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By Arcy, D&apos Banister

The productive potential of the Nation's principal active and inactive silver mining districts has been evaluated, using 1964 economic conditions and assumed silver prices ranging up to $3 per ounce. On this basis, the United States has an estimated 5 billion ounces of unmined silver, excluding minor byproduct silver in gold deposits. Approximately 3.5 billion ounces are contained in deposits requiring higher silver prices to be economically minable, and about 1.3 billion ounces are in currently operating mines. An analysis of silver consumption trends since 1954 indicates that the free world industrial market will climb to nearly 800 million ounces annually by 1985. U.S. industrial silver consumption has been projected to increase at an annual rate of 4 percent from 1965 to 1985. Average annual increase for the remainder of the free world has been 8.1 percent since 1953; this is expected to level off with an estimated average increase of 5 percent to 1975 and 4 percent from 1976 to 1985. Foreign silver production has, in the past, exceeded consumption, but in 1960 the supply deficit was over 100 million ounces. U.S. production, also traditionally exceeding demand, was suddenly overtaken at the start of World War II. By 1964 the annual deficit, excluding coinage, was over 84 million ounces. World coinage requirements of silver are fast declining and expected to total only 25 million ounces annually by 1985. In fact, coins are already becoming major short-term source of silver to fill the large deficit between industrial demand and current production. The larger, long-term deficit (to 1985, the limit of this study) must be balanced by silver from the hoards and new production from silver deposits. Eventually all of the deficit must be met by new production or silver prices will rise until consumption is greatly curtailed. To balance free world supply and demand, it is estimated that the free world must produce an additional 85 million ounces by 1975 and 375 million ounces by 1985. The estimated proportion expected from U.S. deposits is 17 million ounces by 1975 and 74 million ounces by 1985.

Jan 1, 1969

By Robert J. Willard

In its search for additional ways to increase understanding of rock behavior, the Twin Cities Mining Research Center has turned to the scanning electron microscope, an instrument rapidly finding application in research concerned with surfaces of materials. Since features indicative of the manner in which rocks fail may be recorded on the surfaces of fragments as disintegration proceeds, this microscope might be used as a tool for seeking and mapping these minute features. In pursuit of such features, we chose to scan a portion of the fracture surface from a quartzite disk compressively loaded to failure between two pins centered along the disk's axis. The resultant fracture appeared as a rough, diametric plane, and the fracture surface near one of the loading points was scanned with the microscope.

Jan 1, 1969

By N. R. Pillai, T. R. Anantharaman

THE striking alterations in the constitution and structure of cast A1-Si alloys brought about by addition of small quantities of some elements, particularly sodium, have been extensively investigated. Many theories' have also been propounded to explain this so-called lLmodification" process, but their main concern has been more to throw light on the action of sodium than to arrive at general criteria underlying this interesting as well as intriguing phenomenon. Such theories have generally dealt with one or more, but not all, factors that seem to have a direct or indirect influence on the cast structure of A1-Si alloys, e.g.., formation of ternary eutectic, removal of oxides, hydroxides, and so forth, by fluxing, morphological changes in silicon, and inhibition of growth of silicon grains through colloidal action, compound formation, preferential adsorption, or reduction of surface tension. Kim and Heine2 were the first to study the modification of A1-Si alloys in a systematic as well as comprehensive manner and to list the important characteristics of a satisfactory modifier. According to them, an important property of the modifying element is its capacity to form a stable compound with silicon in the appropriate temperature range. Other subsidiary requirements are that the element should get adequately dispersed in the melt at the inoculating temperature and also must not form stable compounds with aluminum. The alkali elements, with the exception of lithium, fulfill these requirements most satisfactorily and have been shown to be successful modifiers by these workers. Sodium is the most effective of these and seems to be in a class by itself for various reasons noted by earlier investigators.37 None of the other elements tried by Kim and Heine, viz., Mg, Ca, Cd, Zn, In, Pb, P, As, Bi, S, and Se, showed any significant modifying action. We wish to report here briefly on substantial modifications in cast eutectic A1-Si alloys brought about by some V group elements, which do not comply with the Kim-Heine requirements. Aluminum and silicon used in the present work were indigenous and had purities of 99.8 and 99.5 pct, re-

