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By R. G. Jones, W. L. Kinney, R. E. Schilson, R. S. Wilson, G. A. Clark, H. Suralo

This paper discusses the results of the Fry conventional or cocurrent in situ combustion test, which was conduct-ed in a 3.3-acre inverted five-spot. The depth of the formation was between 880 and 936 ft; the oil had a specific gravity of 28.6° APl and a viscosity of about 40 cp at the reservoir temperature of 65°F. Preceding the combustion test, air injection tests were conducted which, in conjunction with geological studies, were used to evaluate the characteristics of the reservoir. Combustion was initiated on Oct. 13, 1961, with ignition being accomplished by a 40 kw electrical heater. The test phase of the project ended on Oct. 1, 1963. During the test, the average air injection rate was 1,520.-000 scf/D. Throughout the test, production of all fluids— gas, oil, and water—was monitored. Cumulative oil production credited to the project was 100,586 bbl. The cumulative air-oil ratio was 11,500 scf/bbl oil, and the oxygen uti1ization efficiency was 87 per cent. INTRODUCTION The Marathon Oil Co. conducted a successful in situ combustion test, beginning Aug. 22, 1961, at the Fry unit, Crawford County, 111. The purpose of the project was to test the feasibility of cocurrent in situ combustion as a means of oil recovery in the Fry type reservoir. Interest in in situ combulstion as an oil recovery tool has been stimulated mostly by the existence of large reserves of heavy viscous crudes with low expected recovery, usually less than 10 per cent. These are the so-called unrecoverable reserves, and most combustion tests to date have been conducted in this type of reservoir.1-4 In contrast, the Fry combustion test was conducted in a reservoir with a relatively high gravity oil having a relatively low viscosity. This paper discusses the performance of the test. The geology of the reservoir and the field operations are discussed in separate papers.5 TEST SITE The Fry combustion test was carried out in a 3.3-acre inverted five-spot portion of a lenticular body of Robinson sandstone. Net sand was 50 ft thick, porosity averaged 19.7 per cent, oil saturation was 68 per cent of pore volume, and water saturation was 20 per cent of pore volume. The oil in place was estimated at 1,040 bbl/acre-foot, or 171,600 bbl within the 3.3-acre pattern. The water in place was 326 bbl/acre-foot, or 53,800 bbl. The oil has a specific gravity of 28.7° API and a viscosity of 40 cp at the reservoir temperature of 65°F. AIR INJECTION PERFORMANCE Air injection took place in two phases, the phases separated by ignition of the reservoir. In the pre-ignition phase, air injection tests were conducted in the summers of 1960 and 1961. These indicated that the Fry reservoir was confined, and a high return rate of injected air could be expected. This proved to be an outstanding characteristic of the project, as cumulative gas production was 95.3 per cent of the air injected. The difference between the cumulative air injected and the total gas produced can be largely accounted for by the quantity of air stored in the reservoir. An estimated 16 X 10 cf of air remained in the burned-out portion of the reservoir and an indeterminate amount of gas was stored in the unburned but pressurized reservoir. Hence, a complete material balance of gases would account for nearly 100 per cent of the air injected. At times during the test, the daily gas production rate was 98 per cent of the daily air injection rate. Fig. 1 presents the air injection history of the Fry com-

Jan 1, 1966

By D. S. Sanders, E. W. Witcomb

FLOTATION tests, from which the flowsheet for the concentrator was determined, were made in a pilot mill at Chuquicamata and later comparative testing of full size flotation cells was done at the Andes Copper Mining Co. concentrator in Potrerillos. The principal sulphide copper mineral is chalcocite with varying amounts of covellite, enargite, and chalcopyrite. The oxidized portion is principally antlerite, a green basic copper sulphate. The gangue minerals include quartz, sericite, pyrite, feldspars and kaolin. Chuquicamata pit ores have proved to be hard grinding. The results of the flotation and metallurgical work prove that good extraction and concentrate grade can be obtained under a rather wide range of conditions. Metallurgy In general the metallurgy of the ore requires a fairly close control of the grind to the primary rougher flotation and of the regrind of the primary rougher concentrate before cleaning. Regrinding is necessary to reduce the insoluble content of the final concentrate since a large part of the middling combinations are between the copper and silica minerals. The alkalinity of the pulps can vary between wide limits and control of the percent solids gives the desired grind. Alkalinity Control Arroyo Salado water is supplied to the concentrator head tanks. It contains about 5000 ppm of salts but test work shows no deleterious effect. Actually this water permits a decrease of as much as 1 lb of lime per ton of ore as compared to San Pedro water, which is used for leaching oxide ore. About one quarter of the water flow through the concentrator will be new water from the reservoir. The remainder will be reclaimed from the thickeners. For primary grinding and rougher flotation, new and reclaimed water are combined in the head tanks. To avoid erratic results, only new water is used in the regrind system. Milk of lime is added to the rod mill feed chute to obtain the maximum benefit of mixing with the ore. This protects the equipment from corrosion due to entrained acids and soluble copper salts. Lime consumption is 3 to 5 lb per ton of ore. Grinding and Flotation The six bin gates over each belt feeder are opened in controlled combination and sequence to keep a live bed of ore in the bin to prevent arching and to obtain mixing. The milk of lime added ahead of the rod mill is regulated to suit rougher flotation requirements. The primary promoter reagent, Aerofloat 238, is added to the 10-mesh discharge of the rod mill as it is laundered to the ball mill scoop box. The classifier overflow is regulated to produce a grind of about 12 to 15 pct +65 mesh and 60 pct -200 mesh. A secondary promoter Z-4 (aml zanthate) and the pine oil frother are added in the overflow launder where a pH of 10 to 11 is maintained. Comparatively heavy beds of froth on the

