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By S. R. Zimmerley, John Gross

The deductions drawn in crushing and grinding operations have heretofore been based on a separation of the products into various sizes. A crushed product may be sized by sieving, by elutriation and by aid of the microscope. To estimate the surface of each size the relation of the surface to the estimated average diameter must be assumed. Such a relation, owing to the irregularity of the particles, may involve two assumptions: First, a factor to convert average diameter to surface for one particular size; and second, a variation in the factor as the diameter of the particle changes. Obviously a surface measurement in which such assumptions and estimates are involved is questionable. In the first paper of this series1 a method has been given by which an accurate measure of surface of quartz can be obtained from its dissolution rate. By the use of this method, surface measurements have been made on a series of sieve sizes of crushed quartz, the results of which are given and discussed in this paper. Prepaeation of the Quartz Sizes The quartz, consisting of large uniform pieces with a density of 2.65 and a purity of 99.5 per cent. SiO2, was crushed to pass 20 mesh and was then sieved. Tyler standard sieves were used, the sieving being done by hand according to the proposed standard method submitted by the senior author to the Milling Committee of the A. I. M. E. A wet split of the sample was made on a 270-mesh sieve. This was followed by dry sieving until less than 0.05 per cent. of the weight of the sample passed through the sieve in 1-min. sieving. The +28-mesh material was discarded because that size did not contain the difficult grains from the 20-mesh sieve.

Jan 1, 1930

Discussion of the paper of DAVID COLE, presented at the New York meeting, February, 1915, and printed in Bulletin No. 9S, February, 191.5, pp. 431 to 444. R. H. RICHARDS, Boston, Mass.-The Butchart riffle seems to violate, according to our preconceived notions, some of the very essential principles of the Wilfley riffle, and therefore ought not to succeed, but it does. On this account it must conform to other very important principles, or it would not succeed. It would beinteresting to know what these principles are which enable it to succeed. E. P. MATHEWSON, Butte, Mont.-I cannot, explain the principles on which this riffle acts, because I have not given it personal attention. All I can say is that I first saw the riffle in operation several years ago at the Steptoe Valley mill in Nevada, and I was told that a man had been around there guaranteeing that these riffles would make the table do twice as much work and do it better than with the ordinary Wilfley riffles. I heard nothing further about it for a long time. I heard about a year ago, from David Cole, the author of this paper, that the riffles were a success, and that he was using them at Morenci, and if, we were interested he would send the inventor to show us how they worked. As we knew of David Cole's reputation, we invited Mr. Butchart to come up and show us how his riffles worked. We did not have sufficient confidence in the invention to guarantee Mr. Butchart his traveling expenses, but lie came up entirely at his own expense and put in a set of the riffles on one table. It was known as a roughing table in our No.

Jan 5, 1915

By J. I. Drever, C. R. McKee

The push-pull test, which is a simple injection and pumping sequence of ground water spiked with solutes of interest, is presented as a method of determining the adsorption characteristics of a formation. Adsorption properties are necessary to predict restoration from both in situ coal gasification and in situ uranium extraction. The major problems in applying laboratory measurements to the field concern scaling the effect of particle size, and obtaining representative samples. Laboratory measurements are conducted on gram to kilogram scale samples, whereas the push-pull test evaluates a sample weighing approximately 130 to 1,000 metric tons, depending on volume injected and porosity. The problems in translating laboratory results to the field appear to be less severe for sedimentary uranium bodies than for coal. Laboratory measurements are useful in delineating possible ranges in adsorption properties, and in planning the field experiment. The adsorption properties of a formation are characterized by the cation exchange capacity (C) and the distribution coefficient measured at low concentration, (kd) 'Laboratory procedures for their measurement on coal and uranium ore are reported. Two field push-pull tests were conducted on uranium formations in Wyoming. Adsorption properties estimated from these tests on the basis of a simple cell model were compared to the laboratory values. In the first case, excellent agreement was observed between the values estimated from the field test and the values measured in the laboratory. In the second case, the value for kd determined in the laboratory was 5 times higher than the field value. It is recommended that push-pull tests be conducted on coal formations being considered for in situ gasification in view of the great uncertainty in extrapolating 1aboratory.adsorption properties to the field.

