. 2) shows that anomalous amounts of these metal ions occur in till over and closely adjacent to mineralized areas of the gabbro. Contouring nickel content alone, or the copper content, outlines the same target area. Contours of the copper content provide a more distinct anomaly than nickel because of the higher copper concentration. The traverses are rather widely spread for interpolation; however, drilling has confirmed the target area essentially as shown.

Jan 1, 1959

By J. A. Pusateri, M. A. Orehoski, N. R. Arant

Plant studies on commercial-size ingots and laboratory experiments with induction furnace heats have demonstrated that the major source of ingot cracks is associated with two conditions arising during top-pouring practice: 1—solidification during pouring, and 2—turbulence created by the impact of the stream. Methods of controlling the two factors were effective in eliminating or significantly reducing ingot cracks. BECAUSE the process of removing surface defects from hot-rolled product is so costly, the steel industry is striving constantly to develop methods of preventing, or at least decreasing, the occurrence of surface defects. Investigations have revealed steel-making and processing variables related to major surface defects, and controlling these variables has led to improvements in surface quality. However, the fundamental causes of major surface defects, such as ingot cracks, have not been determined; consequently such defects persist. At the Research and Development Laboratory of the United States Steel Corp. in Pittsburgh, a seam research program was initiated to determine the fundamental causes of certain major defects. As a part of the program, ingot cracks in killed, finegrained C1020 steel were selected for study. A cost survey indicated that, of the steels produced in sizable tonnages, carbon steels in the range of 0.18 to 0.23 pct C content require the most conditioning. Since this is particularly true of C1020, any im-provement of surface quality that might be effected from the study would be beneficial. Also, since the frequency of ingot cracks is exceedingly high for this grade, the steel would provide an excellent opportunity for a thorough study of the ingot-crack-ing problem. Why steels in this carbon range tend to exhibit more ingot cracks than do other steels was not considered in the investigation; the mechanism of ingot-crack formation was of paramount importance. Also, only the top-pouring practice was considered in the investigation, because this pouring procedure is used more extensively than others. In this study, ingot cracks are defined. as deep surface defects that sometimes are observed in an ingot prior to rolling but usually are observed during the initial stages of rolling on the primary mills. These defects may occur at any angle to the rolling direction but are most prominent in the transverse or nearly transverse direction. The appearance of ingot cracks on the rolled product varies with respect to their angle of formation and with the extent of rolling after their first occurrence. Ingot cracks are also termed "deep seams," "arrowheads," "irregular cracks," and "transverse cracks." Fig. 1 shows ingot cracks in a rolled bloom. This report summarizes: l—the exploratory investigation of commercial-size ingots; 2—the labor-atory investigations related to determining the source of ingot cracks and developing corrective methods; and 3—the plant evaluations of laboratory methods of decreasing ingot cracks. Exploration of lngot Cracks in Commercial Ingots Materials and Experimental Work: At the Du-quesne Works of the United States Steel Corp., five heats of killed, fine-grained C1020 steel were selected for the exploratory phase of the seam-research program. The heats were made by open-hearth practices that are considered most conducive to good surface quality. They were top-poured into 22x25 in. big-end-up hot-topped molds. One as-cast ingot and four other ingots rolled to the following cross-sectional sizes were set aside from each heat: 16x20 in.; 9 1/2x10 in.; 5x5 in.; and 2x2 in. The processing of the heats, from the time of charging in the open hearth furnaces to the end of the rolling operation on the primary mill, was observed carefully and recorded. The cast ingot and the four rolled ingots from each heat were examined for surface defects. The cast ingots were split longitudinally near the vertical center plane to expose the ingot structure beneath badly cracked regions. Also, a series of transverse sections was cut at about 1 in. intervals in a badly cracked area of one ingot. All sections were ground, polished, examined by sulphur printing and deep etching, and photographed. The rolled ingots

Jan 1, 1955

By John E. Hockett

The need for basic information about the relationship between resistance to dejormatim (flow stress), temperature, strain, and strain rate, for the solution of metal-fovming problems, is pointed out. Some early attempts to satisfy the need are mentioned. A brief description of a machine called a Cam Plastome-ter is given, including the processing of results of testing in the machine. Next, a program of testing aluminum in compression over a wide range of constant true-strain rates (0.1 to > 200 sec-1) and a modevately broad range of temperatures (223° to 673°K) is described. The results of this program are presented in the form of true-stress us true-strain cuvves. The data in these curves are presented in the form of relationships between true stress and true-strain rate in sermilogarithmic and log-log form, as functions of temperatures—for several true strains. Finally, true stress, for a given true strain, is displayed as a function of log true-strain rate and absolute temperature, i.e., a surface. SINCE the publication of Hill's book1 on plasticity theory, increasingly rapid advances have been made in analytical solutions to forming problems. Methods in common use are the slab method, the uniform deformation energy method, the limit analysis method, the slipline field method, and the semiexperimental method called "visioplasticity". These approaches, and examples of their use, are covered in detail by Johnson and Melloor2 and by Thornsen, Yang, and Kobayashi.3 unfortunately, practically all of the above work has had to rely upon a number of basic assumptions, e.g., homogeneous deformation and Coulomb (sliding) friction; and virtually no dependence of the mechanical behavior of the deforming metal, upon temperature, strain, and strain rate, has been included. It is with this dependency that this paper is concerned. Loizou and sims4 looked at the above relationship for lead using both a constant compression-speed Cam Plastometer and a constant true-strain-rate Cam Plastometer designed by Orowan.5 Alder and Phillips8 investigated the relationships for aluminum, copper, and steel in the same constant true-strain-rate Plastometer. cook7 tested twelve steels at temperatures ranging from 1170° to 1473°K in the same Plastometer over a range of true-strain rates of 1.5 to 100 sec-'. The writer tested commercially pure aluminum at room temperature and depleted uranium at temperatures from 573" to 873°K at strain rates from 10-3 to 1.0 sec-1 in a Cam Plastometer designed and built at Los Alamos Scientific Laboratory.8 During the past few years the Cam Plastometer at Los Alamos has been used for a number of relatively minor experiments on brass, mild steel, duralumin, Armco iron, and depleted uranium. In this time the machine has been continually modified and improved. It was decided to utilize fully the wide range of strain rates now available with the machine by testing a material about which some information was already in the literature. Prior work on commercially pure aluminum6 appeared to deserve confirmation and expansion. So it was decided to explore the resistance to compression of this material over the currently available range of constant true-strain rates and a convenient range of temperatures. This paper is a report of that exploration. I) EQUIPMENT AND PROCEDURE The principal item of equipment is, of course, the Cam Plastometer, the working part of which is shown in Fig. 1. In this figure, an aluminum specimen may be seen between two tungsten carbide platens, in position for a room-temperature test. Above the upper carbide platen is a load cell. Output from the load cell is amplified and applied to a galvanometer in a recording oscillograph. Auxiliary equipment includes the oscillograph, the control console, a counter, and a time-mark generator. The counter is first used in adjusting the time base. Then it registers the count, of sixty pips per revolution generated by the rotating cam, in each second. These pips and the time base are also applied to galvanometers in the oscillograph. Thus, load, time, and cam position are recorded simultaneously. Heating of a specimen prior to compression is done