Jan 1, 1952

By N. A. D. Parlee, I. D. Shah

The solubilities of oxygen in liquid Ag-Au, Ag-Pt, and Ag-Pd alloys have been determined in the range of 940° to 1200°C at 1 atm pressure of oxygen using an improved Sieverts technique. The additions of gold (0 to 57 pct), platinum (0 to 27 pct), and palladium (0 to 22 pct) to liquid silver continuously decrease the solubility of oxygen in liquid silver. Activity coefficients and interaction coefficients of oxygen in these alloys and have been calculated. The interaction coefficientscan be described by the following equations: Approximate second-order interaction coefficients (pM have been calculated. The contribution of the product, pMxNM, to In yo only becomes significant at high alloy concentrations. RECENTLY several investigators1"3 have redeter-mined the solubility of oxygen in liquid silver. In general the recent findings1" for Po, = 1 atm are in good agreement with the equation:4 log %O = 695.4/T + 1.086 [1] It is established1, 2 that the solubility of oxygen follows Sieverts' law reasonably well, at least up to 1 atm partial pressure of oxygen. It should be noted that a very slight deviation from Sieverts' law has been reported by Lupis and Elliott.3 Only recently has the solubility of oxygen in Ag-X binary liquid systems received much attention, and only the Ag-Cu, Ag-Au, Ag-Pt, and Ag-Pd systems have been studied. Par lee, Sacris, and zoellners reported that the solubility of oxygen in liquid silver increases progressively with the small additions of copper (0 to 0.5 pct) up to the point where the copper oxide phase appears. Lupis and ~lliott~ have reported that the solubilities of oxygen in liquid silver decrease progressively with the additions of gold, platinum, and palladium. However, their investigation was limited to 0 to 5 pct of these alloying elements, a range too limited to satisfy the requirements of the research program of this laboratory, where the solubilities of oxygen in the range of 0 to 30 pct were required for the calculation of chemical diffusion coefficients of oxygen in these alloys. The present paper deals only with the solubilities of oxygen in these alloys while another paper will deal with the diffusion of oxygen in these alloys. EXPERIMENTAL METHOD A Sieverts technique was employed which involved an improved design of the reaction tube, Fig. 1, as described briefly in a previous communication.4 Liquid melts (70 to 100 g) were held in Norton Alun-dum crucibles. The induction furnace used had a maximum output of 2.5 kw with very fine control. This induction system had excellent stability and the final equilibrium temperatures measured by calibrated Pt-Pt, 10 pct Rh thermocouples are believed to be within ±2C. These thermocouples were checked against the melting point of pure gold wire, and the results agreed with standard tables (±l°C). Each run involved a careful sequence of operations. The sample was heated to and held at about 900°C in vacuum for 3 to 4 hr with the thermocouple in a retracted position. After melting, the melts were usually exposed to a small amount of oxygen (0.5 to 2.0 cu cm) and then degassed slowly for 1 to 2 min to remove any oxidizable volatile impurities such as carbon and sulfur as CO, CO2, SO2, and SO forth. Argon gas was then allowed to enter the system. The protection tube containing the thermocouple was then

Jan 1, 1969

[ PRESIDENTS DAVID THOMAS 1871 'R. W. RAYMOND 1872-1874 'A L. HOLLEY 1875 'ABRAM S. HEWITT 1876 'T. STERRY HUNT 1877 'ECKLEY B. COXE 1878-1879 'WILLIAM P. SHINNY 1880 'WILLIAM METCALF 1881 'RICHARD P. ROTHWELL 1882 'ROBERT W. HUNT 1883 'JAMES C. BAYLES 1884-1885 ROBERT H. RICHARDS 1886 'THOMAS EGLESTON 1887 'WILLIAM B. POTTER 1888 'RICHARD PEARCE 1889 'ABRAM S. HEWITT 1890 'JOHN BIRKINBINE 1891-1892 'H. M. Hows 1893 'JOHN FRITZ 1894 'J. D. WEEKS 1895 'E. G. SPILSBURY 1896 'THOMAS M. DROWN 1897 'CHARLES KIRCHHOFF 1898 'JAMES DOUGLAS 1899-1900 'E. E. OLCOTT 1901-1902 'ALBERT R. LEDOUX 1903 'JAMES GAYLEY 1904-1905 'ROBERT W. HUNT 1906 'JOHN HAYS HAMMOND 1907-1908 'D. W. BRUNTON 1909-1910 'CHARLES KIRCHHOFF 1911]