Jan 1, 1979

By Rodney P. Smith

The rate of motion of the boundary between a single-phase a-iron region and a two phase a-iron plus ?-iron, or a-iron plus cementite region has been measured on decarburization at several temperatures between 500" and 865°C. These data, together with data for the carbon content of a-iron at the boundary, yield the diffusivity of carbon in a-iron. The activation energy for carbon diffusion is 19.8 kcal per mole for the temperature range —50° to 150°C and increases to an average value of 23.0 kcaL per mole for the temperature range 727" to 865°C. AS part of an investigation of the diffusivity of carbon in iron using a steady-state method,' the diffusivity of carbon in a-iron was determined at the temperatures 802" and 851°C. The diffusion constant thus obtained was larger, by nearly a factor of two, than that predicted from the combined results of stanley2 and of Wert.3 It seemed desirable, therefore, to continue the investigation. Since the temperature range in which the steady-state method can be conveniently used is limited, we have chosen a decarburization method, based on the laws of diffusion in metal accompanied by a phase change.4,5 If the initial carbon content of the Fe-C alloy is such that two phases coexist at the decar-burizing temperature* and decarburization is car- ried out such that the surface is maintained at substantially zero wt pct. C, the carbon distribution after a time, t, will be as shown in Fig. 1. The boundary between the single-phase and two-phase regions moves from y = 0 to y = x in the time, t, where x is proportional4 to tl". If the initial carbon (content of the sample is Ci, and CB is

Jan 1, 1962

By Eugene A. Stephenson

Critical analyses of the work expended in producing oil by the utilization of gas energy have appeared in the publications of Shaw,' Pierce and LewisI2 and Herold,3 authors who have ably discussed the factors which must be taken into consideration in comparing energy consumed per barrel in various wells which are flowed by means of gas-lift. However, two distinct phases of oil production are concerned with the ratio of gas energy consumed to oil produced. One of these phases is the gas-lift, which utilizes the differential gas pressures for the purpose of flowing oil, whether these pressures be natural reservoir pressures or be induced by artificial compression of gas or air. The other phase has to do with prorating oil production in pools which are operated either as units, or are subject to such restrictions as those imposed at Oklahoma City by the Corporation Commission, or by similar controlling groups in other fields. An abundance of literature is available relative to the problems of flowing wells by gas-lift, but the first suggestion that the energy of the gas within the oil and gas pool might serve as a basis for proration, appeared in the timely article by Mc Williams.4 Much of the dissatisfaction with proration in certain fields arises because some operators feel that besides the hazard to the wells which accompanies the test, the method of allocating production on the basis of the " potential" gage is inequitable and gives some operators a distinct advantage over others.5 The most severe penalty may be exacted from the most progressive operators or those who attempt to produce their oil with a minimum quantity of reservoir gas. If no difficulties ever developed in drilling, shutting off water, or in well completion, it might