Jan 1, 1969

By R. Ward Grosz

Reasonable and timely solutions to the complicated mathematical calculations involved in the mine planning, economic evaluation and slope stability studies related to the Ruth Mine would not have been feasible without the modern digital computers. The Ruth Mine was a prosperous underground copper operation in east central Nevada from 1915 to 1948, when rising mining costs finally exceeded the value of the ore. A substantial reserve of porphyry copper remained in the ground, but until recently all economic evaluations indicated that it was at best a marginal operation and a relatively poor risk of capital. There has been a steady progress in improving all aspects of surface mining since the first steam shovel started stripping overburden; however, developments in just two rather specialized areas proved to be critical in changing the Ruth Mine from a reserve of mineralized rock to an economically attractive orebody. One involved the progress made in recent years in the science of slope stability. Applying the latest techniques in this field to mine planning resulted in reducing the stripping ratio from 6.0:l to 4. 2:l. The other major factor was the efficiency and cost performance of large capacity haulage trucks which made it feasible to go down over 1100 ft. in an open pit and recover ore with a high stripping ratio economically.

Jan 1, 1969

By Diessel C. F K, Ng N

The commonly used Stopes-Heerlen coal petrographic classification and nomenclature has over the years been subject to variable interpretations. This paper discusses the problem with specific reference to the inertinite maceral group. The effect of various interpretations of the Stopes-Heerlen system on maceral analysis is discussed and illustrated by means of comparative analyses conducted by a number of laboratories in Australia. An attempt is made to define the reflectance thresholds used by the authors to subdivide the inertinite group; the genetic and technological significance of these thresholds are compared. The difficulties of distinguishing structured and non-structured macerals of the inertinite group is discussed in terms of possible improvements to the present Stopes-Heerlen system by extending the classification to include transitional maceral types.

Jan 1, 1969

By J. Hudy

An investigation has been made to determine the applicability of the Cendrex X-ray instrument for the measurement of the ash contents of washed bituminous coal products. The results obtained for selected products from five preparation plants in the northern Appalachian region are described. Emphasis of the study was placed on low-ash bituminous coals suit-able for utility or metallurgical markets. There was good agreement between the results obtained by conventional ash determination methods and by the Cendrex for all the products tested. A principal disadvantage of coal in competition with other fuels has been its inconsistent quality, especially with respect to ash content. Mine rnechanization and production from coalbeds of inferior quality have accentuated this failing. Present quality control methods in coal preparation plants are inadequate because (1) control samples taken over a production shift only serve to give the average quality of the product, (2) conventional sampling and analysis data are usually not available at the time a shipment is scheduled, and (3) the plant operator does not have the use of such data when the coal is being processed so that operating conditions may be adjusted for correcting variations in quality. Thus, the development and use of continuous-control monitoring instruments is of prime importance. The Federal Bureau of Mines arranged to investigate an instrument using x-rays for rapid continuous ash determinations. Developed by the Dutch State Mines and first described in 1958,' this instrument, which has found widespread acceptance in Europe, is designed to provide ash analysis of any desired coal feed or product stream with only a five-minute time lag between sample collection and analytical results. With limit controls, this unit could be used to feed back signals to preset the separating gravity of coal washers, control the ratio of various coals needed to produce an acceptable blend, and permit the sorting of a washed product into two qualities, one which is below and the other which is above a prescribed ash content. This unit can also be used discontinuously for rapid determination of coal samples taken in the usual manner. THEORY Di jkstra and Sieswerda of the Dutch State Mines studied the effect of chemical composition and ash content on the absorption coefficient of coal with the transmitted radiation method.' They found that with an X-ray wavelength of 1.79 A and values calculated for the absorption coefficients of ash and combustibles, the absorption coefficient of coal gave a linear relationship when plotted against the ash content. Thus, a method of measuring the absorption coefficient of coal could also be used to measure the ash content. However, practical attempts to measure the ash content of coal by comparing the intensities of the transmitted X-rays failed. The absorption coefficient of coal can also be obtained by irradiating a layer of coal with x-rays and measuring the intensity of the diffused reflection (backscatter method). The relationship between the diffused reflection and the ash content is actually hyperbolic but approximates a straight line over a narrow range. A measuring circuit that balanced the difference in intensity of the reflected radiation from a standard surface against that from a coal sample was used. By plotting this difference of reflected radiation against the ash content, a curve which approximated a straight line over a range of 8 percentage points of ash was obtained. DESCRIPTION OF EQUIPMENT The apparatus performs two distinct functions: (1) the preparation of the sample to a suitable size consist and moisture content for delivery to the x-ray element, and (2) the measurement of the ash content by the x-ray element. In a continuous operation the coal sample is delivered to a conditioner where it is dried to a maximum of 1% surface moisture and pulverized in a high speed mill to -48-mesh. This material is fed, at a rate of 250-300 gpm onto a rotating disk, shown in Fig. 1, where it is mixed with material already present. The mixture is rotated on the disk and

