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By Lawrence A. Shepard, Richard H. Krock

A series of ductile, two phase W-Ni-Fe composites, sintered in the presence of a liquid phase, were tested in tension. Identical room temperature stress-strain curves were obtained for specimens containing from 80 to 92 wt pct W (58 to 75 vol pct W particles). The composites exhibited a maximum elongation of 29pct at room temperature, and 10.7 pct at 77 °K. The tungsten particles in the composite elongated by the same amount at these temperatures. Single-phase alloy specimens matching the composition of the composite matrix showed about one half the flow stress of the composites. The test results demonstrated that the mechanical properties of W-Ni-Fe composites are determined by the tungsten particles alone and are independent of matrix volume fraction or mean free path over the composition range studied. A general prediction of the plastic behavior of two-phase alloys or composites from a knowledge of the properties, size, shape, and dispersion of the individual components is not, at present, possible. The excellent theoretical and experimental exposition of the dispersion-strengthening problem applies only to cases where the stronger phase is present as fine particles and in volume fractions of a few percent. Materials in which the stronger phase constitutes a significant fraction of the volume, although of broad engineering interest, have received comparatively little analytical attention. This important group of materials is the concern of the present study. The degree of deformation of each phase during the plastic working of a ductile two-phase alloy has been established by Boas and Honeycombe,1 Clare-brough,2 and Clarebrough and berger.3 These workers empirically correlated the recrystallization temperature of the individual phases with the degree of cold work sustained by each. It was shown that the deformations of both phases are equal and therefore the same as that sustained by the composite whole when the volume fraction of the stronger phase exceeds 35 pct. At yielding, however, deformation begins in the weaker phase. A direct correlation of composite strength, as a function of deformation, with the strength of the individual components cannot be made. In the presence of stronger phase particles, the flow stress of the weaker matrix phase is enhanced by an additional hydrostatic component. The development and potential magnitude of matrix strength promotion upon straining has not even been experimentally established. Quantitative work in this field has been confined to ceramic-metal composites. These materials fracture at strains considerably below 1 pct by cracking of the ceramic particles.4-6 An indication of the potential constrained matrix strength capacity is given by the observation by Nishimatsu and Gur-land4 that the maximum tensile strength of a WC-Co composite is almost double the bulk strength of the cobalt matrix. The relationship between composite strength and geometry is ordinarily expressed in terms of the mean-free matrix path (referred to subsequently as MFP) between the stronger particles.* This factor takes into account both the volume fraction of matrix phase and the average size of the particles. unke17 concluded that composite strength varied directly with the decreasing log MFP, following the Gen-samer8 relationship. However, Gurland and ~radzil~ reported a strength maximum at an MFP of the order of 1 p in WC-Co composites. A ductile two phase metallic composite was chosen for the present investigation of composite mechanical properties with the view of avoiding the difficulties and ambiguities noted above. The W-Ni-Fe heavy alloy of Green, Jones, and pitkin9 contains 80 to 94 wt pct W, and nickel and iron in a weight ratio

Jan 1, 1963

By J. Szekely, V. Stanek

Steady state heat transfer and fluid flow rates are predicted for the counter-current contacting of gas and solid streams. For a .fixed pressure drop across the bed the convective heat transfer rate is affected by the gas flow rate, which in turn is affected by the temperature distribution in the system. Variations in bed voidage and in particle size were found to change the predicted temperature profiles quite markedly, in particular when the thermal capacities of the gas and solid streams were equal. IN Part I we examined the effect of step and pulse changes in the inlet gas temperature on transients in the flow of gases through fixed packed beds. Here we shall discuss heat flow and fluid flow interactions in the counter-current heat exchange between packed solids and a gas stream. Counter-current heat exchange in packed beds has been extensively studied. In his now classical paper, Furnas' assumed constant property values and developed a simple analytical. expression for the temperature profiles in the gas and in the solid stream. A highly sophisticated analysis of counterflow systems, allowing for transients and interparticle conduction was developed by Amundsen. In preparing a very readable review of this topic Elliott' also presented a number of elegant solutions, including the case involving heat generation. A great deal of work has been done on the application of these concepts to the modelling of the blast furnace. However, in all this previous work the mass flow of the gas was regarded as a quantity independent of the gas-solid heat exchange process. In the following we shall consider counter-current heat exchange between a gas stream and a packed bed of solids, under conditions where the pressure drop across the bed is specified, rather than the mass flow of the gas. FORMULATION Consider a packed bed, extending from y' = 0 to y' = L, in which moving solids and a moving gas are contacted in a counterflow arrangement. Let cold solids, with an initial temperature Tsi and mass flow GA, enter at y' = L, and hot gas with an initial temperature of Tgi and mass flow Gg enter at y' = 0. In contrast to the problems considered in Part I this system has a nontrivial steady state and we shall restrict our attention to the study of the pressure drop flow relationships and the resultant temperature distributions for steady state conditions. Under these conditions the formulation of the problem requires the statement of the following: 1) heat balance on the gas 2) heat balance on the solids 3) the mechanical energy balance equation and in addition the knowledge of the equation of state, and a functional relationship between viscosity and temperature and an expression for the heat transfer coefficient in terms of the other parameters. On neglecting temperature gradients within the solids and for a constant mass flow of the gas, the solution to this problem is well known.'" The expressions for the temperature profiles of the gas and solid streams may be put in the following form: where Tg and T, denote the dimensionless gas and solid temperatures respectively, y is a dimensionless distance, and R is the ratio of the thermal masses. These quantities are defined as follows: For the particular case of equal thermal mass capacities by the gas and the solid, that is R = 1, the Eqs. [1]and[2] simplify to Eqs. (71 and[8], respectively: i.e., the resultant profiles are linear. As for most practical cases , solutions given by Eqs. [7] and [8] will contain only the inlet temperatures as parameters. For a fixed, predetermined value of C;b the above