Jan 1, 1968

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 P. A. Flinn

ALTHOUGH many physical properties of superlat-tices have been studied intensively, relatively little attention has been paid to their mechanical properties until recently. Even for the well-known transformation in 0 brass, the effect of the transformation on plastic behavior has only lately been extensively investigated.''' A partial analysis of dislocation structure in superlattices has been given by cottrel13 and his theory agrees well with the experimental results on CU3AU.4,5 His analysis, however, is implicitly limited to low-temperature effects, since it does not include the behavior of dislocations at temperatures high enough for diffusion, and hence climb, to occur. The work of Herman and Brown2 on the creep of 0 brass indicates that important effects occur under such conditions, and consequently, the theory should be extended to include them. Such high-temperature effects cannot be observed in Cu3Au, since it disorders below the temperature at which diffusion occurs at a reasonable rate. There are materials of the same structure, however, such as Ni3A1, which retain their order up to, or close to, the melting point. GEOMETRY OF THE COMMON SUPERLATTICES The two best-known ordered structures are the 0 brass type, B2, shown in Fig. 1, and the Cu3Au type, Ll2, shown in Fig. 2. In the B2 structure the (000) and (1/2, 1/2, 1/2) sites are different in that they are occupied by different types of atoms. The symmetry of the structure is then lowered from a body-centered cubic, A2, in which the sites are equivalent, with atoms located randomly in the sites, to simple cubic. This lowering of symmetry has the consequence that two types of regions may occur within a crystal: regions where A atoms are in the (0, 0, 0) sites, and regions where they are in (1/2, 1/2, 1/2) sites. The boundary between two such regions will contain bonds between like atoms, and be a surface of higher energy. These regions are known as antiphase domains and the boundary as antiphase boundary. In the B2 structure, boundary formed during the ordering process should disappear as a result of domain growth, since any domain growing to the boundary of two others will join one and engulf the other.' In any well annealed crystal, only a single domain should exist, with antiphase boundary present only in connection with dislocations, as discussed below. The L1, structure is related to the A1 (face-centered cubic) in much the same way as the B2 is to the A2. The face-center sites are occupied by A atoms, and the corner sites by B atoms. The symmetry is again lowered to simple cubic, and antiphase domains can exist. In this case, however, there are four initially equivalent sites in the unit cell: (0,0,0), (0, 1/2, 1/2), (1/2,0, 1/2) and (1/2, 1/2, 0). In the ordered structure any one may be occupied by a B atom and the other three by A atoms. Thus four types of antiphase domains can occur in this structure. This is sufficient to permit a metastable "foam structure" to exist within a crystal.''7 Antiphase boundaries along three different planes are shown in Figs. 3, 4, and 5.* *The presence of a layer of disordered material between antiphase domains, as suggested by Jones and Sykes8 does not seem likely. Such a layer would be a region of unnecessarily high energy which could readily be reduced by the formation of the type of boundary discussed here.__________________________________________________________ The notation (111) [110] means a boundary lying along a (111) plane between antiphase regions related by a 1/2 [I10] translation. It may be seen in Figs. 3 and 4 that an antiphase boundary usually results in incorrect nearest neighbors (shown connected by braces). However, as pointed out by Wilson, a boundary of the (001) [I101 type can exist

Jan 1, 1961

By Robert E. Green, P. W. Kingman

Application of a constant geometry compression test to single crystals of aluminum of selected diameters from 1/4 to 1/64 in. showed the presence of a diameter-dependmt size effect. The most pronounced effects were found in those crystals oriented for single slip, while for specimens possessing orientations in the comers of the standard stereographic triangle virtually no size effect was exhibited. The yield stress of the crystals oriented for single slip was found to increase with decrease in specimen diameter, while the strain-hardening rate was found to be lower for the smaller specimens. The experimental results are in general agreement with those of other investigators obtained from lensile tests on copper and aluminum crystals. THE earliest systematic investigation of a possible size effect on the plasticity of metals was that of no,' who in 1926 performed tensile tests on cylindrical aluminum single crystals with diameters of 3 to 8 mm. Ono concluded that the gross stress-strain curve did not show a diameter dependence, but that the resistance to slip for strains of 0.1 pet and less appeared higher for 3-mm-diam crystals than for larger sizes. Later studies of aluminum by Maddin et al2 tentatively concluded that a size effect exists, but the conclusions were again open to question because of inconsistencies in the experimental data. Wu and Smoluchowski3 had previously shown that the slip system activated in a single-crystal sheet specimen of aluminum is a function of the specimen cross section in the slip direction, but no stress-strain data were obtained. Subsequently Fleischer and Chalmers4 studied the effect of the length of the slip direction of the primary-slip system on the stress-strain curve by testing aluminum crystals with geometrically dissimilar cross sections. In the course of this investigation a size effect was indicated in rather large crystals; however, the number of these tests was small. Other investigators have indicated that a size effect in aluminum is appreciable only for diameters of 0.5 mm or less.5, 6 Size-effect studies have also been carried out on copper crystals, the most detailed being that of Suzuki et a1.7 who performed tensile tests on specimens of many diameters ranging from 2 to 0.12 mm. Suzuki found a strong size dependence in the easy-glide region, both the extent of the easy glide and the hardening rate in easy glide were size-dependent, and the size effect was found to be orientation-dependent. Suzuki's results are in agreement with the less extensive observations of Pater-sonB and those of Garstone et al.9 A size effect was found by Rebstock using tubular copper crystals.'0 Size effects have also been noted in a brass,6, 11 in cadmium,12'19 and in hexagonal crystals.14 All the previously cited works have been entirely concerned with the variation of specimen cross section. The effects of specimen length and the change of specimen geometry which results from using progressively thinner specimens while maintaining the same specimen length have been largely ignored. A theoretical discussion of the effects of specimen length and geometry has been given by Hauser and Jackson,15 who predict a grip effect on easy glide as a function of specimen geometry provided that the specimen dimensions are large compared with the spacing between the slip bands, and by Fleischer and Chalmers,18 whose analysis of grip effects resulting from lattice rotation predicts an increase in easy glide with an increase in specimen length. A study of size and geometry effects in aluminum crystals by Kitajima and shimba17 indicated increasing amounts of easy glide in specimens of increasing length and identical cross section, and nearly identical stress-strain curves for specimens of different sizes having constant length-to-diameter ratios. Since the present study is primarily concerned with diameter dependence, the following factors were taken into account: specimen material, specimen geometry, testing method, range of sizes to be tested, and possible influence of surface and volume effects. Aluminum was chosen because of the present lack of conclusive results and the seeming possibility of size effects at relatively large diameters, the