Jan 1, 1940

By A. H. Underwood, M. –Ls. Trépanier

INTRODUCTION The King and Beaver mines of Asbestos Corporation Limited (ACL) were joined in 1957 to form the King-Beaver mine. In 1964, ACL purchased the Johnson's Asbestos Company. The combined underground workings are a part of the King- Beaver mine. Asbestos ore is mined at the rate of 4080 metric tons per day (mtpd) to provide 15% of the company's daily requirement in the Thetford Mines area. Figure 1 shows the location of Thetford Mines. Two shafts service the underground. No. 3 shaft, 457 m deep, is used for personnel and material transportation, downcast ventilation, and ore hoisting. No. 4 shaft, 820 m to the south, is 389 m deep. It is used for material transportation and upcast ventilation. Figure 2 shows the relative locations of the shafts and the underground workings. The ore is mined by block caving. HISTORY The orebody outcropped at surface and was first mined as an open pit. Underground mining commenced when open pit mining became impractical. Shrinkage stoping, used initially, was unsatisfactory in the highly fractured ore. Sublevel stoping improved ore recovery and safety, but did not overcome the adverse effects of the un- stable rock. Observations of the rock failures indicated that block caving would be satisfactory. This was confirmed by careful investigation and testing. A method of block caving similar to that used at the Miami Copper Company was adopted. The first block commenced production in June 1933. BLOCK CAVING General A large block of ore is undercut above pre- pared drawpoints. The ore above the undercut caves by its own weight. Caving progresses up- ward as the caved ore is drawn. A large proportion of the rock breaks up in the caving action so that it will pass through the drawpoints. Oversize blocks are broken by drilling and blasting or mudcapping. Figure 3 shows the progressive stages of block caving. In the central part of the ore zone, the vertical dimension of a block is determined by the 132 metres between production levels. When isolated ore pockets are developed, the vertical dimensions of a block depend on the extension of the ore zone above the undercut. The minimum horizontal dimension of an under- cut determines the cavability of the overlying block. When necessary, caving is assisted by drilling long horizontal holes into the block above the undercut and blasting them. This procedure speeds up or restarts caving. It will not ensure complete caving of blocks having undercuts less than 30 m wide. Orebodies suitable for block caving are highly fractured and wide enough to cave freely without excessive dilution. Undercutting must

Jan 1, 1981

Discussion of the paper of M. B. YUNG, presented at the Pittsburgh meeting; October, 1914, and printed in Bulletin No. 93, September, 1914, pp. 2451 to 2458. T. T. READ, New York, N. Y.-I might .point out that this paper of Mr. Yung's is on a field that is comparatively little known. It is not as well known as the Kochiu tin field, of Yunnan, which is probably the third . in tin output of the world. This field under discussion is considerably further west and the tin which is produced here is, according to Mr. Yung, of somewhat higher grade than the Yunnan tin, and is used by the refiners at Hong Kong to improve the grade of the Yunnan tin. Most of you know that the tin from the Yunnan is shipped to Hong Kong, where it is refined and shipped to Europe. Mr. Yung points out that the Fu Chuan deposits are entirely alluvial and not found in any veins. They .differ in that from the Kochiu deposits, which Leclere says are "nullement alluvionels; leur origéne filonienne est de plus evidentes." Granite is the country rock here; doubtless the tin occurred in veins in the granite, and the deposits have resulted from the disintegration of the granite. This is a country of strong erosive agencies. The country is semi-tropical, and the rainfall is heavy, so that one would naturally expect deep surface erosion of this kind.

Jan 4, 1915

By B. T. Brady

Experimental data 1,2 on the energy dissipation in polycrystalline materials over a large frequency spectrum (10-2 cps to 106 cps) suggests that the quality factor [(e= Q )] is independent of the frequency providing both fluid-saturated and ferromagnetic materials are excluded from the test data. Additional data 3 suggest that the quality factors are less at high pressures than at low pressure, i.e., Q increases as the pressure increases. Observations on the dissipation of single quartz crystals with their polycrystalline counterparts indicate that the energy dissipation is less for the single crystal than for the aggregate .2 Both of the above observations, particularly the latter, are indicative of the fact that the dissipation increases with increasing surface contact within the polycrystal, i.e., a frictional attenuation scheme may be operative. Knopoff and MacDonald 4 have shown that a friction model gives rise to a quality factor frequency independence property. A partial listing of some values of Q, observed for both metals and non-metals, is given in Tables I, II, and III. In Tables I and II, the data all show Qs>Qp, i.e., the energy loss per cycle for compressional body waves is greater than that for shear waves of the same frequency. Most samples in Table III show the same effect. It is objective of this paper to suggest: (1) a frictional attenuation scheme may account for the observed losses incurred during the propagation of low amplitude stress waves in dry brittle rock and, in particular, that such a scheme can account for the observed relative magnitudes of the quality factors for P and S wave motion; (2) a friction scheme can readily explain the difference between the dynamic and static moduli in dry brittle rock; (3) a friction scheme, while in itself an intrinsically