Jan 1, 1970

By Charles R. Holmes

MORE than 70 igneous pipes and dikes are known to occur in Cambrian sediments throughout an approximately circular area of about 75 sq miles in southwestern Ste. Genevieve County and southeastern St. Francois County, Mo., across the southern portion of the Farmington anticline, which is outlined in fig. 1. From evidence obtained from fossil fragments taken from some of the in-trusive~, and from the similarity in composition of the more basic intrusives to those of known age in surrounding states, these pipes and dikes are believed to be at least post-Devonian and probably Cretaceous in age. As first postulated by Rust,' these intrusives are believed to represent explosion tubes, or diatremes, punched through great thicknesses of solid rock by gaseous pressure. The particular intrusive studied is located about 1 mile north of the small town of Avon at an elevation of 880 ft in the EVz SEy4 NEY4 of see. 2, T. 35N, R. 7E. Outcrop is through the Bonneterre dolomite in two separated exposures. The larger outcrop extends east and west for about 50 ft along a tributary in a small ravine (fig. 2). The smaller exposure occurs as a few scattered patches over an area 20 ft square about 100 ft to the north. The area between the exposures is covered, but scattered patches of the Bonneterre dolomite outcrop throughout the area surrounding the diatreme. Where exposed, contact relations show the surrounding dolomite to be shattered and metamorphosed to a fine-grained rock for a distance of 15 to 20 ft from the intrusive. The igneous rock occurs as a dark greenish-gray porphyry near the center of the diatreme and as a fine-grained, greenish-gray material containing lapilli and metamorphosed fragments of dolomite near the contact with the country rock. The most abundant original mineral of the porphyritic rock is olivine now largely serpentinized as the result of extensive hydrothermal alteration at time of emplacement. The most common constituent of the fine-grained rock, which occurs near the border of the intrusive, is calcite. Mica is a common constituent of both types of rock, occurring as tufts or flakes. Magnetite makes up about 2 pct of the diatreme and occurs as small irregular grains or streaks of tiny grains. Singewald and Milton' have termed the rock of this body an "augite-free alnoite." Susceptibility measurements of pulverized specimens were made from selected samples taken from both the diatreme and the surrounding country rock. The susceptibility of the Bonneterre dolomite was found to be less than 40xlO-6 cgs (centimeter-gram-second) units and that of the metamorphosed contact dolomite less than 200x10-6 cgs. Measurements of individual samples of the igneous rock showed a wide variation in susceptibility between limits of 1000x10-6 cgs to 8000x10-6 cgs, with the maximum difference occuring in samples taken only a few feet apart. The maximum value was exhibited by a highly weathered sample taken from the northern outcrop, while minimum susceptibility was determined from a partially weathered sample taken only a few feet away. These extremes are believed to represent small local concentrations of stringers and grains of magnetite crystals in the igneous rock. A detailed magnetic survey of the horizontal and vertical components of the earth's magnetic field was made over the diatreme area. Stations were occupied at 20-ft intervals as shown by the grid on fig. 2. When greater detail was desired, intervening stations were also occupied. The field instruments were supplied by the Department of Geophysics, St. Louis University. The magnetometers are the Schmidt balance type constructed by the Ruska Instrument Co. These instruments are temperature compensated and have a standard sensitivity of 10 gamma. Calibration of the instruments

Jan 1, 1951

By Charles R. Holmes

MORE than 70 igneous pipes and dikes are known to occur in Cambrian sediments throughout an approximately circular area of about 75 sq miles in southwestern Ste. Genevieve County and southeastern St. Francois County, Mo., across the southern portion of the Farmington anticline, which is outlined in fig. 1. From evidence obtained from fossil fragments taken from some of the in-trusive~, and from the similarity in composition of the more basic intrusives to those of known age in surrounding states, these pipes and dikes are believed to be at least post-Devonian and probably Cretaceous in age. As first postulated by Rust,' these intrusives are believed to represent explosion tubes, or diatremes, punched through great thicknesses of solid rock by gaseous pressure. The particular intrusive studied is located about 1 mile north of the small town of Avon at an elevation of 880 ft in the EVz SEy4 NEY4 of see. 2, T. 35N, R. 7E. Outcrop is through the Bonneterre dolomite in two separated exposures. The larger outcrop extends east and west for about 50 ft along a tributary in a small ravine (fig. 2). The smaller exposure occurs as a few scattered patches over an area 20 ft square about 100 ft to the north. The area between the exposures is covered, but scattered patches of the Bonneterre dolomite outcrop throughout the area surrounding the diatreme. Where exposed, contact relations show the surrounding dolomite to be shattered and metamorphosed to a fine-grained rock for a distance of 15 to 20 ft from the intrusive. The igneous rock occurs as a dark greenish-gray porphyry near the center of the diatreme and as a fine-grained, greenish-gray material containing lapilli and metamorphosed fragments of dolomite near the contact with the country rock. The most abundant original mineral of the porphyritic rock is olivine now largely serpentinized as the result of extensive hydrothermal alteration at time of emplacement. The most common constituent of the fine-grained rock, which occurs near the border of the intrusive, is calcite. Mica is a common constituent of both types of rock, occurring as tufts or flakes. Magnetite makes up about 2 pct of the diatreme and occurs as small irregular grains or streaks of tiny grains. Singewald and Milton' have termed the rock of this body an "augite-free alnoite." Susceptibility measurements of pulverized specimens were made from selected samples taken from both the diatreme and the surrounding country rock. The susceptibility of the Bonneterre dolomite was found to be less than 40xlO-6 cgs (centimeter-gram-second) units and that of the metamorphosed contact dolomite less than 200x10-6 cgs. Measurements of individual samples of the igneous rock showed a wide variation in susceptibility between limits of 1000x10-6 cgs to 8000x10-6 cgs, with the maximum difference occuring in samples taken only a few feet apart. The maximum value was exhibited by a highly weathered sample taken from the northern outcrop, while minimum susceptibility was determined from a partially weathered sample taken only a few feet away. These extremes are believed to represent small local concentrations of stringers and grains of magnetite crystals in the igneous rock. A detailed magnetic survey of the horizontal and vertical components of the earth's magnetic field was made over the diatreme area. Stations were occupied at 20-ft intervals as shown by the grid on fig. 2. When greater detail was desired, intervening stations were also occupied. The field instruments were supplied by the Department of Geophysics, St. Louis University. The magnetometers are the Schmidt balance type constructed by the Ruska Instrument Co. These instruments are temperature compensated and have a standard sensitivity of 10 gamma. Calibration of the instruments