Jan 1, 1931

By Jerome Alexander

THE object of this paper is to show that many of the important phenomena of metals and alloys are due to the facts that, at some stage, metals and alloys, or some of their constituents, are in a colloidal state and that a portion of the metal or alloy tends to remain in this state. The so-called amorphous phase in pure metals is an isocolloid, consisting of colloidal groups of metal molecules that may be dispersed in still more finely subdivided metal; these colloidal particles are not truly amorphous, but may consist, in part, if not entirely, of ultramicroscopic crystals; as a result the expressions amorphous phase and amorphous theory might be replaced by the expressions colloidal phase and colloidal theory. Any substance is in the colloidal state when the constituent particles consist of molecular or atomic groups, whose size varies approximately from about 100µµ down to about 5µµ, that is from just below the limit of microscopic resolvability to the dimensions commonly ascribed to the larger molecules. Colloidality involves no assumption as to the shape, internal structure, or orientation of the colloidal particles; size alone is the critical factor. A colloidal system may therefore contain crystalline groups, or amorphous groups (non-crystalline, random or haphazard clusters), or a mixture of the two. All colloids consist of at least two phases, the subdivided substance, or dispersed phase, and the substance into which this is subdivided, the dispersion medium. It is not necessary that there be any chemical difference between the dispersed phase and the dispersion medium. As molecular forces are extremely powerful, their application may produce marked changes in the physical properties of metals. It is doubtful whether metal in the interior, especially of large masses, possesses the same properties as that on or near the surface, which alone is open to, inspection.

Jan 10, 1920

By W. F. Domis, F. von Gemmingen, R. W. Whitmore, F. Garofalo

Constant-load creep-rupture tests at 1100°, 1300° and 1500°F were made on a Type-316, 18 Cr-8 Ni-ZMo, austenitic stainless steel to determine the relationship between ruptzire life and other aspects of creep behavior, The test program was designed on a statistical basis to check the variability of various creep properties and to determine emprically the dependence of minimutn creep rate and ruptzire life on initial stress, The dependence of the rupture life, tn, on the initial stress, a,, is found to be related to the stress dependence of the wrinimum creep rate, i,, and secondary creep strain, The instabilities or breaks found in the conventionual log - logt, plots can be traced to either a change in the linear dependence of log i, on log a, or to a change in secondary creep strain. In the alloy tested, rupture is found to be predowmanantly of the inter crystalline type, For this material, the secondary creep strain is -found to depend on the nature of the grain boundary precipitate, which affects grain boundary migration. It has been shown for a variety of metals and al tested at elevated temperatures under creep conditions that the empirical relationship exists between rupture life, tr, and minimum creep rate, i,. This relationship, in which C and a are in some cases independent of stress or temperature, shows in a general way that creep rupture depends on creep behavior prior to tertiary creep stage. To determine more fully the factors which control creep rupture requires, therefore, more knowledge of the relationship between rupture and creep behavior. To obtain such information, constant-load creep-rupture tests have been made on a Type-316, 18 Cr-8 Ni-2 Mo, austenitic stainless steel at 11000, 1300°, and 1500°F. These tests were designed on a statistical basis to determine the variability of the various creep properties measured and to determine empirically the stress dependence of minimum creep rate and rupture life. As a result of this work, various empirical relations have been established defining more closely the factor, C, in the relation between rupture life and minimum creep rate. This factor is found to be proportional to the amount of strain during secondary creep. The variation of secondary creep strain with rupture life and temperature is determined and its effect on rupture behavior discussed. The variability in minimum creep rate and rupture life is also dis- cussed and the dependence of these quantities on initial stress is interpreted. TEST MATERIAL AND TEST PROCEDURES The material tested is an austenitic stainless steel, AISI Type 316, of the following composition: C, 0.07 pct; Mn, 1.94 pct; P, 0.01 pct; S, 0.021 pct; Si, 0.38 pct; Cr, 18 pct; Ni, 11.4 pct; Mo, 2.15 pct; All 0.003 pct and N, 0.043 pct. The material was received as a hot-rolled 0.5-in. diam bar which was sectioned into 3.25 in. long blanks. Each blank was heat treated by holding 1/2 hr at 2000° F followed by water quenching. A 3/8-in. coupon was removed from each heat-treated blank and the microstructure was examined, the grain size determined, and the hardness measured. The microstructure was found to be uniform from blank to blank and the grain size was found to range from 4 to 6 ASTM numbers. Hardness, measured using a 20-kg load, varied between 127 and 148 Vpn. Tensile creep-rupture specimens having a 0.25 in. diam within a 1.5-in. reduced section were machined from the heat-treated blanks. Constant-load tests were made on these specimens at 1100°, 1300°, and 1500 F. Six specimens were tested at each stress level. Three creep-rupture machines were employed for tests at each temperature, two specimens being tested in each machine for each stress level. To minimize any effect due to local inhomogeneities along the length of the as-received bar the specimens were randomized before test. Each specimen was tested to rupture and in most cases an autographic extension-time curve was obtained. For very low stress levels at 1500°F no auto-