Jan 1, 1964

By K. R. Evans

The yield and fracture characteristics of a Ti-8 pct A1 alloy have been examined at room temperature as a function of exposure temperatures to 1700°F. Em-brittlenzent of the alloy is observed to occur following exposures below 1280°F, the critical temperature for formation of ordered Ti3Al particles. Presence of Ti3Al particles results in an increase in the yield and flout stresses which, for a given exposure time, are a maximum at the critical temperature. Embrittlement is attributed to the occurrence of plastically induced fracture controlled by the increase inflow stress. This interpretation is compatible with the decreasing ductility and increasing crack popagation rates observed with increasing exposure time below the critical temperature. Slip line observations and measurements of the gain size dependence of the yield stress indicate that the slip character of the alloy is not influenced by exposure treatments below the critical temperature. ThE potential usefulness of Ti-A1 alloys in structural applications has prompted considerable interest in studies of their microstructure and mechanical characteristics. The relatively recent surge of interest in the system and at the same time its complexities are indicated by the fact that despite numerous recent efforts14 there has not even been general agreement upon a phase diagram for the system. However, most of the Ti-A1 alloys of commercial interest range in aluminum content from 5.0 to 8.5 wt pct where most investigators achowledge the existence of the ordered Ti41 phase. Goldak and parrs confirmed the existence of Ti41 from X-ray diffraction analysis of the stoichiometric composition while Blackburn6 has determined its presence in commercial Ti-8 pct A1 alloys by electron diffraction analysis and dark field transmission microscopy. The embrittlement of Ti-8 pct A1 alloys was initially reported by Crossley and carew7 who showed that aging in the temperature range of 750" to 1110°F resulted in extreme brittleness. This behavior was later confirmed and correlated by Soltiss to the presence of long-range order in the commercial Ti-8 pct Al-1 pct Mo-1 pct V alloy (Ti-8-1-1) which exhibited anomalous creep and yield strength behavior at 950°F. This investigation was designed to study the mechanical characteristics of a binary Ti-8 pct A1 alloy in order to further examine the nature of the embrittlement behavior reported for the alloy system. EXPERIMENTAL PROCEDURE A Ti-8 pct A1 binary alloy was obtained from the Wah Chang Co. in the form of 0.050 in. sheet. The chemical composition of the alloy is given in Table I. Heat-treatment of the alloy was conducted in evacuated vycor capsules for the tensile sDecimens (1.25 bv 0.25 in. gage section) and in evacuated stainless steel jackets for the crack growth-rate panels. All specimens were annealed at 1700°F for 24 hr and water quenched before an exposure at elevated temperatures. Tensile testing was conducted at room temperature in an Instron testing machine equipped with a pushbutton control for instantaneous control of the cross-head motion. In this manner the change in stress, Aa, accompanying an increase in strain-rate by a factor of 10 was measured immediately after yielding. The crack growth-rate panels used were 3 by 18 in. with a precrack 0.33 in. long cut into the center of the panel. The panels were cycled at a maximum gross stress of 40,000 psi at a maximum to minimum tension stress ratio of 20. Cycling of the specimens was continued until the crack propagated the width of the panels. The crack length was intermittently measured during slow crack growth. EXPERIMENTAL RESULTS Correlation of Embrittlement to the Critical Temperature for Ordering. Blackburn6 has found that the critical temperature, T,, for the formation of Ti41 in a Ti-8 pct A1 alloy with an interstitial content on the order of that given in Table I is approximately 1245°F. The relationship between the ductility of the binary alloy used in this investigation and T, was estimated from tensile tests on specimens which were exposed for 24 hr at various temperatures followed