Jan 1, 1951

By J. C. Wilhoit, E. M. Galle

A three-dimensional photoelastic study was made to determine the stress state around the wall and bottom of a wellbore due to fluid pressure within the wellbore and unequal principal geostatic stresses. Models simulating the wellbore were made from a phthalic anhydride-cured epoxy resin. The frozen stress technique of three-dimensional photoelastic-ity was used to determine the stresses within the model. Two separate problems were solved: (1) hydrostatic pressure on all sides of the model with the exception of the inside of the hole, and (2) uniaxial compression perpendicular to the center line of the hole. The results are presented in the form of contour curves for each stress component. The curves cover a region which extends several hole radii from the bottom and wall of the hole. By proper use of these results, the state of stress may be calculated for any point on the wall or bottom of the hole, as well as for any point within the material that surrounds the hole. A systematic method is given for calculating these stress components for any combination of fluid pressure within the wellbore and system of unequal principal geostatic stresses, provided one of the principal geostatic stresses is parallel with the wellbore. The results show that stresses around the wall and bottom of a wellbore, induced by an uneyual system of principal geostatic stresses, are appreciably different from those induced by geostatic stresses that are hydrostatic. For uneyual principal geostatic stresses, the experimentally determined stresses on the wall of the hole several radii from the bottom are in good agreement with the stresses calculated by elastic theory. INTRODUCTION Interest in the problem of determining the stresses around and near the bottom of a wellbore, due to geostatic loading and fluid pressure within the wellbore, originated in the petroleum industry. The stresses on the wall of the wellbore are of interest due to their relation to lost circulation during drilling, the fracturing of formations during squeeze cementing and hydraulic fracturing of producing formations. The stresses on the bottom of the hole are of interest to the drilling segment of the industry because to produce a hole in the earth it is necessary to remove material from the bottom of the hole. This removal of material is produced by structural failure of the rock, whatever the criterion for failure may be. Cunningham and Eeninkl have shown that for certain conditions the effect on drilling rate of the bottom-hole stresses caused by a hydrostatic overburden pressure is small compared to other effects. This question, however, needs further experimental and analytical investigation. Much information concerning the stresses on the walls of wellbores has been published considering both equal and unequal principal geostatic stresses. The problem of determining the stresses around the bottom of the wellbore is considerably more complicated. However, previous investigators have obtained numerical and experimental solutions to the problem for equal principal geostatic stresses. whitworth2 and woods3 have obtained numerical solutions. word415 obtained a three-dimensional photoelastic solution, Durelli and Deily 6 obtained surface stresses only by photoelastic means, and Cheatham and Wilhoit7 determined the stresses around the bottom of a short cylindrical cavity. While Miles and McGuire, Harrison and Kieschnick and Hubbert and Willis 10 obtained the stresses on the wall of a wellbore for unequal principal geostatic stresses, they did not concern themselves with the stresses near the bottom of the hole. The estimates made by Hubbert and Willis of the differences between the principal geostatic stresses indicate that, to obtain a satisfactory solution for the stresses around the bottom of a wellbore, unequal principal geostatic stresses should be considered. This work is directed toward obtaining such a solution. The materials in the earth's crust are nonhomo-geneous, permeable and anisotropic. Previous

By J. B. Cheatham, J. W. McEver

A laboratory investigation of the behavior of casing subjected to salt loading indicates that it is not economically feasible to design casing for the most severe situations of nonuniform loading. When the annulus is completely filled with cement, casing is subjected to a nearly uniform loading approximately equal to the overburden pressure, and, although the modes of failure may be different, the design of casing to withstand uniform salt pressure can be computed on the same basis as the design of casing to withstand fluid pressure. Failure of casing by nonuniform loading in inadequately cemented washed-out salt sections should be considered a cementing problem rather than a casing design problem. INTRODUCTION Casing failures in salt zones have created an interest in understanding the behavior of casing subjected to salt loading. The designer must know the magnitudes and types of loading to be expected from salt flow and he must be able to calculate the reaction of the casing to these loads. In the laboratory study reported in this paper, short-time experimental measurements of the load required to force steel cylinders into rock salt are used as a basis for computing the salt loading on casing. These results must be considered to be qualitative only since rock salt behaves differently under down-hole and atmospheric conditions and also may vary in strength at different locations. The beneficial effects of (1) cement around casing, (2) a liner cemented inside of casing, and (3) fluid pressure inside of casing in resisting casing failure are considered. ROCK SALT BEHAVIOR UNDER STRESS The effects of such factors as overburden loading, internal fluid pressure, and temperature on the flow of salt around cavities have been studied extensively at The U. of Texas. Brown, et al.1 have concluded that an opening in rock salt can reach a stable equilibrium if the formation stress is less than 3,000 psi and the temperature is less than 300°F. At higher temperatures and pressures an opening in salt can close completely. These results indicate that calculations based upon elastic and plastic equilibrium for an open hole in salt should be applied only at depths less than 3,000 ft. In most oil wells the tem- perature will be less than 300F in the salt sections, therefore no appreciable temperature effects are anticipated. Serata and Gloyna2 have reported an investigation of the structural stability of salt. .They assume that the major principal stress is due to the overburden. Other stresses can be superimposed if additional lateral pressures are known to be acting in a particular region. In the present analysis an isotropic state of stress is assumed to exist in the salt before the hole is drilled, since salt regions are generally at rest. This assumption is partially verified from formation breakdown pressure data taken during squeeze-cementing operations in salt. Experimental measurements of the elastic properties of rock salt indicate a value of 150,000 psi for Young's modulus and a value of approximately 0.5 for Poisson's ratio. A value of % for Poison's ratio with finite Young's modulus would indicate that the material was incompressible. Values ranging from 2,300 to 5,000 psi have been reporteda for the unconfined compressive strength of salt. These variations may be due to differences in the properties of the salt from different locations or at least partially to differences in testing techniques. Salt is very ductile, even under relatively low confining pressures. For example, in triaxial tests reported by Handin3 strains in excess of 20 to 30 per cent were obtained without fracture. When casing is cemented in a hole through a salt section, the casing must withstand a load from the formation if plastic flow of the salt is prevented. To determine the forces which salt can impose on casing, circular steel rods were forced into Hockley rocksalt with the longitudinal axis of the rods parallel to the surface of the salt. The force required to embed rods 0.2 to I in. in diameter and 1/2 to 1 in. long to a depth equal to the radius of the rods was found to be F/DL =28,700 psi (± 3,700 psi) , .... (1) where D is the diameter, and L is the length of the rod. CASING STRESSES Since an open borehole through salt at depths greater than 3,000 ft will tend to close, cemented casing which prevents closure of the hole will be subjected to a pressure approximately equal to the horizontal formation stress after a sufficiently long time. As a first approximation the horizontal stress can be assumed to be equal to the overburden pressure. This is in agreement with the suggestion by Texter4 that an adequate cement job can prevent plastic flow of salt and result in a pressure on the casing approximately equal to the overburden pressure. He also advocated drilling with fully saturated salt mud