Jan 1, 1962

By Richard R. Zupp, David A. Stevenson

An experimental method to determine the carbon activity in various solid solutions was developed. Samples of the solid solutions and an Fe-C reference sample were equilibrated with respect to carbon content by annealing them in a Hz-CHI gas mixture in a closed cell. The carbon content of each sample was determined, and the carbon activity was obtained from the carbon content of' the reference sample and well-established data for the dependence of the carbon activity on the carbon content in Fe-C alloys. The influence of vanadium on the activity of carbon in austenitic Fe-C-V alloys at 1000°C was determined by this technique. A general semiempirical correlation was developed to describe the dependence of the activity coefficient of- carbon on the composition of ternary austenitic iron-base alloys containing interstitial carbon and a substitutional solute. The correlation is particularly useful in predicting the partitioning of- carbon between various alloys. THE influence of substitutional solutes on the activity of interstitial solutes in metallic solid solutions is important in the theory of alloy phases. Solid solutions of particular interest are the fcc austenite phases of ternary Fe-C-Z systems, in which carbon is the interstitial solute and Z represents any substitutional solute. Carbon-activity data are also needed in these solid solutions to solve practical problems; the quantitative treatment of diffusion-controlled transformations' is an examvle. Experimental information is available for ternary austenitic solid solutions containing Mn,2 Si,2 and A16 as the substitutional solute. Because qualitative preliminary studies indicated that vanadium appreciably decreases the carbon activity,14 the present investigation was undertaken to determine the influence of vanadium on the activity of carbon in austenite. Although Flender and ever" measured carbon activity over a range of compositions in the Fe-C-V system, they were primarily interested in determining phase boundaries in the ternary system, so most of their measurements were outside the composition range for stability of single-phase austenite. Petrova and Shvartsman' also made limited measurements of the carbon activity in Fe-C-V alloys. The dependence of the carbon activity on the carbon content of an alloy may be determined by passing COCOz or H2-CH4 gas mixtures of carefully measured composition over the alloys, determining their equilibrium carbon content, and utilizing the relevant equilibrium relationships. smith16 used this technique with both CO-COZ and HZ-CH4 gas mixtures to determine the dependence of carbon activity on carbon content in pure Fe-C alloys. His data, which are in good agreement with those of some previous and subsequent investigators,6'17 but not with those of others,lfl'ao are usually considered to be the most reliable. Although the same method can be applied to Fe-C-Z alloys, it is difficult experimentally, because the appropriate gas mixtures are almost pure CO or Hz. A simpler technique is to simultaneously equilibrate the Fe-C-Z alloys and pure Fe-C alloys with the gas mixtures, and then use Smith's data to determine the carbon activity in the pure Fe-C alloy. A number of investigators have employed this technique. others Have used the partitioning of carbon at the interface of a diffusion couple prepared from an Fe-C alloy and a Fe-C-Z alloy. In the present study, a closed-cell method was developed by which carbon was selectively transferred via a gas medium between pure Fe-C alloys and Fe-C-V alloys which were not in physical contact. A similar method was developed independently by Heckler and winchel14 and used to study the Fe-C-Ni system. EXPERIMENTAL METHOD A schematic diagram of the experimental arrangement is shown in Fig. 1. In a typical experiment, a 5-g Fe-C sample was placed in one compartment of a quartz cell, and a 5-g Fe-V sample was placed in each of the other compartments. The cell was evacuated, outgassed, backfilled with approximately 125 Torr of hydrogen, and sealed. After being placed in a fur-