Jan 1, 1968

PURPOSE OF UPDATED ESTIMATE FOR MINERAL INVENTORY BLOCKS During the production stage of an open pit porphyry copper mine it was observed that the expected production grade, as determined from the block inventory estimates, often differed greatly from the head grade of ore delivered to the mill. It was determined that, for purposes of production scheduling and monthly forecasting, better in situ grade estimates for mining blocks were necessary. Because all of the bench blastholes were being sampled, and periodic holes were being drilled into the next underlying bench, much more sample data existed than was being used for estimating the grade of nearby mining blocks. It was reasoned that, by periodically updating the mineral inventory block file over the benches scheduled for mining in the next time period using all existing data, better estimates and forecasts for production grade could be made. BLASTHOLE SAMPLE DATA MANAGEMENT The collars of all blastholes in each mined bench were surveyed and assays run on the cuttings representing the full 12-m (40-ft) bench height. The blastholes range from about 5 to 6 m (16 to 19 ft) apart along the front of the bench as well as perpendicular to the front. Overbreakage often left larger spacings between successive blasts. Fig. 17-1 is a plan map of blastholes on a typical mine bench. All blasthole data were keypunched to a format resembling that of the 12-m (40-ft) composite assay data file as follows: [Collar Coordinates Compite Assoy Hole ID Northing East Elewotion Total Copper Oxide Copper] Because of the many blasthole samples available, and in order not to use excessive computer time for running kriged estimates for 30.5 X 30.5 X 12-m (100 X 100 X 40 ft) blocks adjacent to and beneath the mined area, the decision was made to average all the blastholes falling with each 15.2 X 15.2-m (50 X 50-ft) mined block, and use the mean value of the samples as a regionalized variable for purposes of assigning kriged estimates and estimation variance to adjacent unmined blocks. In other words, instead of using individual blasthole samples for making kriged estimates, the holes were grouped by blocks and assay values were averaged and assigned to the centroid of the holes within the block, which was then treated as a single regional variable for purposes of kriging. See Fig. 17-2. VARIOGRAM COMPUTATIONS AND KRlGlNG RESULTS With the many blasthole samples it was possible to compute directional and vertical experimental variograms for both sulfide and nonsulfide copper assays falling within the enriched mineral zone for the full 12-m (40-ft) sample support. Due to the close spaced drilling, excellent definition of the experimental variograms was possible, and the spherical model exhibited good fits. A three-dimensional kriging program was then run over the two or three mine benches involved in the inventory update, and estimated grades reassigned to all mining blocks falling within the range of the new blasthole assay data according to the anisotropisms of the deposit. Better confidence limits could then be assigned to scheduled mining blocks and better short- range forecasts made. An interactive kriging computer program was also applied for the purpose of determining the kriging variance or estimation of error for larger, irregular mining blocks representing the monthly production from a particular bench. The interactive program permitted the operator to enter the limits of the irregular block onto the screen of a cathode ray tube (CRT) as a series of points around the perimeter of individual gridded blocks making up the larger irregular block. The computer then was programmed to calculate the kriging variance of the larger block using all samples fall- ing within range. Thus the limits of estimated grade could be established at any confidence level. Fig. 17-3 illustrates the output from the interactive kriging program showing the sample points entering into the grade and kriging variance computations, and also the kriging coefficient assigned by the computer to each sample.

Jan 1, 1980

By Rex E. Cheek, Donald E. Menzie

The fluid mapper, a model relatively new to the petroleum industry, was used to study the effect of various mobility ratios on the areal sweepout efficiency for two typical spacing patterns. The experiments indicated the areal sweepout for the five-spot pattern varied from 51.8 per cent at a mobility ratio of 0.093 to 89.1 per cent for a ratio of 24.4. In the direct line-drive pattern, the areal sweepout varied from 58.7 per cent at a mobility ratio of 0.089 to 92.0 per cent at a ratio of 24.8. The fluid mapper may prove useful to determine quickly the effective areal sweepout for any well spacing. INTRODUCTION The effect of the mobility ratio on the areal sweepout efficiency during primary depletion of a water drive reservoir and during secondary recovery operations has recently become more widely recognized The mobility ratio, M, is defined as: _ kjp (displaced fluid) k/u (displacing fluid) where k = effective permeability u = viscosity When the displacing fluid is miscible with the displaced fluid, the permeabilities are equal and the mobility ratio may be expressed as a ratio of viscosities: u (displacing fluid) u (displaced fluid) The mathematical analysis for calculating the areal sweepout efficiency with mobility ratio other than unity is quite tedious.5,11 An experimental method by using a potentiometric model2 in a step-wise manner and in using an X-ray shadowgraph model3,12 with continuous fluid flow has been published. Several types of models have been used to study oil and gas reservoir performance. These models may be classified as physical, electrolytic, potentiometric, X-ray shadowgraph, and fluid mapper. The X-ray shadowgraph and fluid mapper are models relatively new to petroleum engineering and have not been used extensively for specific applications. The theory of the fluid mapper indicates it may be adapted to a study of areal sweepout efficiencies for various mobility ratios as well as other complex problems in petroleum engineering. The use of the model and results obtained when using displacing and displaced fluids of equal densities but different viscosities are discussed. FLUID MAPPER DEVELOPMENT H. S. Hele-ShawV eveloped a fluid mapper model based on the hydrodynamic theory. This theory is that in the steady flow of a viscous fluid between horizontal parallel plates spaced a very small distance apart, the effect of viscous shear is of such magnitude in the vertical plane that the motion in the horizontal plane is practically undisbrted streamline flow. Techniques developed by Hele-Shaw were not expanded and no additional developments in fluid mapper models were forthcoming until A. D. Moore, University of Michigan, published a series of papers starting in 1949, which describe the construction of a flexible and inexpensive model'h nd the fluid mapper technique for the solution of certain problems.' The essential components of the fluid mapper as developed by Moore are::.ln 1. A base slab. made of dental stone (calcium sulphate and water). which is shaped to represent the prototype. 2. Plate glass slightly larger than the slab and spaced