Jan 1, 1965

By J. B. Agan, R. J. Fernandes

This paper utilizes the layered-system approach, modified to include areal sweep efficiency, to determine the miscible-slug size required and to predict the perfort7zance of a miscible-slug process in a highly stratified reservoir having a permeability variation of 0.76. The slug size in each layer was determined from theoretical calculations and laboratory data which showed that, to maintain miscibility in the reservoir, the slug size had to be 8.2 per cent of the floodable hydrocarbon pore volume. Economic considerations, however, such as the value of the miscible product injected, the cost of injection and the cost of reprocessing the miscible product, limited the amount of miscible product which could be injected into the lower-permeability layers. This resulted in subjecting only 60 per cent of the reservoir to a slug size sufficient to maintain miscibility. Utilizing the relationship of producing gas-oil ratio and areal sweep efficiency as a function of pore volume injected (as obtained from data published by Dyes, Caudle and Erickson2), the theoretical performance was determined. This prediction is compared with actual performance to date. Actual performance reflects an increasing percentage of tniscible product in the produced fluid to a particular level, which remains static for a short period and then increases again to a higher level. This performance suggests that the reservoir has performed as a layered system. It is concluded that the layered-system approach can be used to predict performance in a highly stratified reservoir and that economic consideration is a limiting factor in determining the amount of the reservoir which can be miscibly swept. INTRODUCTION The Paloma zone in the Paloma oil field, Kern County, Calif., is comprised of several sand members separated by siltstone, shale and/or cherty sections. Rapid facies changes within the zone indicate that the sediments were deposited in a "near shore" environment. As a result, the Paloma sands have a high permeability variation, and the Paloma zone is comprised of several sand reservoirs. Since one of the sand reservoirs containing crude oil was not receiving the benefits of gas injection, consideration was given to recompleting certain wells to isolate the sand in order to perform a miscible-phase injection project and, thereby, to increase its ultimate oil recovery. Before proceeding with the project, a review of the literature was made to determine the miscible-slug size that would be required to maintain miscibility throughout the displacement process. Although the review showed that considerable information was available for homogeneous systems, insufficient information was available to determine slug-size requirements and to predict performances for a highly stratified reservoir. This paper has been prepared to describe the method used to determine the miscible-slug-size requirement and to predict the performance of the miscible-phase injection project initiated in the Paloma oil field. Although the Paloma project has only been in operation since Aug., 1958, sufficient production history has been obtained so that a comparison can be made with the predicted performance. DESCRIPTION OF RESERVOIR The reservoir in which the miscible-phase project was initiated in the Paloma field is shown on Figs. 1 and 2. Reservoir properties are as follows: average sand thickness, 43 ft; porosity, 19.1 per cent; water saturation, 47.2 per cent: oil viscosity, 0.328 cp; reservoir temperature, 250°F; reservoir pressure, 3,500 psi: gas saturation, 21.2 per cent at time of miscible product injection; and total net hydrocarbon pore volume, 19,993,000 reservoir bbl. LIMITATIONS The method described herein utilizes a layer-system approach, where injection into and production from each layer is assumed to be proportional to the layer's fractional capacity. The effects of increased fluid mobility on injection and production rates, in layers which have had breakthrough, are not reflected in this method. There has been considerable controversy over the slug size necessary to maintain miscibility throughout the displacement process. In this method, the slug-size

By C. D. Hall, F. E. Dollarhide

Conventional static tests of fluid-loss agents do not realistically simulate conditions in a fracturing treatment. The dynamic tests reported here show that fluid-loss volume is better represented as proportional to time, rather than as the square root of time. This leads to a different equation for fracture area. The leak-off rate increases with increasing shear rate at the fracture wall, but appears to approach a limiting value. Pressure effects are minor. Spurt loss ordinarily is not affected by the flow velocity in the fracture and is inversely proportional to concentration of agent. The filter cake, once it is well established, is resistant to damage by the flow of plain fracturing liquid (without fluid-loss agent). The latter two findings indicate that a treatment employing a high-concentration spearhead followed by plain fluid can offer a more economical treatment under suitable conditions. INTRODUCTION The successful design of hydraulic fracturing treatments depends on accurate knowledge of the fluid-loss properties of the fracturing fluid. Howard and Fast,' in giving the basic equation relating fracture area to fluid and treating parameters, described three mechanisms which might control the rate of fluid leak-off from the fracture. One mechanism usually is dominant in a given well treatment. For each mechanism, the leak-off velocity is inversely proportional to the square root of time, and the proportionality constant is designated as the fracturing-fluid coefficient. For the wall-building type of fluid-loss agent, the coefficient is determined by a filtration test in a pressure cell, usually with a rock wafer or core as the filter medium. In these static tests, the cumulative volume generally is proportional to the square root of time, after an initial spurt volume. The static-fluid-loss test is not representative of the con,-&tions under which a fluid-loss agent performs in a fratturing treatment. The marked difference between the dynamic- and static-fluid-loss behavior of drilling fluids reported in the literature2,3 implies that dynamic testing is also needed with fracturing fluids. We have therefore undertaken a study of the dynamic-fluid-loss behavior of fracturing fluids. The testing apparatus has also afforded opportunity to evaluate the resistance of the filter cake to removal or damage by flowing fluid containing no fluid-loss agent, with and without sand. The results of these studies offer a means for more accurate evaluation of fluid-loss agent performance, and point the way to a "spearhead" fracturing technique which may offer more economical treatment for some wells. EXPERIMENTAL METHODS The dynamic-fluid-loss testing method is applicable to any type of wall-building fracturing fluid. The present study aimed first at finding what phenomena are involved, and therefore has been limited in the number of materials tested. All of the results specifically reported herein are for kerosene containing a commercial solid fluid-loss agent, which is commonly used at 50 lb/1,000 gal of oil. Another agent in liquid form, used usually at 20 ga1/1,000 gal oil, has shown all the same phenomena in dynamic tests, and generally the same level of fluid-loss control as the solid agent. The dynamic-fluid-loss core cell used in all tests is shown in Fig. 1. The fracture was simulated by the an-nulus between a 2.03 in. OD sandstone core and the surrounding pipe. Annulus widths of 0.234 and 0.117 in. were used, and the core was 3.5 in. long. The annular geometry provides a uniform fluid velocity and a well-defined shear rate over the entire filtering surface, and permits a large filter area (144 sq cm) in a reasonably compact cell. The leak-off fluid passed into a 0.5 in. diameter axial hole in the core. A hollow steel rod through this hole was threaded into a rounded "streamliner" upstream of the core, and into a mounting stud downstream. The streamliner and the stud had the same outside diameter as the core. In all tests except those where sand was circulated, the mounting stud had protruding rings which constricted the annulus, to minimize any tendency for channeling of the fluid to the side exit port. The ends of the core were sealed by Neoprene, steel and Teflon washers. The leak-off fluid was conducted from the hollow rod to an exit tube, through a metering valve (a fine-pitched needle valve) and a quick-opening toggle valve in series, and into graduated cylinders for volume measurement; Two separate circulating systems were used in the experimental program. The extensive initial testing was done at 50 to 150 Psi. The fluid was circulated by a variable speed Moyno pump, and the flow rate was read by a rota-meter flow meter. The filtration Pressure was supplied by holding a back-pressure with a throttling valve. The discharge streamcould be diverted into any of four sections