Jan 1, 1970

By S. Shapiro, J. A. Ford

The crystallo graphy of several grains of the lamellar Ni-Ni3 B eutectic solidified under conditions appvoachirt equilibriun has been examined.. A preferred interlace relationship has been observed in this system which may be described as: A detailed study of this interface by means of an atomistic model reveals the interface Plane to be puckered and more accurately describable as: Analysis of the atomic configuration on these planes reveals that this interface conforms to the orientation criteria proposed for directionally solidified lanzellar eutectics. In addition, a model is proposed to help explain the growth of a "puckered" interface. DURING the past several years an increasing number of unidirectional solidification experiments on eutectic alloys have been reported in the literature. The primary emphasis, in most cases, has been the effect of growth variables on microstructure. Some authors have, however, studied the crystallographic orientations and interfacial relationships resulting from these experiments. Four crystallographic studies have been published;'-4 in each of these there is a factor which tends to prohibit the extension of the observations beyond the particular system. In the Al-CuA12 system, the approximately equal volume fractions of the phases have resulted in sorrie controversy as to which phase constitutes the matrix. In the Mg-Mg,Sn eutectic the presence of several interconnecting lamellar systems2 complicates the analysis. The two remaining eutectics. 1nSb-b and Al-Ali, are both rodlike (the latter exhibits a plate morphology at low solidification rates): the matrix in each of these alloys is the simpler (fcc) phase. Studies of nucleation in eutectic alloys indicate that the more complex constituent is the nucleating -.phase.' For the purpose of an analysis of interface crystallography it was deemed desirable to study a lamellar system in which the matrix was the more complex and, presumably. the nucleating phase. Recently it has been shown that there is a eutectic in the Ni-B system between Ni3B and i; preliminary investigation by the authors indicated that the matrix in this eutectic is the boride phase. The structure of Ni,B is reported to be orthorhombic, the compound being isostructural with cementite. This eutectic is therefore analogous to that between austenite and cementite. Furthermore, the Ni-B system is not susceptible to a competing eutectic reaction as occurs in the Fe-C alloys; nor does it exhibit a eutectoid decomposition. For these reasons the study of the interfacial relationship in the Ni-Ni3B eutectic was undertaken. PROCEDURE Ingots of nominal composition 3.5 and 3.6 wt pct B were induction-melted in boron nitride crucibles within a graphite susceptor under a boric oxide slag; a dynamic argon atmosphere was maintained over the melt to prevent rapid oxidation of the susceptor. The raw materials used were 99.97 pct Ni from Huntington Metals Division of International Nickel Co. and 99.8+ pct B chips supplied by the United Mineral and Chemical Co. The analyses of the starting materials are listed in Table I. The melt was held at 1500cC for 2 hr to insure complete reaction and allowed to cool to room temperature. The castings were chemically analyzed for boron and were metallographically examined for uniformity. The metallographic samples were mechanically polished through 0.1 p A1,0, and etched with Carapella's reagent. Each master casting was cut up to make several specimen blanks which were remelted, in boron nitride crucibles, to form ingots of 1/2 to 3/4 in. in diarn by 7 in. long. These ingots were unidirectionally solidified using a modified vertical Bridgman technique. The rate of solidification was assumed to be equal to the uniform rate at which the crucible-susceptor assembly was withdrawn from the induction coil. This rate was varied from 1.18 to 2.21 cm per hr. In order to perform these experiments it was found necessary to redetermine the eutectic composition. This was accomplished by the zone-melting technique described by Yue and lark.' An ingot of 4.5 wt pct B was zone-melted in a horizontal boron nitride boat 7-1/2 in. long with a 112-in.-square cross section. A

Jan 1, 1967

By Yoichi Ishida, Ching-Yao Cheng, John E. Dorn

Tile creep behavior of a iron was investigated over the range of temperatures from 375° to 1150°K. Apparent activation energies for creep, obtained by the effect of sudden changes in temperature on the creep rate, revealed the presence of- four distinguishable regions. The creep behavior of a iron in Regions II (480° to 774°K) and 111 (775° to 1045°K) was found to correlate well with a model where the creep rate is controlled by the nonconsevualive motion. of jogged screw dislocations. An anomalous increase in the apparent activation energy fur creep in Region III was found to be in harmony with the known decrease in the free activation energy for self-diffusion over the Curie transformation range. Furthermore, the creep rates in Regions II and III were found to increase with stress due not only to the effect of stress on the activation energy but also to an increase in density of mobile dislocations. The evidence suggests that pipe diffusion along moving dislocations could be a significant factor over the lower temperatures of Region II. ALTHOUGH the creep properties of iron and steel have been of interest to metallurgists for some time and an extensive literature is now available, most of the published information has not produced much toward understanding the fundamental dislocation processes controlling the creep behavior of these materials. Whereas the activation energy for high-temperature creep of metals usually agrees well with that for self-diffusion, Sherby, Orr, and Dorn1 deduced from the data of Tapsell -and c1enshaw2 that the activation energy for creep of Armco iron is about 78,000 cal per mole and more recently Lytton and sherby3 reviewed the data of Jenkins and Mellor4 and found an activation energy for creep of a iron of 80,000 cal per mole. Both values are substantially greater than the activation energy for self-diffusion in a iron. Because of the limited data suitable for purposes of identifying the controlling dislocation mechanisms of creep and the unusually high activation energies for creep quoted above, it was considered desirable to reinvestigate in detail the creep of a iron by more reliable techniques which would provide sufficient data for determination of the creep mechanisms. EXPERIMENTAL TECHNIQUE Creep specimens were prepared from 3/8 by 4 in. iron bar stock of the following composition by weight percent: 0.001 C, 0.0120 0, 0.001 N, 0.004 S, and 0.003 P. The as-received bars were cold-rolled to a thickness of 0.100 in., annealed under argon for 30 min at 1113°K, cold-rolled to a final thickness of 0.063 in., and machined into tensile specimens having gage section 0.250 in. wide and 1.70 in. long. Finally they were recrystallized under argon at 1113°K. Specimens to be crept above 1060°K were recrystallized at 1173°K. Both recrystallization treatments gave the same reproducible equiaxed ASTM No. 4 grain size. Creep testing was conducted in machines fitted with Andrade-Chalmers arms that maintained a constant stress to within ±0.2 pct of the reported values. Deformation over the specimen gage section was sensed with a linear differential transformer and recorded auto-graphically as a function of time. The strains deduced from these measurements were sensitive to ±5 x 10-5. During creep the specimens were contained in an argon-filled chamber which was immersed in a temperature-controlled molten tin bath. Creep temperatures, as measured by thermocouples attached to the specimen, were maintained to within ±10.25°K of the reported values. For activation-energy determinations rapid changes in temperature of about 12°K were obtained within 30 sec by direct resistance heating of the creep specimen, and maintained to ±1°K of the reported values. Observations of structural details of specimens before and after creep tests were made by electrolytic polishing and etching in acqueous ammonium persulfate. EXPERIMENTAL RESULTS A typical example of the determination of apparent activation energies, Q, by the effect of small changes in temperature is illustrated in Fig. 1. Q is defined by