Jan 1, 1969

By C. van Dijk

In Sept., 1960, a steam-drive project was started in the solution-gas drive area of the Schoonebeek field. A part(ern of three five-spots and one four-spot was selected covering an area of 65 acres. The pay in the project area has good lateral continuity and dips slightly to the northeut; it is about SO ft thick and permeability increases from 1,000 and at the bottom to approximately 10,000 md at the top. The oil originally in place was 12.6 X 10' bbl. The oil has an in situ viscosity of about 180 cp. At the start of the steam drive the cumulative primary production due to. solution-ga.7 drive amounted id 4 Percent of the oil originally in place. Reservoir pressure had dropped about 120 psi and no significant primary re-.serves remained. Some 11.3 million bbl of steam (all steam quantities are expressed in barrels of water vaporized) have been injected, resulting in production of an additional 4.1 X I0 9bl of oil, or 33 percent of the oil originally in place. This corresponds to a cumulative oil-stearn rario of 0.37 bbllbbl. It appears that the steam preferentially moves r updip while liquids are produced mainly from downdip wells observations indicate that tile steam flows through only the upper part of the formation. The lateral steam distribution in the pattern is satisfacrory since several prodriction wells hardly reacted and, hence, cori tributcd little to the oil production. Production performance and results from material balance calcutlations agree satisfactorily with the results of large-,scale laboratory experiments. On the basis of these experirmental results the .steam drive, together with a cold water follow-up. is expected to bring ultimate recovery to a value of crt leas: 50 percent of the oil originally in place. No serious production problems have been encountered. However, due to mechanical fuilure, two old prodriction wells and one injection well had to be replaced. An extension of the. steam drive in this area is under connstruction. Introduction The Schoonebeek oil field, discovered in 1943 and developed after World War 11, is situated in the eastern part of the Netherlands. The main oil reservoir in this field is the Valanginian sand. A completely sealing fault divides this reservoir into two areas (Fig. 1): the southwestern part of the sand body where primary production is ob- tained by means of a solution-gas drive, and the remain. der where edge-water drive is the production mechanism. In the greater part of the field the reservoir consists of a single, unconsolidated sand body. The net thickness ranges from 30 to 100 ft and the top is between 2,400 and 2,800 ft below sea level. Formation permeability varies from approximately 10,000 md at the top to values of the order of 1,000 md at the bottom, and porosity is about 30 percent. The reservoir contains a paraffinic oil of 25" API gravity with an in situ viscosity of 160 to 180 cp. Initial oil saturation was high (85 to 90 percent). The relatively large quantity of oil in place (more than 10' bbl), and the low ultimate primary recoveries expected from this field — approximately 15 percent stock-tank oil initially in place (STOIIP) for the water-drive area and 5 percent STOIIP for the solution-gas drive area — clearly indicate ample scope for secondary recovery. Because ies-ervoir and crude characteristics made this field suitable for thermal secondary recovery, a hot-water drive project was started in the water-drive area about 10 years ago. A few years later a steam drive and an in situ combustion project were started in the solution-gas drive area. This paper deals with the performance of the steam-drive project, which was started in Sept., 1960, and which is still in operation. Design of Steam-Drive Project, An experimental investigation of the steam-drive process carried out by schenk in 19561 indicated that under schoonebeek conditions steam injection could be an attractive secondary recovery method. the findings and encouraging results of a pilot test in the Mene Grande field in venezuela,i led to the design of a steam-drive project in the schoonebeek field, Pruject Site and Pattern In 1958 the reservoir pressure in the solution-gas drive area had decreased to about 120 psi, and oil production rates of wells in this area had dropped to 7 to 10 B/D. The cumulative primary production was about 4 percent STOIIP, leaving an oil saturation of approximately 85 percent. In view of the large amount of oil left behind in the reservoir, the solution-gas drive area was selected for the planned steam-drive project. The area in the vicinity of Well S1 3 (Fig. 2) was considered to be suitable since it is at least partly isolated from the rest of the field by faults and the sand is relatively thick (about 80 ft).