Jan 1, 1965

By J. G. Eenink, R. A. Cunningham

One phase has been completed of a laboratory invesrigation of formations with relatively high permeability under conditions of overburden, formation and mud coltrmn pressures. The following statements are based on these tests within the limitations described. Drilling rate decreased when mud column pressure was greater than formation pressure. The decrease was primarily due to a layer of cuttings and mud particles held to the hole bottom by the difference in pressure. Much of the force of the bit was wasted in this layer and was unavailable for penetrating virgin formation. Adequate jet velocities helped clean the filter cake and chips away and resulted in increased drilling rate — the higher the jet velocity the faster the drilling rate. Drilling rate increased slightly when formation pres sure was greater than mud column pressure. The i11(reuse resulted from cleaning the hole bottom as formarion fluid flowed into the borehole. Overburden pressure had practically no effect on drilling rate. INTRODUCTION Some formations are difficult to drill in a wellbore hole but are easily drilled under atmospheric conditions in the laboratory. The reasons for this apparent difference in drillability are not fully understood. An increase in formation compressive strength causes a reduction in drilling rate. It has been shown by Griggs1, Handin2 and others3-1 that formation strength increases under conditions of high hydrostatic stress. Based on these results, a decrease in drilling rate would be expected with increased drilling fluid pressure in formations of low permeability having low formation fluid pressure. Such a decrease has been shown by Murray. et a1 and Eckel" This effect holds even when using nitrogcn under high pressure as the drilling fluid (unrc-ported tests from the Hughes laboratory). Poor bottom-hole cleaning may account for decreased drilling rates. Even though it may not be easily explained, evidence of poor cleaning can easily bc seen. One evidence is the increased drilling rate that accompanies decreased balling obtained with addition of oil in some muds used to drill shales.4,7,3 Many variables can affect drilling rates. These may include mud composition and properties, formation properties, bit types and operating conditions, formation fluid, mud column and overburden pressures. These must be studied a few at a time under carefully controlled conditions which simulate actual conditions as closely as possible. The purpose of this work was to investigate effect of overburden, formation and mud column pressures on drilling rates in permeable formations. These tests were suggested by conditions shown in Fig. I. Represented is a borehole drilled into a formation with relatively high permeability. In the vicinity of the hole bottom there exists a mud column pressure, P a formation fluid pressure, P and an overburden pressure, The mud has low water-loss properties and sufficient weight to more than overbalance the formation pressure. Laboratory investigation included a range with formation pressure greater than mud column pressure. NOMENCLATURE Pm mud column pressure = pressure of drilling fluid or mud at hole bottom Pf, formation pressure = pressure of fluid in intersticies of formation

By F. J. Martin, W. G. Hubler

The Beattie mine is at about the center of Duparquet township in the Province of Quebec, Canada. It is 22 miles northwest of the town of Noranda. The elevation is approximately 1200 ft. above sea level. This locality, long considered a favorable one from the geological point of view, has been prospected for over 20 years, but no discoveries of economic importance were made until the present orebody was found by John Beattie in 1930. The specific gravity of the ore is 2.77. The gold occurs in intimate association with the sulfides, pyrite and arsenopyrite, which in turn are very finely disseminated in a silicified porphyry. The bulk of the gold is associated with the pyrite, only a small proportion being with the arsenopyrite. There are small amounts of magnetite, ilmenite and chalcopyrite present in the ore. There is also some hematite in the ore that is mined from near the surface in the open pit. Metallurgical Problems and Methods or Attack 1. The ore is extremely hard and resistant to grinding. 2. The sulfide minerals are finely disseminated in the gangue. 3. The gold, in turn, is so intimately associated with the sulfides that grinding to even 5 microns will not release all of the values for cyanidation. 4. It is necessary to make a high ratio of concentration in order to obtain a product sufficiently high in gold to meet high shipping and treatment charges. Hardness of the Ore.—Owing to the extreme resistance of the ore to grinding, it was recognized that grinding costs would be high. Microscopic tests showed that grinding to 95 per cent minus 325 mesh would be necessary to liberate a sufficient amount of the values in order to obtain a tailing assaying 0.02 oz. gold per ton, which is considered to have the economical minimum gold content that can be obtained. It is not feasible to grind this hard low-grade ore (0.18 to 0.20 oz.) to 95 per cent minus 325 mesh, so it was necessary to overcome the problem in another way. The following method was decided upon: (1) Fine crushing to minus 1/4 in.; (2) relatively coarse primary grinding; flotation of low-grade concentrates in the primary and rougher circuits and discarding the

Jan 1, 1935

By John K. Berry

The handling and disposal of mine water is a much larger problem than is apparent at first glance. Many more tons of water are removed from underground coal mines in the United States each year than tons of coal. In the old anthracite region of Pennsylvania the average was around 36 tons of water for each ton of coal produced, while bituminous mines average about 5 or 6 tons. Water encountered in the mines may come from several different sources. In mines with light cover and without a firm solid roof, rain may seep directly into the workings. This is also true of deeper mines where pillar falls have broken the roof to the surface. The top under creek beds is generally faulty and broken and water comes through the roof at this point. Deeper mines are frequently overlain by water-bearing strata and pillar breaks and faulty top can admit water, while places running to the dip often accumulate water which comes up through the bottom. In all cases, except where passing under a year-round stream, the amount of water made is usually pretty closely connected with the weather-more water during the rainy season, less in the dry, although the deeper a mine is, the longer it is before changes in rainfall are felt. Another source of water, not connected with seasonal changes, is old water, accumulated over a period of time in abandoned workings of the mine, or from flooded adjacent mines. Here the water filters through the coal, the parting, or comes up through cracks in the bottom. Similarly, core holes, drilled to prospect the property, can be a source of unexpected water and modern safety requirements for dust-allaying water at the working faces can turn a pleasant working area into a soggy mess over the weekend if the system is not properly maintained and operated. Why water must be disposed is obvious. If allowed to accumulate, sooner or later the mine will fill up, or at least it will become "roofed" in low places, blocking ventilation and traffic. But it must also be controlled long before it reaches this stage. Water standing in the working faces is unpleasant for the men who have to work there and also cuts down on the amount of work they can do, as they must watch where they step all the time. It is especially unpleasant in low coal.