Jan 1, 1956

By B. Yarar

Samples of coal from an adit in the Fording River District of British Columbia showed hydrophilic properties between depths of 0-24.5 m (0-80 ft) and was naturally hydrophobic at greater depths. Laboratory experiments indicated that weathered samples (i.e., those mined at 0-24.5 m) could be upgraded by froth flotation at pH32 following slimes removal. The i.e.p. of samples varied regularly between pH = 1.6-4.1, the weathered fractions being at the lower end of the pH scale. These values followed a pattern comparable with the flotation behavior of samples. A patchwise structure for coal surfaces determining the resultant disjoining pressure which in turn determines flotation-non-flotation relationships is postulated.

Jan 1, 1983

By J. M. Cases

Study of the normal interaction between flotation collectors and the silicates through measurement of the electrokinetic potential carried out by the streaming potential and flotation recovery methods indicates that the interaction is wholly 07 partly of electrostatic origin. In some cases, it partly consists of the chemical affinity of the polar head of the collector for the active surface sites. Reagents composed of a polar head and a paraffinic chain and forming micelles in solution were used as flotation collectors. They are sodium dodecylsulfate (anionic collector) and dode-cylammonium chloride (cationic collector). The adsorption isotherms on biotite of alkylamine chloride having 10 to 18 carbon atoms in their chain all show a sharp change in slope relevant to the condensation of alkylammonium ions into bidimensional phase.1-1 Condensation is possible because of the relative homogeneity of the adsorbing surface and of the very strong lateral binding forces through Van der Waals type bonds in the adsorption layer. The different isotherms are seen to coincide when, instead of the equilibrium concentration, the under-saturation ?µ = kT In C/C, is plotted in abscissa, C representing the concentration of the solution with which the adsorbed layer is in equilibrium and C, the saturation concentration of micelles in solution or. critical micellar concentration. More particularly, the undersaturation ?,u1*, corresponding to a surface coverage 6 of 0.5, is equal to Since silicates immersed in aqueous solutions show a surface charge which is a function of pH, it is of primary importance to study the influence of this parameter on the adsorption of collector ions acting as Strong electrolytes in the pH range where they are utilized. The aim of this present paper is to determine by studying electrokinetic phenomena and recovery curves effectuated with a cationic collector and a anionic collector, the nature of the normal adsorbate-adsorbent interaction. Tables 1 and 2 sum up part of the results previously obtained'H11 for the determination of the point of zero charge of the silicate studied by the streaming potential method. Throughout the remainder of this paper, the surface charge will be considered positive for all values of pH below the point

Jan 1, 1971

By George M. Fowler, R. E. Illidge

Part I. Developing BY GEORGE M. FOWL INTRODUCTION The Tri-State district comprises an area of about 2000 square miles in southwestern Missouri, southeastern Kansas, and north [ ] eastern Oklahoma. The part that is in and contiguous to Missouri is still sometimes designated as the Joplin district (Fig. I). EARLY OPERATIONS Mining operations in what is now the Tri-State district date from about 1848 and have been continuous to the present. Apparently the first discoveries of ore were made about the same time near the present sites of Joplin, Oronogo, and Granby. Lead minerals were found at grass roots, probably in shattered rock in shallow excavations, then these minerals were followed in shear zones to deeper horizons. The mining of zinc followed. Before 1874, zinc ore was worthless and discarded as waste. According to published records, the total production of lead to that date was 49,000 tons of metal from 70,000 tons of concentrates. PRODUCTION The aggregate ore production from the Tri-State district was recorded at interval

Jan 1, 1943

The Reconstruction and Research Division of the United States Council of National Defense has, up to date, prepared two reviews on the above subjects: one covers foreign countries and the other covers the activities in the States. These reviews contain information appearing in various Governmental and public periodicals. While the information on foreign countries is necessarily incomplete and fragmentary, its summation is perhaps the most complete work of this kind so far accomplished. The information from the states consists mainly of bills and ordinances introduced in the state legislature, municipal councils, legislature committee reports, programs suggested by governors, and other state and local officials and local organizations It is realized that a good deal of this information will be useful to engineers studying conditions in the various states, and especially to those who want an insight into the general condition in all the states. For instance, the reconstruction problem in each state involving highway, reclamation, buildings, etc., are covered in detail.