Jan 1, 1967

By W. A. Sheaffer

Electric furnace installation and tough-pitch copper-casting operation at Canadian Copper Refiners Ltd. are described. General layout, power supply and control, refractories, induction pour hearth, casting equipment, metal temperature control, and oxygen-content control are discussed. E LECTRIC furnace at Canadian Copper Refiners Ltd. was put into operation in August 1949. The installation was designed primarily to melt electrolytic copper cathodes and to produce vertically cast tough-pitch shapes. To meet emergencies during reverberatory furnace shut-downs, provision was made for casting horizontal tough-pitch wire bars. Due to the ease with which metal temperatures, melting rates, oxygen content, and casting hours can be altered to suit production demands, the electric furnace has met the requirements admirably. General Layout The plant has been described by H. S. McKnight' and by J. H. Schloen and E. M. Elkin.2 Since these papers were written, the electric furnace has been installed in a 140 ft extension of the original casting building. The extension, 264 ft in width, is divided into one 24 ft and four 60 ft bays, each a continuation of similar bays in the older building. Fig. l, a partial floor plan of the extension, shows the location of major equipment. Power Supply and Control Power for the electric furnace and its auxiliary equipment is delivered by Quebec Hydro over two 12 kv three-phase, 60 cycle pole lines. One line is in use, while the second serves as an emergency standby. Connections for the electric furnace from these lines, which also feed the refinery power house, are made to a substation on Canadian Copper Refiners Ltd. property. Connections between this substation and the furnace transformer room are in underground conduit. The are-furnace transformer, 550 v auxiliary-equipment transformer, and 12 kv switchgear are in the transformer room near the furnace. Stepdown from 12 kv to are-furnace voltages is done by a 7500 kva oil-immersed water-cooled three-phase 60 cycle transformer. This unusually high kva rating is available because the arc furnace and transformer were adapted from a steel-melting unit. Secondary voltages are available in 16 steps between 251 and 95 v (across phases). A four-position tap changer, operated from the furnace switchboard is connected to taps yielding 199, 164.5, 127, and 115 v, respectively. The transformer primary feeder is equipped with a General Electric Magne-Blast circuit breaker. The pour hearth, casting wheel, bosh conveyor, and other auxiliary equipment are fed by a 12 kv to 550 v, 750 kva three-phase 60 cycle transformer. Graphite electrodes, 14 in., with tapered nipples are held in the are-furnace electrode arms with steel wedges. The arms, fed from the transformer secondary busbars by flexible cable bundles, are actuated by winch cables. Direct-current motors operating the winches are supplied by a 250 v motor-generator set. Power input to the furnace is controlled from the furnace switchboard. The board has the usual combination of remote controls for the 12 kv breaker and transformer tap changer, meters, overload relays, automatic and manual electrode motion controls, switchgear, etc. When power is on the furnace, automatic electrode feed is used; the power draw on a given voltage tap then is governed by current-limiting rheostats. The rheostats work through a Westinghouse bal-lanced-beam control circuit which, in turn, operates reversing contactors in the winch motor circuits. Arc Furnace The arc furnace is a standard-type NT Pittsburgh 'Lectromelt with inside shell diameter 12 ft 3¾ in. By hydraulic-lift cylinders, the furnace can be tilted forward to 39 ½ ° and backward to 5" from horizontal. A roof-swing cylinder is also installed but not used. Fig. 2 shows refractory-lining details. With the lining as shown, operating life between repairs is 6 to 9 months of two-shift casting operation. Charge slot, skim door, and roof refractories then are replaced completely, and any necessary repairs made to side walls. Bottom life is longer and the original under courses are still in service, while the top course was replaced in October 1951. The launder is lined with high chrome-magnesite trough brick backed by fireclay and insulating brick. The trough is covered with fireclay brick and asbestos sheet. At intervals, openings 12x6 in. are left in the permanent covering. These are covered with

Jan 1, 1956

By C. W. Mueller, P. H. Robinson

A technique was developed for depositing single -crystal films of silicon on single-crystal sapphire substrates via the pyrolytic decomposition of SiH4/H2 mixtures. Electron diffraction and X-ray Laue reflection examinations of these films revealed single-crystal patterns. These films were characterized by measuring conductivity type, thickness, resistivity, and Hall mobility. Chemical etching, dislocation staining, and electron-microscopy examination have indicated the presence of low-angle grain boundaries and microtwinning in the silicon films. The role of the sapphire substrate with respect to its quality, orientation, surface finish, and thermal and chemical treatment was investigated. Hall mobility as a function of sapphire orientation was measured. A mobility equal to 88 pct of bulk silicon mobility was attained. Insulated-gate field-effect transistors which have a transconductance of 4000 pmho at 6 ma were fabricated using these films. THE technology of the fabrication of microelectronic circuits with active and passive components directly on a single wafer of semiconductor material has attained a high degree of perfection during the last few years. One inherent difficulty with the single-wafer approach has been undesirable coupling between components arising from the common base material. Several techniques have been developed for minimizing this coupling and obtaining good electrical isolation between components; however, these result in extra capacitance being added to the circuit. The extraneous capacitance of the connecting leads, resistors, and capacitors degrade circuit performance and limit the high-frequency operation of these circuits. Recently there has been considerable interestl-3 in the deposition of silicon films upon insulating substrates. The use of silicon as the semiconductor allows the subsequent utilization of the large amount of technology which has been developed for silicon for the fabrication of good active components. A sapphire substrate supplies an excellent insulating material which at the same time gives a thermal-conductivity improvement of an order of magnitude over glass-type substrates. This paper will describe the results obtained for the deposition of single-crystal silicon layers upon single-crystal sapphire substrates as well as the characterization of these films. I) APPARATUS The 'system used for the growth of silicon films on sapphire substrates by means of the pyrolysis of SiH4/H2 mixtures is shown in Fig. 1. The all-quartz reaction chamber is water-cooled and includes a quartz optical-flat window for use in conjunction with a 5 kw, 2.5 Mc per sec constant-temperature controlled rf generator. The temperature sensor for the rf generator is a thermopile which is focused through the quartz optical flat onto the susceptor surface. With this system the rf generator will hold the temperature of the susceptor to about +0.3°C at 1200°C. The susceptor is supported on a quartz sled inclined to the gas flow to increase the uniformity of the deposition. The water jacket surrounding the reaction chamber is used to keep the quartz wall temperature low enough to limit the decomposition of the silane to the rf-heated susceptor which contains the sapphire substrates. This eliminates the reaction of silicon with the hot quartz to form SiO which deposits out on the apparatus walls, thus obscuring vision, and interferes with the optical measurements of the temperature as well as with the growth process itself. Provision is also made for "n"- and 'p"-type doping by using mixtures of either phosphine or diborane in hydrogen which are added to the silane during the growth process. The hydrogen used is the purest commercially available tank hydrogen further purified by use of a palladium diffuser. The susceptors which were used include 1) spectro-scopically pure graphite, 2) high-purity molybdenum, 3) high-resistivity silicon using a low-resistivity insert to facilitate coupling to the rf generator, 4) silicon carbide-coated graphite. The latter two susceptor materials produced silicon films on sapphire substrates with more reproducible resistivities. Prior to silicon deposition all connecting lines as well as the reaction chamber are thoroughly flushed with argon and then hydrogen. After the hydrogen flow is set, the growth temperature is adjusted to 11009 to 1150°C, and when thermal equilibrium is reached the silane flow is started. The flow rate of the hydrogen must be fast enough so that turbulent flow occurs in the size of reaction tube used, otherwise a streaked nonuniform silicon deposit occurs. After the deposition