Jan 1, 1973

By Kenneth A. Gutschick, Robert S. Boynton

Lime has become a very general loosely used term that includes virtually all finely divided types of limestone as well as burned forms of lime. However, actually (and according to Webster) lime is only calcined limestone (known as quicklime, calcium oxide, or calcia). It also embraces the secondary product of quicklime-namely hydrated lime or slaked lime (calcium hydroxide). Fundamentally there are two basic types of limestone-high calcium and high magnesium (dolomitic). The dolomitic quicklimes and hydrated limes correspond to their "high calcium" counterparts in terminology. The only difference is that the dolomitic types are a combination of the elements, calcium and magnesium, whereas high calcium limes contain only 0.5 to 2 pct of magnesium. Both types, which are made through calcination at high temperatures, are shown chemically as follows: [ ] In the above reactions either type of limestone is burned (calcined) in furnaces known as lime kilns so that the carbon dioxide content of the stone is expelled as a gas. With high calcium limestone 44 pct of the weight of the stone is lost; with dolomitic limestone the loss is 48 pct. Also, both reactions are chemically reversible since quicklime absorbs carbon dioxide readily and in so doing transforms itself back to the original carbonate form. Most quicklimes correspond in size to the original rock, which varies from one to eight inches, depending upon the type of kiln employed. Slight shrinkage occurs during calcination. A few limestones when calcined will decrepitate (break down) into a fine powdery form; however, chemically it is the same as the pebble or lump-sized material. For some uses the lumps of quicklime are pulverized and packaged. Since quicklime has great affinity for moisture and carbon dioxide, it is perishable. When it absorbs moisture and CO2 slowly from the atmosphere, the resulting product is "airslaked." Consequently, it must be stored in dry, moisture-proof areas that are free from CO2. Because of its fugitive nature, it is usually consumed within a few weeks after manufacture. A more stable form of lime is hydrated lime-commercially made by adding water to the quicklime until the lumps break down into a fine, white powder. This product, which is usually packaged, can be stored more safely; and many of its uses are interchangeable with quicklime. The irreversible chemical reactions of hydrated lime for both high calcium and dolomitic types are: [ ]

Jan 1, 1960

By C. F. Knutson, Martin Felsenthal, J. D. Lung, J. D. Sudbury

This paper has been written to summarize the laboratory and field studies leading to injection of Pacific Ocean water into the Third Grubb formation. Laboratory tests for studying the permeabilities of cores to Pacific Ocean water are described. Resu1ts of these tests showed that the water could be successfully injected if it is chertzically stable, sterile, and properly filtered. Clay swelling was shown to be a comparatively minor factor in permeability reduction. Studies leading to development of an economical system for properly conditioning the ocean water are discussed. It was necessary to control pH, calcium carbonate deposition, bacterial growth, iron solubility. oxygen, and suspended .solids. A relatively simple system combining the use of sulifur dioxide, a quaternary rlmmonium chloride, and filtration was shown to adeqrrately control all these factors. This combination has not previozrsly been used as a water treating technique. Evaluation tests of the water conditioning system prior to injection are described, and results of such tests are presented. Control measures needed to insure a continusously adequate water treatment are reviewed. INTRODUCTION The utilization of sea water for waterflooding has only recently been attempted. Knowledge of treating requirements has been limited, and in most cases no water treating has been done. Prior to the initiation of the Third Grubb zone pilot water flood at Ventura, Calif.,1,2 extensive laboratory research was done in an effort to define the treatment necessary to provide a suitable injection fluid. Close coordination and cooperation between field and research personnel were found to be the foremost requisites in developing the most economical and practical method for treating ocean water. LABORATORY STUDIES Plugging Tendencies of Untreated Ocean Water A program of laboratory studies was initiated for the purpose of evaluating whether ocean water could be injected into the formation for prolonged periods of time without causing plugging of the pore spaces of the formation. Because of the fairly low permeability of the formation (averaging about 40 md), it was realized from the outset that a water of exceptionally high quality was needed. Ocean water used in the laboratory studies was carefully filtered through ultrafine fritted glass filters, having nominal maximum pore sizes of 1.4 microns. Permeability tests were then performed on representative core material from the formation. It soon became apparent in these tests that filtration alone was not a sufficient treatment for the ocean water. Prolonged injection of the filtered water caused rapid plugging of the core samples. The permeability decline of a typical sample is illustrated by Curve A in Fig. 1. The several factors which can contribute to this plugging tendency are briefly reviewed below: Interaction with Formation Clays An evaluation of clay swelling effects on liquid permeability was made using core samples from the Grubb formation. An oil was chosen for determining the reference liquid permeability because it would not tend to react with any clays that might be present in the formation. The samples were then extracted, dried, and resat-urated with either treated ocean water, formation water, or fresh water. Permeabilities to the various waters were then determined. Results of this test series are summarized in Fig. 7. The difference between the oil permeability and water

Jan 1, 1957

By William H. Spice

The year 1942 in the South Central Texas area was marked by a sharp curtailment of exploratory drilling as compared with the past several years. In the 33 counties that compose this district, 17 of which are nonproducing counties, only 51 exploratory wells were drilled during the year 1942. This compares with 118 exploratory wells drilled during 1941, or a decrease of more than 50 per cent. At the end of the year 10 active exploratory wells were drilling in this area, as against 19 being drilled at the end of 1941. Of the exploratory wells drilled, two brought in oil wells and were new field discoveries and one was a gas well extending a recently discovered shallow gas area in the western part of the district. This compares with five new oil fields, one new . gas field and two extension wells drilled in 1941. Both new field discoveries were small and in areas outside of the general trend of the main producing horizon of the district in Edwards limestone: One new field, the Imogene, in Atascosa County, is a deep Edwards limestone prospect at 7500 ft., and the other new field, the Poth, in Wilson County, is a sSEa110w Wilcox (Eocene) prospect at 4000 ft. Subsequent drilling in each field to the end of I942 has proved disappointing. There were no new discoveries along the old Balcones fault-line trend, although 35 of the exploratory wells were drilled in counties along this trend. Approximately 38 wells were drilled in or adjacent to the proven fields of the district, of which 18 were oil wells, 2 were gas wells and 17 were dry holes. The district produced 6,186,178 bbl. of oil during 1942, which was a 7 per cent decrease under production for 1941. Approximately 4,961,000 bbl. of this total production, a slight increase over 1941, was produced by the four Edwards-limestone fields, Luling, Branyon, Salt Flat and Darst Creek, and the rest of the production came from the other 42 active fields in the district. During the year, 20 new producing wells were completed and 221 wells were abandoned in the producing fields. This alarming excess rate of abandonment~ over completions will be further reflected undoubtedly by a further decreased rate of 1943 production under 1942. Two active fields in the district in which more than one producing well was completed during the year were Bee Creek and Washburn. The majority of exploratory work in the district was confined to areas along the Wilcox trend, with a certain amount in progress along the deeper Edwards limestone trend. The successful completion of sevemi wells in the Washburn field from multiple sands in the Lower Wilcor (Eocene) has stimulated exploratory work along this trend, while the completion of a small well in the Imogene field from the Edwards limestone at 7500 ft. has renewed interest in this horizon at depths greater than generally are producing in the district. New Fields ounty. ble Oil and Refining Company's No. I