Jan 8, 1919

By R. S. Wagner, W. C. Ellis

A new mechanism of crystal growth involving oapor, liquid, crnd solid phases explains many observations of the effect of implurities in crystal growth from the vapor. The role of the impuuitq is to form a liquid Solution with the crystalline tnalerial to be grown from the vapor. Since the solution is n prefevred site for deposition firorti the uapor, the liquid becorrles supersaturated. Crystal growth occurs by precipitatzon from the supersaturated liquid crt tlie solid-liquid zntevfnce. A crystalline defect, such as a screw dislocation, is not essetztial for VLS (vapor -liquid-solid) growth. The concept of the VLS mechanism is discussed in detail with reference to tire controlled growth of silicon crystals using gold, platinum, palladium, nickel, silver, or copper as an implurity agent. RECENTLY a short communication' described a new concept of crystal growth from the vapor, the VLS mechanism. In this paper we present a detailed description of the process and its application to the growth of silicon crystals and we discuss its relevance to existing concepts of .'whisker" crystal growth. Crystal growth from the vapor is usually explained by a theory proposed by Frank2 and developed in detail by Burton, Cabrera, and Frank.3 In this theory a screw dislocation terminating at the growth surface provides a self-perpetuating step. Accommodation of atoms at the step is energetically favorable, and is possible of much lower supersatu-ration than required for two-dimensional nucleation. Crystals of a unique form resulting from aniso-tropic growth from the vapor are "whisker" or filamentary ones. Such crystals have a lengthwise dimension orders of magnitude larger than those of the cross section. For most filamentary crystals both the fast-growth direction and directions of lateral growth have small Miller indices. The special growth form for a whisker crystal implies that the tip surface of the crystal must be a preferred growth site. sears4 proposed that, according to the Frank theory. a whisker contains a screw dislocation emergent at the growing tip. Such an axial defect provides a preferred growth site and accounts for unidirectional growth. The hypothesis was extended by Price. Vermilyea. and Webb," still implying the presence of a dislocation at the whisker tip. They postulated that impurities arriving at the fast-growing tip face become buried while those arriving on the surface of slow-growing lateral faces accumulate and thereby hinder growth. These considerations led to a whisker morphology. There is increasing evidence that most whisker crystals grown from the vapor are dislocation-free. Webb and his coworkers6 searched for an Eshelby twist7 in zinc? cadmium, iron. copper, silver, and palladium whisker crystals. They found unequivocal evidence for an axial screw dislocation in only one element, palladium. However, not every palladium crystal examined contained a dislocation. Observations with the electron microscope have failed to show dislocations in whisker crystals of zinc, silicon.9 and one morphology of AlN.10 Since many whiskers are completely free of dislocations, an axial dislocation does not appear to be required for whisker growth of many substances. A significant advance in understanding whisker growth has been a recognition of the need for impurities. This requirement has been clearly demonstrated for copper,11 iron,13 and silicon9-1 whiskers. For silicon, detailed studies proved conclusively that certain impurities, for example, nickel or gold, are essential. Another pertinent phenomenon which has received little attention is the presence of a liquid layer or droplets on the surface of some crystals growing from the vapor. Crystals in which this has been observed include p-toluidine,14 MoO3,15 ferrites,16 and silicon carbide.'" The liquid layers or globules were considered to be metastable phases, molecular complexes, or intermediate polymers originating from condensation of the vapor phase. The possibility has been suggested that the halide being reduced is condensed at the tip18 or adsorbed on the surface11 of a growing metal whisker, for example copper. The literature on whiskers discloses illustrations of rounded terminations at the tips. These appear. for example, on crystals of A12O3,19,20 sic,21 and BeO.22 For BeO, Edwards and Happel suggested that during growth of the whisker the rounded termination consisted of molten beryllium enclosed in a solid shell of BeO. A recent paper9 on the growth of silicon whiskers contains many observations pertinent to an understanding of the mechanisnl of whisker growth. These observations are summarized as follows. 1) Silicon whiskers are dislocation-free. 2) Certain impurities are essential for whisker growth. Without such impurities the silicon deposit is in the form of a film or consists of discrete polyhedral crystals.