Jan 1, 1967

By D. C. Seidel, E. F. Fitzhugh

The Colorado School of Mines Research Foundation has developed a hydrometallurgical process for recovering nickel from oxidized ores, including both the iron-rich laterites and magnesium-rich, soft silicates. Known as the HSO-HTCP (Hydrothermal Sulfidization Oxidation-High Temperature Cementation in Pulp) Process, the system consists of feed preparation, sulfidization, oxidation, precipitation (cementation), and calcination and melting. This paper deals primarily with the sulfidization and oxidation phases of the process. Nickel sulfide ores lend themselves readily to concentration before smelting or pressure leaching, but neither of the major oxidized ore types — the iron-rich laterites and magnesium-rich, soft silicates-has been directly concentrated. Upgrading of crude ore in current practice is limited to cobbing lumps of the harder, lower grade rock (protore) from the softer, enriched silicate ore, because only a small percentage of the nickel in these ores occurs in discrete, contrasting mineral particles. There is no apparent mineralogical contrast in the superficial, iron-rich lateritic ores and, in fact, there is no firm assurance that the nickel atoms are within the lattices of the limonite minerals, or else irregularly adsorbed on the limonite. Within underlying, "rotten rock" silicates, occasional veinlets of gamierite and related nickeliferous silicates are found.' The gamierite veinlets, however, are only incidental, and the majority of the nickel atoms occur as erratic replacements of magnesium atoms in the micaceous chlorites of the ore mass. Pyrometallurgical processes account for nearly all the nickel currently being recovered from oxidized ores. Plants in New Caledonia, Oregon, Japan, Brazil and Greece smelt the ores to make ferronickels or a sulfide matte,2 and the ammoniacal leaching3 at Nicaro, Cuba, is preceded by a reducing roasL4 The only fully hydrometallurgical installation has been the politically ill-fated Freeport Nickel Co. enterprise, and this process was limited to lateritic ores.5p6 A hydrometallurgical technique which might handle both laterite and the typically richer silicate ores has been an enticing goal. The technique described here was developed at the Colorado School of Mines Research Foundation, Inc. on behalf of the Republic Steel Corp. It uses sulfur, heat, air and metallic iron to recover nickel from these ores. Inasmuch as the ores are treated as aqueous slurries, the cost of drying a plant feed that normally carried 30% or more moisture is eliminated, and there are no dust problems. Patent applications have been filed by Republic Steel Corp. on the procedures used for getting the metal into solution and on the subsequent recovery without liquids-so l ids separation of the slurry. It is referred to as the HSO-HTCP Process (Hydrothermal Sulfidization Oxidation — High Temperature Cementation in Pulp). THE PROCESS FLOWSHEET The results of various experimental studies have been combined to form the continuous flowsheet illustrated in Fig. 1. This flowsheet serves as a general pattern showing the sequence of the operations which include: (1) feed preparation; (2) sulfidization; (3) oxidation; (4) precipitation (cementation); and (5) calcination and melting. This paper deals primarily with the sulfidization and oxidation phases of the process. Feed preparation: In general, the silicate ores can be considered as earthy rather than hard, and preparation might be carried out before the addition of water in a trommel, or with water in a scrubber or log washer. This breaks up the earthy particles, allowing the hard lumps to be separated by screening. The oversize material from most ores is relatively barren and may be discarded. If there is occasion to control the iron-magnesium ratio in the plant feed, laterite, which normally breaks up readily into fine sized particles, and silicates are mixed in suitable proportions. The fine product slurry from the initial steps is mixed with elemental sulfur and fed to a conventional ball mill, although the amount of actual grinding that takes place is relatively small. The object of milling is to complete the disintegration to natural particle size and to produce an intimate mixture of the ore and elemental sulfur. This pulp, which is almost entirely -200 mesh, has a pH of about 7.0 and normally can