Jan 1, 1943

By William H. Spice

The year 1942 in the South Central Texas area was marked by a sharp curtailment of exploratory drilling as compared with the past several years. In the 33 counties that compose this district, 17 of which are nonproducing counties, only 51 exploratory wells were drilled during the year 1942. This compares with 118 exploratory wells drilled during 1941, or a decrease of more than 50 per cent. At the end of the year 10 active exploratory wells were drilling in this area, as against 19 being drilled at the end of 1941. Of the exploratory wells drilled, two brought in oil wells and were new field discoveries and one was a gas well extending a recently discovered shallow gas area in the western part of the district. This compares with five new oil fields, one new . gas field and two extension wells drilled in 1941. Both new field discoveries were small and in areas outside of the general trend of the main producing horizon of the district in Edwards limestone: One new field, the Imogene, in Atascosa County, is a deep Edwards limestone prospect at 7500 ft., and the other new field, the Poth, in Wilson County, is a sSEa110w Wilcox (Eocene) prospect at 4000 ft. Subsequent drilling in each field to the end of I942 has proved disappointing. There were no new discoveries along the old Balcones fault-line trend, although 35 of the exploratory wells were drilled in counties along this trend. Approximately 38 wells were drilled in or adjacent to the proven fields of the district, of which 18 were oil wells, 2 were gas wells and 17 were dry holes. The district produced 6,186,178 bbl. of oil during 1942, which was a 7 per cent decrease under production for 1941. Approximately 4,961,000 bbl. of this total production, a slight increase over 1941, was produced by the four Edwards-limestone fields, Luling, Branyon, Salt Flat and Darst Creek, and the rest of the production came from the other 42 active fields in the district. During the year, 20 new producing wells were completed and 221 wells were abandoned in the producing fields. This alarming excess rate of abandonment~ over completions will be further reflected undoubtedly by a further decreased rate of 1943 production under 1942. Two active fields in the district in which more than one producing well was completed during the year were Bee Creek and Washburn. The majority of exploratory work in the district was confined to areas along the Wilcox trend, with a certain amount in progress along the deeper Edwards limestone trend. The successful completion of sevemi wells in the Washburn field from multiple sands in the Lower Wilcor (Eocene) has stimulated exploratory work along this trend, while the completion of a small well in the Imogene field from the Edwards limestone at 7500 ft. has renewed interest in this horizon at depths greater than generally are producing in the district. New Fields ounty. ble Oil and Refining Company's No. I

Jan 1, 1943

By Y. H. Liu, R. Kiessling

The chromium, iron, and tungsten borides have been treated with ammonia at different temperatures. They are attacked, forming metal nitride and boron nitride, and the results are summarized in the tables. In the tungsten-nitrogen system a new phase has been observed, closely related to the known ß phase. THE present investigations were begun to determine whether any ternary phases exist in the transition metal-boron-nitrogen systems for the metals chromium, iron, and tungsten. Attempts to prepare such phases were made by using the borides of the metals as starting materials and ammonia as the nitriding agent. Although no new ternary phases have been found to exist, the results may be of some interest with regard to the technical use of the borides. General Procedure A steady stream of dry ammonia was passed through a silica reaction tube, the central part of which was kept at the reaction temperature while its ends were water-cooled. Weighed amounts of the borides were placed in a silica or porcelain boat and heated at different temperatures for a period of 10 to 24 hr. The boat was then rapidly removed from the reaction zone to the quenching zone, the water-cooled end of the tube, by means of a simple magnetic device. The nitrogen content of the products was determined by the increase in weight of the specimens, and the phase analysis was carried out by X-ray methods. For this analysis a Guinier-type camera, constructed at this Institute, was used with a bent, ground quartz crystal monochromator. The general reaction, which occurred in all the experiments, may be summarized as: metal boride + nitrogen -* boron nitride + metal nitride For the higher temperatures pure metal was formed instead of metal nitride. It is sometimes difficult to Discussi detect boron nitride among the reaction products by X-ray methods. Prolonged exposures of some specimens showed, however, that the strongest reflections of boron nitride were present. Additional evidence for its presence was given by the increase in weight of the specimens after nitriding. This increase was always greater than that corresponding to nitride formation only and was often in close agreement with the formula given above. Finally, a white powder, which was shown by X-ray methods to be boron nitride, was left if the reaction products after nitriding Fe,B at 448°C and FeB at 768°C were dissolved in diluted sulphuric acid. Ch rom iu m - Boron - N itrogen Five phases have been found to exist in the Cr-B system,' , and all were used as starting materials. Investigations on the Cr-N system have shown the existence of two nitrides with ideal composition Cr,N and CrN.".' * The results are summarized in Table I. All the borides are attacked and decomposed into chromium nitride and boron nitride, and the kind of nitride formed depends only on the temperature and not on the boride used as starting material. The lowest reaction temperature, however, is different for the different borides. Thus the 6 phase begins to react at about 735 "C, the r phase at about 800°, the S phase at about 900°, the 7, phase