Jan 1, 1965

By J. O. Nelson, C. J. Altstetter

Single crystals of hcp cobalt, 3 mm in diameter and up to 35 cm long, were grown using an electron-beam, zone-melting technique. The martensitic-phase transformation was studied in single-crystalline and polycrystalline specimens by making length-change measurements as a function of temperature under various elastic compressive stresses. Upon thermal cycling, single-crystalline or polycrystalline specimens repeatedly transformed almost entirely on the same variant of close-packed plane provided the maximum temperature did not exceed 600°C. Cycling to 1000°C resulted in transformation on more than one {111} variant. This behavior is termed multivariance. The multivariant transformation occurred very rapidly at an M, temperature 2° to 6°C lower than the M, of a transformation which would result in a single-crystal product. Elastic compressive stresses (up to 253 g per sq mm) tended to lower the A, and raise the M, temperatures, decreasing the width of the temperature vs dilatation hysteresis loop. The transformation habit plane and transformation shear direction of an as-grown single crystal were not grossly affected by elastic compressi?ie stress. This was evidenced by similar dilatations on the temperature us dilatation loops joy specimens with and without compressive stress. A dislocation mechanism is proposed to explain the observed results. IT has been shown that, on heating, cobalt transforms martensitically from the hcp to the fcc phase.' The transformation habit plane is (0001)hcp || (lll)fcc and the transformation shear direction is (1010)hcp || (112)fcc. The transformation involves a shear of 1g°28', which may be achieved by a shearing of a/6(112) of every two planes with respect to the plane beneath, thus changing the ABABAB stacking of hcp to the ABCABC stacking of fcc. Associated with the phase change is a 0.3 x 10"3 contraction in the habit plane and a 4.2 X 10"3 expansion perpendicular to the habit plane resulting in a 3.6 x X volume increase on heating.' On cooling, an identical volume decrease takes place. The temperature at which the fcc phase begins to form on heating (A,) is reported as 430°C, and the temperature at which the hcp phase begins to form on cooling from an elevated temperature (A&) is reported as 390oC1,3 Consequently, temperature vs dilatation plots have the form of a hysteresis loop. If heating or cooling is reversed during a transformation, a smaller hysteresis loop results. Upon heating, the transformation is always complete; whereas, fcc is often retained at room temperature as a metastable phase entrapped in the polycrystal-line hexagonal matrix.1,4,5 Two obstacles in the theory of the allotropic-phase transformation of cobalt have been: 1) a detailed knowledge of the product nucleus, and 2) a plausible method of propagation of the transformation. Bilby,8 christian, 7 and seeger 8,9 have suggested a "pole mechanism" as a means of propagation of partiai dislocations from plane to plane. A pole dislocation and a Shockley partial come together at a node. The a/6(112) Shockley partial rotates about the pole dislocation effecting the transformation shear. The pole dislocation must have a 2a/3(111) screw component which causes extension of the transformed region by two atomic planes with each full rotation of the Shockley partial. Bollmannl0 suggested, on the other hand, that transformation propagation occurs due to the stress fields of intersecting (111)-type stacking faults. As faults intersect, a stress distribution is set up about their intersection which is in turn reduced by the emergence of another fault on the second nearest plane. This process continues with the final result of a complete phase transformation. In view of the similarities between deformation and transformation in cobalt, the effect of stress on the transformation would, hopefully, yield valuable information concerning nucleation and propagation. In the present work single-crystalline and polycrystalline specimen length changes were measured as a function of temperature at various compressive loads. PROCEDURE Several orientations of single crystals of hcp cobalt in lengths up to 25 cm were grown by electron-beam floating zone melting from 99.95 and 99.999 pct, 3-mm-diam cobalt rod as supplied by Johnson

Jan 1, 1964

Jan 1, 1920

By G. S. Cole, H. Biloni, G. F. Bolling

An experimental investigation of sovlze low .melting point alloys sJtows that a substvucture of isolated depressions can be the first manvestation of constitutional supercooling on solid-liquid interjaces veuealed by decanting. Electron-tni cvop vobe and wletallo gvaplic esanzinations, in tlze bulk belzind the interjace, oj the segregation associated with these isolated areas substantiate tlzei&apos;v depressed nature, since a solute of ko < 1 is enriched, and a solute of ko > 1 depleted. In contrast, the pox structuve, a set of projections often veported in the literature, leaves no trace oj. segvegation. These obserl;atims, accovlrpanied by a brief review of recent literature, point to inconsistencies between experirrental obsevvation and the idea that the fornzation of a projection is a causal step in the development of a cellular substructure. An argument is presented to show instead how it is plausible for substantial depvessiom to form in the pvesence of constitutional supercooling at dislocations threading the solid-liquid interjace. THE development of constitutional supercooling during growth from the melt leads to the formation of the cellular solidification substructure. This well-founded association between structure and instability has been basic in understanding cellular substructure and micro segregation; however, the initial formation of structure seems unclear. Rutter and Chalmers,&apos; in definitive experiments and theory, noted that in the presence of constitutional a planar interface might break down: "resulting in the formation of a small projection on an initially plane or uniformly curved interface." That is, the breakdown from a planar to a cellular interface was implied to be initiated via a projection into the unstable liquid. Later, Walton et (11. found that a structure of isolated projections, termed "pox", appeared at solid-liquid interfaces decanted under growth conditions near the onset of constitutional supercooling; the pox were taken as the indication of the instability promoted by the supercooling. Tiller and Rutter4 in their extensive work studied the shape transitions at decanted interfaces which were generally observed to proceed as— pox, "irregular cells", elongated cells, regular (hexagonal) cells, and so forth. The pox varied in size from lo-&apos; to 1CT4 cm, and tended to disappear as cells increased in number and regularity, but as noted,4 the first real array of cells did not seem to be a development from the pox. In fact these authors implied a lack of connection because they stated that the pox are denser on "irregular cells", and as cell boundaries increase in number (i.e., the cells become smaller) there is less need for the pox which do dis- appear. Thereafter, most authors dealing with either experiment or theory have accepted the reality of pox and have used them as a criterion for the onset of constitutional supercooling. In contrast, Spittle, Hunt, and smiths have now suggested that pox are irrelevant artifacts comprised of such things as entrapped oxide. This proposal invokes the observations of weinberg6 and chadwick7 each of whom have shown that the act of decanting leaves a residual liquid on a decanted interface; the remnant solid layer of the order 10 p may thus contain particles that might have been transported from the external surfaces, or elsewhere, during decanting. With the incentive of this suggestion,= some further experiments and a reexamination of the literature have been conducted, in order to question the validity of pox as evidence of an instability and to examine the initial development of the cellular substructure. 1) EXPERIMENTS Single crystals of zone-refined tin (-99.9999 pct) were grown from the melt in a controlled fashion with various, small concentration additions of lead and antimony, for which ko < 1 and > 1, respectively. The crystals were decanted at conditions near the onset of constitutional supercooling and were thus appropriate for observation of slight perturbations. It was possible to observe two types of small departure from smooth or "planar" interfaces in both cases of lead or antimony additions. Some were projections and others, if in regular array of any type, were depressions. The crystals were etched with suitable reagents progressively dissolving the decanted interface surface; projections left no record, but depressions were continuously associated with spotlike areas contrasting with the rest of the interface. Traverses were made with the beam of an electron microprobe across the regions of contrast; with lead addition the persistent spots were lead-rich, and with antimony addition the persistent spots were antimony-poor. This is consistent only with a dominant role for depressions, because if the projections had left spots but were incorrectly catalogued, a reversed observation should have been made; that is, the Pb(ko < 1) should have been depleted and the Sb(ko > 1) enriched. In the work of Cole and inegard, and elewhere, regular arrays of structure associated with the initial stage of instability have been shown, in photographs and represented as pox or projections. We believe this to be erroneous, by inference, since whenever a regular array was observed, in the present examination, it consisted of depressions, regardless of the nature of the solute, ko 1. Fig. 1 is reproduced8 as an ideal example of the possible optical illusion involved; the observer can satisfy himself from the distribution of illuminated areas that the markings are depressions. Fig. 2 from the present investigation is an interference photograph of an interface similar to that in Fig.