Jan 1, 1969

By C. D. Allman

Specifications for coal at the Grand Lake thermal electric station read in part: "Coal will be Rom Minto Bituminous (strip operation). Maximum lump 3x3x4 ft. Very corrosive, abrasive and when damp, sticky. Coal may consist of frozen lumps of coal, snow and ice." To maintain quality control it was necessary to develop an automatic sampling system capable of: 1) sampling from one 10-ton truckload every 1½ min; 2) permitting an operator to automatically take a sample from each truckload; 3) depositing the sample in a pre-selected container, one of a possible 10; and 4) performing the sampling operations in accordance with latest ASTM specifications for sampling coal with an ash content of 35%. This paper tells how these and other problems were resolved and describes the equipment used. The New Brunswick Electric Power Commission issued detailed specification No. 5351-5009 outlining the scope of work and general requirements for a mechanical coal handling system to be installed at the Commissions Grand Lake Generating Station. The thermal station is located at Newcastle Creek, some 40 miles east of Fredericton, N.B. Canada, on the shore of Grand Lake. This particular location is immediately adjacent to the Minto strip mining coal area of New Brunswick. Contained in the specifications, but not detailed specifically was an automatic coal sampling system. The system outlined, was to be designed and specified by the individual equipment tenderers. In conjunction with the Hardinge Co., the Barber-Greene Co. designed a sampling system which was contained in the general contract proposal. The system as designed originally, however, presented certain limitations to a continuous coal handling system and was ultimately changed. However, it was only through preliminary study and design that problems created by the specifications were determined, and these problems discussed and finally negotiated with the NBEPC engineering staff created the subsequent sampling system now being installed by Barber-Greene. It must be considered that where the original specifications did not detail the mechanical equipment, it was necessary to present a system which would correspond to the intent of specification and for which Barber-Greene would be responsible as to function, but remain in a competitive position with regard to the tender considered primarily on a price basis. The system now being installed, contains basically all the components which were detailed originally, with the exception of the holding bin arrangement, which was changed to allow a continuous operation of the entire coal handling system. SPECIFICATIONS The specifications covering the sampling system follow. 4.5 Sampler: An automatic sampling system shall be installed capable of sampling one-truck load of coal every 1½ min. When the coal is dumped into the receiving hopper, the operator shall push a button and the sampler shall automatically take a sample of that particular coal when it reaches the sampler. Then the sample taken shall be crushed and reduced in quantity to a workable sample and deposited in a pre-selected container, one of a possible ten. All samples and sampling operations shall be in accordance with the latest edition of ASTM designation 492 for sampling coal with an ash content of 35%. The coal for the initial sample shall have maximum sized lumps of about 3/4 in. and the final sample shall be adjustable from 2 to 5 lb per sample and capable of passing through a sieve with 1/8-in. diam openings. It should be noted that, because of the time delay between the time the sample is requested and when it is actually taken, the operator may call for one or two additional samples from different coal before the first sample is completely refined and in the final sample can. Coal is received from a number of different suppliers on the same day, therefore, the system shall be designed so that there is no possibility of mixing or contaminating the coal from the different suppliers. All coal rejected from the sample shall be returned to the main conveyor. All chutes, hoppers, etc. shall be designed in accordance with Section 4.6 of these specifications. 4.6 Chutes, Hoppers, etc. All chutes and hoppers

Jan 1, 1963

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The effects of grain size and shape on alloys of titanium with nitrogen and aluminum have been determined. Increasing a grain size decreases strength and hardness and increases impact resistance. Quenching from the ß field produces subgrain markings delineating a plates in Ti-N alloys but not in Ti-AI alloys. This suggests a precipitation from the high nitrogen alloys. ALPHA titanium alloys are single-phase alloys with the hexagonal-close-packed structure of a titanium. If these alloys are worked and annealed within the a field, equiaxed structures result in which strength is derived from the solid solution of the alloying elements present. Strain hardening can be used to increase further the strength of a titanium alloys. This is the only other mode of strengthening the a type of alloy. Quenching from the ß field has been noted by many investigators to have little effect on the strength of iodide titanium and on commercial titanium. Ti-A1 alloys were found to be little different in hardness, whether annealed in the a field or quenched from the ß field.' These facts illustrate a characteristic of a titanium alloys: they are insensitive to heat treatments from the ß field. Underlying this heat-treatment insensitivity are the facts that the a-ß field is generally narrow in a titanium alloys, the transformation-temperature range increases with a-stabilizing content, and the a solubilities of the alloying elements are greater than the ß solubilities. When quenching is done from the ß field, there is no supersaturation of the alloying elements in the acicular transformation structure produced. Welds in a titanium alloys generally are ductile, because no transformation hardening occurs during cooling.1,2 Other desirable features of a alloys are: no thermal-stability problem, excellent toughness, and retention of strength at elevated temperatures better than a-ß or ß alloys of comparable room-temperature strength. The prime factors governing the properties of a titanium alloys are the amount and kind of solute present. This can change the a phase from a soft, tough material into a hard, brittle material with no apparent change in microstructure. Moreover, brit-tleness can exist over a wider alloy-content range, without change of phase, than in most other metals. The solutes for a titanium may be divided into interstitial and substitutional types. Oxygen and nitrogen dissolve interstitially in rather large amounts, extending well through the brittle range, and the transformation-temverature ranges are raised in the process.:' , carbon has a maximum interstitial solubility of about 0.5 pct at the peritectoid temperature, while at lower temperatures the solubility decreases to about 0.2 pct.3,5 Substitutional a solutes include aluminum and tin. Aluminum has a high a solubility of 25 pct Al, and increases the transformation-temperature range markedly.6,7 Tin has a high a solubility of about 20 pct, but has a relatively innocuous effect on the transformation-temperature range.' The choice between interstitial and substitutional solutes generally has been conceded to the substitutional solutes because of a belief that they do not have as adverse an effect on ductility and notch toughness. However, a recent investigation8 on the effect of hydrogen on titanium has shown that this element, which is not under compositional control, has a powerful detrimental effect on notch toughness. Hydrogen was shown to form a hydride which is practically insoluble (about 0.002 pct) in a titanium at room temperature, although the solubility at the eutectoid temperature of about 300°C is relatively high, about 0.16 pct. Limited data were presented on the effect of hydrogen on a alloys, where the same impairment of toughness as in unalloyed titanium is found. The work reported here describes the effects of interstitial and substitutional solutes on 1—the mechanical properties of high purity titanium free of titanium hydride and 2—the influence of structural variables on these properties. Nitrogen was selected as an example of an interstitial solute with high solubility and aluminum as a substitutional solute with high solubility. All compositions were well within the ductile range, since it was not intended to study the brittleness problem here, but to study only the factors influencing optimum mechanical properties. Procedures The alloys were prepared from iodide titanium as 1/2 Ib ingots double melted to insure homogeneity.