Jan 1, 1952

Discussion of the paper of DWIGHT T. FARNHAM, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 93, September, 1914, pp. 2357 to 2364. DAVID T. DAY, Washington, D. C.-Do you know anything about the character of that clay as to organic matter? H. RIES, Ithaca, N. Y.-No; it is a dark brownish clay, sandy in its nature. The brownish coloring is probably due to organic matter. Some lignite is also present. DONALD W. Ross.*-I have worked at the plant under consideration. I have not seen Mr. Farnham's paper; but in answering the question as to the organic matter, I might say there is practically no organic material scattered through the shale. There are, however, several layers of carbonaceous shale and rather low-grade coal interbedded with the formation. There are two very serious drawbacks-one which threatens to shut down the plant and another which merely means the expenditure of money. The first is taking care of the sediment from the washing away of the overburden. The government is doing extensive work at different points about Lake Washington with a view to creating a fresh-water harbor for Seattle. I understand that they keep at the Denny-Renton people to keep the channel of Cedar River clear. The Denny-Renton Co. can hardly help filling up the channel so long as they continue their hydraulic work, so this is probably one of their most serious problems. The other is this: There is a large percentage of what I should call micaceous shale or sandstone-a sandstone which contains a large amount of light-colored mica. Of course only a limited amount of this can be used in the manufacture of paving brick. As they shoot down the bank after the overburden of gravel and loam is washed away, these large boulders of micaceous sandstone come down. The strata have apparently been crushed where the clay pit is located so that the exact formation cannot be readily determined. These pieces of sandstone, 5 or 6 ft. in diameter, have to be blasted and removed from the shale. They bother both in the open pit and in the tunnel mining. In the tunnel mining of the shale blocks frequently cover the holes in the roof of the tunnel through which the shale is loaded into cars.

Jan 4, 1915

By A. R. T. Denues

LIQUID-OXYGEN explosives commonly consist of a carbonaceous absorbent enclosed in a canvas wrapper and soaked with a liquid con-taining more than 90 mol per cent of oxygen. Investigation of these explosives in this country was initiated in 1917 by George S. Rice, then Chief Mining Engineer of the Bureau of Mines. The early development is summarized in two papers.1,2 Their characteristics, advantages and disadvantages were considered in a recent bulletin of the Bureau of Mines.3 Other publications of this Bureau4,5 treat the technology of these explosives and contain adequate references to pertinent literature. These investigations defined the properties of liquid-oxygen explosives and improved them greatly; however, an outstanding disadvantage is their high inflammability, a property of critical practical importance. These explosives as hitherto prepared are easily inflamed; the combustion resulting from an accidental ignition is particularly dangerous because of the ease with which it passes into detonation. For this reason the Bureau of Mines undertook a cooperative investigation, which has resulted in the development of fire-retardant treatment for the minimiza-tion or elimination of this hazard without materially impairing the explosive properties, including the ease of detonation. This presentation will offer a general description of the investigation and the outstanding results. Further phases will appear in subsequent short papers, and the entire investigation including the results of detailed experiments will be available in a forthcoming bulletin of the Bureau of Mines (Bull. 429). The effects produced by fire-retardant treatments of the carbonaceous absorbent and of the canvas wrappers were investigated separately, and the efficacy of combinations of these treatments with particular reference to the possibility of inflammation and to the development of detonation from inflammation was studied. The experimental explosive was pre-pared from a granular carbonaceous absorbent and the results described may be more or less unique for such a material. An extensive preliminary

Jan 1, 1940

By H. R. Drullard

TO obtain the best results from hammer drills, close attention must be paid to two factors in drill maintenance, which are of equal importance; one is lubrication, the other is the shank. With the exception of stoping drills, most modern rock drills require both oil and grease. The oil ports are in the lubricator, on or behind the hammer cylinder; the grease port for the lubrication of the chuck sleeve and rotating mechanism is on the chuck end. Ordinary machine oil is not adapted to rock drills; a heavier more gelatinous oil such as castor machine oil or liquid grease should be used. The lubricators should be filled once for every 12 or 14 ft. (3.5 to 4 m.) of hole drilled. Grease guns should be used to fill the port in the chuck end once a shift; a medium (No. 3) grease is well adapted to this purpose. Hard grease must not be put into the lubricators, as it will not flow through that part. Contrary to the popular belief, oiling a machine once or twice a shift does not provide sufficient lubrication; the drills should be oiled once for every 12 or 14 ft. of hole drilled. The rotating handle of a stoping drill is an oil reservoir and is provided with a port for oiling. The rotating handle is packed with wick-ing, or similar material, which causes the oil to feed slowly from the handle to the other parts of the machine. Stoping drills require oil at least twice a shift; lighter oils than castor, such as Arctic Ammonia, may be used. Drills used in shaft sinking can be oiled satisfactorily by placing a good-sized, drop, sight lubricator on the station above the sinking operations and connecting it with the air-line supplying the sinking drills. If this lubricator is properly filled and adjusted, a uniform oiling of the sinking machines will be effected without the necessity of oiling the drills individually. The grease end should be filled at the station or surface before each drilling period. The shift boss should see that the machines are greased and also that the lubricators at the station function properly. The life of the air-drill hose is somewhat shortened by this method, as oil attacks the inner tube; but as some oil is always present in the compressed air, this is not a serious objection to the method.

Jan 1, 1922

By G. L. F. Powell

Bulk samples of silver have beat undercooled lo a large degree in contact with crystalline siliceous and ceramic oxide materials, indicating lhat stable oxides and oxide compounds are not the heterogeneous nucleants which normally catalyze cryslallization within a feu degrees of the equilibrium freezing point. Since 400-g samples were undercooled 250°C in contact with cristobalite, it is concluded that the undercooling required for homogeneous nucleation of sil11er is greater than 250°C. Undercooling was Jacilitated by precleaning the crucibles with a high-fires -sure blast of gas. IN numerous experiments on the undercooling of metal melts it has been assumed that a solid glassy surface, being non crystal line, will have no effect in catalyzing crystal nucleation from the melt. Conversely, it is usually accepted that any crystalline surface, in contact with a metal melt, will catalyze nucleation of metal crystals from the melt at degrees of undercooling less than that at which homogeneous nucleation will occur. Both these assumptions were implicit in the claim that homogeneous nucleation was observed in experiments1'2 on the undercooling of small metal droplets (10 to 100 mp diam). The droplets were thought to be freed of suspended crystalline particles which would otherwise catalyze heterogeneous nucleation. They were supported on flakes of silica glass which were assumed to be amorphous, and therefore incapable of acting as substrates for heterogeneous nucleation. In later experiments, large samples of molten metal were undercooled to temperatures similar to those achieved by the droplet technique by melting in a fused-silica crucible3 or a boro-silicate glass slag.4 Since these samples were usually fully enclosed in glass at the moment of freezing, it seemed possible that nucleation was homogeneous when maximum degrees of undercooling were achieved, despite the large size of the samples (up to 500 g). In experiments on the undercooling of silver5 the metal was contained in vitreous silica crucibles, the

Jan 1, 1968