Jan 1, 1967

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 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 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 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 S. Feuerstein, L. Rice

The effect of low pressures on the flow and fracture behavior of molybdenum is described. For poly crystalline samples, room-temperature tensile tests indicate greater ductility under 10 Torr than under intermediate pressures up to and including atmospheric pressure (760 Torr). In addition, tests conducted at 760 Torr under atmospheres of air, dry nitrogen, and purified argon exhibited no apparent difference in mechanical properties. Critical tests involving baking in situ as well as those involving single-crystal deformation further imply that the ductility effect is a pressure-dependent phenomenon related only to the fracture process. This dependency is discussed in terms of adsorption and diffusion contributions. THE effect of very low pressures on material properties has heretofore been presumed to be important only for substances possessing relatively high vapor pressures at ambient temperatures. Research has therefore been concentrated primarily on organic solids and liquids, and in some instances on metals such as zinc and cadmium. Most vacuum-effect studies' on the mechanical behavior of metals have been performed under conditions of either cyclic loading or creep rupture at elevated temperatures, i.e., over extended time periods. These studies were not restricted to high vapor pressure materials but also encompassed such metals as gold, copper, and nickel. Very little concern, however, was placed upon the importance of a vacuum environment on the mechanical behavior of metals subjected to a simple unidirectional deformation at ambient temperatures. A tension test is generally of short duration as compared to a creep test, and at room temperature vacuum effects if any would be expected to be surface-limited. In early 1963, Kramer and podlaseck2 reported a change in the bulk flow behavior of aluminum single crystals during room-temperature tension tests. The deformations were performed under pressure conditions of 760 to 3.4 X 10-8 Torr and indicated for the first time a vacuum surface effect contributing to the bulk tensile behavior of metal specimens. As a consequence, an experimental program was initiated in this Laboratory to study the effects of ultrahigh-vacuum conditions on the mechanical behavior of metals. The results of a preliminary study on poly-crystalline molybdenum3 revealed, unlike Kramer's observations of changes in the stress-strain behavior, only an increased ductility under ultrahigh vacuum. Flow behaviors were nearly identical for all tests re- gardless of pressure. This paper presents comprehensive results obtained in this area of research. 1) EXPERIMENTAL PROCEDURE Three material categories were used in this study: sintered and are-cast polycrystalline molybdenum of nominal purity 99.93+ pct and single-pass electron-beam zone-refined molybdenum single crystals having a nominal purity level of 99.99+ pct. The interstitial levels (weight percent) as determined by the Materials Testing Laboratories, Division of Magnaflux Corp., were as follows: sintered molybdenum (C— 0.005, H—0.0004, O—0.015, N—0.008); and arc-cast molybdenum (C-0.0038, H-0.0003, O-0.015, N-0.023). Single-crystal molybdenum obtained from Materials Research Corp. had a typical interstitial analysis of C-0.0015, H-0.00007, O—0.00045, and N-0.0001. Tensile specimens having a 5 mm diam by 50.8 mm length were prepared from these materials. An average grain diameter of 0.059 mm was obtained for the sintered specimens following a 4-hr, 1600°C heat treatment. Grain sizes from 0.019 to 0.149 mm were obtained in the arc-cast specimens following heat treatments from 1100° to 1600°C for 1 hr. This series of specimens was used exclusively for the grain-size effect studies. All samples were electrolytically polished in 97 pct sulfuric acid solution prior to testing. Experiments were performed at room temperature in an ion-pumped ultrahigh-vacuum system positioned in an Instron tensile machine, Fig. 1. A constant strain rate of 4.2 x 10-4 sec-1 as derived from crosshead displacement was assumed for the deformations. Starting vacuums ranged from 2 to 0.5 X 10-10 Torr. These pressure measurements were made using corrected values4 of an NRC Redhead gage. Comparative readings were also made against a G.E. triggered dis-

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