Jan 1, 1967

By Janshi Sen

VERTICAL-INTENSITY magnetometers, such as the Hotchkiss Superdip and the Askania vertical field balance, are now [ ] widely used, because vertical-intensity charts give definite information for the location of upper pole, dip and strike, and approximate shape of the deposit. Again, a slow and steady increase of dip over a large area indicates a large deep-lying deposit, while a large dip limited to a small area and falling away rapidly suggests a small and shallow one. The complication comes more from the richness of the ore. A large body of lean ore near the surface might produce the same vertical-intensity chart as a rich ore at depth. This paper presents a method for calculating the maximum depth of a single-pole deposit and another for a two-pole mineral body, by utilizing data of both vertical and horizontal intensities as obtained by a Thalen-Tiberg magnetometer. As shown on the left side of Fig. 1, lean ore, rich ore and a single pole produce the same magnetic field. The depth of the pole, [ ] h, can be calculated from the following relation: [h=a=tan¢=G-F h=aXFy] where G is the vertical intensity at point A due to the pole; F, the horizontal intensity of the same; and a, the distance from the point of maximum vertical intensity or the vertical projection of the pole on the surface to the point of observation A. If an entirely covered deposit is indicated by magnetic measurements and boring cost estimated from the calculated depth is so reasonable as to encourage drilling, the ore should be struck somewhere within the limit of the calculated depth by the borehole. A number of such points as A should be taken for calculation, erratic results should be rejected and the average figure used for cost estimation.

Jan 1, 1944

Truman H. Aldrich W. Lawrence Austin W. S. Ayres John Henry Banks Andrew A Blair Walter M. Brodie R. C. Canby

Jan 1, 1932

By Arthur F. Taggart

The following conclusions on the work of the Hardinge mill are based on data furnished to the writer by the Hardinge Conical Mill Co. in the form of the mesh cards hereto appended. Energy units (E. U.) and relative mechanical efficiencies (R. M. E.) are computed by the "volume method" of Stadler.&apos; Screen apertures used are the average apertures of testing screeps of the meshes given. i . Card 122. June 28, 1912. Vipond Porcupine Mines Co., Ltd., Schumacher, Ont., Canada. Ore from mill bin. Gangue, quartz and basalt. 4.5 ft. by 13 in. ball mill, Capacity, 48 tons per 24 hr. Charge, 4,000 lb. balls. Speed, 33 rev. per minute. Horsepower, 15 to 17. Water, 100 per cent. by weight. (50 per cent. ?) Product deslimed and oversise reground in pebble mill, see Card 113. Feed to mill through 2-in. mesh. Mesh Feed, Per Cent. Discharge, Per Cent.. + 1in. 5.50 ....... + 3/4. 28.00 + in. 30.00 ...... + 1/4in. 19.72 ....... + 10 10.87 2.10 + 20 2.42 8.00 -20 3.51 .....,. + 40 ....... 22.68 + 60 ...___ 10.50 4-80 ....... 11.80 + 100 ....... 3.90 -100 ....... 40.15

Jan 1, 1916