Jan 1, 1955

By Donald B. Evans, Robert D. Pehlke

The solubility of nilrogen in liquid binary alloys of iron with Litanium. zivconium, columbium, vanndiurn, and tantalum was measured for alloy composiLions up to the solalbility limils of lhe alloy nitrides. All five alloying agents were found to decrease markedly the activity coefficient of nitrogen in liquid ivon. The metal/nitvogen mole ralios in the alloy nitrides formed were generally .found to be slighlly greater than 1.0, but in no case greater than 1.5. From the experimental data, the standard free energies of fortmation of titanium and zir-conium nitrides have been calculated for the Lemperaluve range 1550° to 1750 C. The solublily Products for columbium, tantalum, and vanadium nitrides are also reported. A number of research investigations have examined the effect of refractory metals on the solubility of nitrogen in liquid iron. Although data on zirconium are not available, investigators are in agreement that titanium, vanadium, columbium, and tantalum markedly increase the solubility of nitrogen in liquid iron. This fact alone makes desirable the acquisition of thermodynamic data for these elements in liquid iron. Since refractory metals are known to be stable nitride formers, they have been suggested as steel denitrifying agents, and some of their nitrides have recently been considered as containment materials for liquid iron and iron alloys. Most available thermodynamic data for these metals relate to their dilute concentrations, but effective thermodynamic treatment of these applications requires data at concentrations near the solubility limit of the alloy nitride. Although some work has been done at relatively high alloy concentrations in liquid iron (particularly for vanadium 2,3 and titanium 2,4), the results have been somewhat contradictory. Disagreement may be partly attributed to the fact that the compositions of most refractory metal nitrides have been shown to be nonstoichiometric, and to vary 2,5-8 depending on the temperature and nitrogen gas pressure with which the solid nitride phase is in equilibrium. One purpose of this study consequently has been to determine the compositions of the refractory metal nitrides precipitated from a liquid iron solution. EXPERIMENTAL PROCEDURE Rao and Parlee2 and Evans and Pehlke 9 have discussed the technique for measuring the solubility product of an alloy nitride phase in liquid iron by finding the point of departure of the nitrogen solubility from Sieverts' law. The method consists of measuring the solubility of nitrogen in a melt of iron containing a known concentration of a second metal as a function of the nitrogen gas pressure over the melt. In this study the second metal was one of the refractory metals titanium, zirconium, columbium, vanadium, or tantalum. When the nitrogen pressure at which the refractory nitride forms is reached, a deviation of the measured solubility of nitrogen in the melt from Sieverts' law is observed in the form of a "pressure halt." The concentration of nitrogen in the melt associated with this breakpoint in the nitrogen-absorption curve is then used to calculate the nitride solubility. The Sieverts method was used to measure nitrogen solubility as a function of nitrogen pressure and temperature. The experimental equipment for this technique has been previously described in detail. 1,9 Charge materials used were vacuum-melted high-purity iron (Ferrovac-E) and the best commercial grades of the refractory metals obtainable (in all cases at least 99.8+ pct pure). Recrystallized alumina crucibles were used to hold all melts except those containing zirconium, for which zirconia crucibles were necessary. Temperatures were measured by a disappearing-filament type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diameter sight hole in the crucible lid. By means of a technique previously described, 9 in which the refractory-metal nitride was precipitated at one temperature then redis-solved by raising the temperature 50°C and precipitated again at a higher temperature, it was possible to obtain data over a temperature range of up to 200°C on a single melt. It was found that this technique could not be used with melts containing zir-

Jan 1, 1965

By Raynor Linzey, Karl M. Busen

The formation of thin films of silicon oxide by anodic oxidation of silicon and the subsequent removal of these films by an etch is a process often used for the evaluation of concentration distributions Profiles) in silicon layers by the differential sheet conductance method. The accuracy of the resulting profile is very strongly influenced by the uniformity of the thickness of the reacted silicon. Normally, it would be expected that for a constant number of coulombs passed the thickness would be the same from oxidation to oxidation. Investigations show that in certain electrolytes, for a given number of coulombs passed through an n-type silicon sample, the thickness of the reacted silicon increased with increasing resistivity. Even for the same resistivity the thickness varied sometimes by a factor of 1.5. When an electrolyte was used which consisted of 10 pct water by volume in ethylene glycol with 4.0 g KNO per 1000 ml of solution, anodiza-tion at 5 ma per sq cm led to satisfying results. Short-time anodizations gave oxide layers of a higher apparent density than those experienced from thermally gown silicon oxides. THE functioning and the electrical characteristics of semiconductor devices are based upon the incorporation of "impurities" into a single-crystalline body of suitable material and on the concentration distribution (profile) of this impurity. The incorporation can be achieved by well-known processes as, for example, by diffusion, epitaxial growth, alloying, or ion implantation. Often the profile resulting from these processes is not known. A powerful tool to learn about a concentration distribution is given by the method of differential sheet conductance which employs successive four-probe measurements on a layer subjected to stepwise removal of thin sublayers. Differential sheet conductance vs position (or penetration depth) of a sublayer is plotted and a smooth curve is drawn through the data. From this curve the profile is then calculated. When the semiconductor material is silicon, the sublayers are removed suitably by anodic oxidation of the silicon and subsequent dissolving of the formed silicon oxide by an etch. The accuracy of the resulting profile is very strongly influenced by the uniformity of the sublayer thickness. Normally, it would be expected that, for a constant number of coulombs passed, the thickness would be constant from oxidation to oxidation. Investigations showed that for sublayers several hundred angstroms thick the reproducibility can be rather poor. Therefore, efforts were made to obtain a reliable technique for uniform removal. The present paper describes such a technique and certain phenomena which were encountered during the investigations. APPARATUS AND TECHNIQUE The first report on the investigation of concentration distributions, where for differential sheet conductance measurements thin silicon sublayers were removed from a diffused layer by anodic oxidation, was given by Tannenbaum. The author reports the removal of sublayers which for the most part were 400 thick. More advanced device designs now require much narrower layers. When it was tried in these laboratories to determine profiles within such layers, difficulties were encountered with respect to sublayers which by necessity had to be thinner than the ones reported by Tannenbaum. The apparatus used for the investigations is sketched in Fig. 1. Two cylindrical containers connected by a wide tube are filled with an electrolyte. The left container receives the cathode whereas the right container is closed at the bottom end by a sample support consisting of a Teflon base and a copper pedestal. The silicon sample (1 by 1 cm) is mounted to the pedestal embedded flush in the Teflon base using silver paint (Degussa) for electrical contact. Pyseal is applied to the edges of the sample to protect the copper pedestal from the electrolyte. The base is mounted to the container using a water-tight silicon rubber gasket. Fig. 2 gives a view of the sample support. The copper pedestal is connected to the positive side of a power supply operating at a constant current output (Kepco Model ABC 425M). The electrolyte which has been reported by Duffek et al. consisted of either 2 or 10 pct water by volume in ethylene glycol and 4.0 g KNO3 in 1000-ml solution. The electrolyte is best prepared

Jan 1, 1967