Jan 1, 1969

By F. D. George, M. J. Salkind

Al3Ni whisker-reinforced aluminum was found to exhibit good Charpy impact toughness and little notch sensitivity even though its room-temperature tensile elongation parallel to the whiskers is only 2 pct. This impact behavior was maintained d liquid nitrogen temperature (-196"C). It is postulated that this behavior is due primarily to the presence of the continuous aluminum matrix which provides sufficient 10calized ductility in the vicinity of the crack tip to absorb considerable energy from the advancing crack. The impact behavior of Al-Alni was found to be quite anisotropic. Of six orientations studied, the transverse orientation having the notch normal to the whisker axis was found to exhibit the lowest impact energy, whereas the transverse orientation having the notch parallel to the whisker axis was found to exhibit the highest impact energy. A significant differnce was noted between the impact behavior of material containing needlelike whiskers and that containing bladelike whiskers. Only two of the six orientations studied exhibited complete fracture for the material containing needlelike whiskers. On the other had, most of the specimens containing bladelike whiskers exhibited complete fracture. It was postulated that the bladelike whiskers block transverse flow, thus reducing the amount of plastic deformation ahead of the crack tip. One of the more significant advantages of composite materials is the prospect of combining high strength with toughness. In general, toughness is associated with materials which exhibit considerable ductility and can deform plastically in the presence of a stress concentration. Very strong materials which resist plastic deformation generally exhibit low toughness. At first glance, then, it would appear as though strength and toughness are mutually incompatible so that useful engineering materials would have to be a compromise between the two. One approach to the problem of combining the high intrinsic strength of ceramics with the toughness of metals was to mix them together to form a cermet. Unfortunately, the toughness of cermets was found to be rather disappointing. Whisker reinforcement of metals, however, appears to be a more promising approach. It has been demonstrated that whisker-reinforced metals produced by unidirectional solidification exhibit enhanced strength due to the presence of high strength nonmetallic whiskers. The total strain capacity of these composites in the direction of fiber alignment is limited to that of the fibers, the matrix being unable to carry the load once the fibers have failed. A characteristic, then, of whisker composites is low ductility in the direction of whisker alignment, on the order of a few percent elongation. This low elongation, which is usually associated with brittle behavior, should not be taken as an indication of low toughness. Such a material can exhibit significant ductility in directions other than parallel to the fibers7 and can therefore possess significant intrinsic toughness. Toughness in a fiber-reinforced metal is derived from several mechanisms. The first is due to the toughness of the matrix itself. A continuous ductile metal matrix can act as an effective crack arrest medium by undergoing localized plastic deformation. Cracks initiated from the surface of the composite or from a brittle fiber failure must travel through the matrix before reaching another brittle phase particle. A second crack arrest mechanism peculiar to fiber composites is due to the fact that, as a crack travels through the matrix and approaches a fiber, the plastic deformation ahead of the crack tip will result in loading of the fiber. This causes the matrix shear strength in the plastic zone to be apparently higher, thus extracting more energy from the crack and diverting the crack at an angle to the original direction of propagation. A third crack arrest mechanism occurs in fiber composites which exhibit a weak bond between fiber and matrix. The idea was proposed by Cook and Gordons that if a crack propagating transversely in a fiber composite were made to turn and run along the fibers by decohesion of the fiber-matrix bond, then toughness would be imparted by the blunting of the crack tip and the creation of new surfaces. The last mechanism, interfacial decohesion, is commonly noted in naturally occurring fiber composites such as wood, bone, and bamboo, and has been observed in man-made composites such as glass fiber-reinforced resins,g silica fiber-reinforced aluminum," laminated steel," and tungsten and silica fiber-reinforced electroplated copper.'' The first mechanism, crack arrest by plastic deformation in the matrix, has been noted in tungsten wire reinforced cast copper." The purpose of this investigation was to quantitatively assess the toughness of a whisker-reinforced metal as a function of orientation. Previous investigation considered only cracks propagating nominally perpendicular to the reinforcement. In this investigation, crack propagation in three mutually perpendicular directions as well as three intermediate orientations was investigated. The system chosen for study was the unidirectionally solidified A1-A13Ni eu-tectic alloy which has a microstructure consisting of 10 pct by volume of A13Ni whiskers in a matrix of aluminum This material exhibits two different kinds of whisker morphology, depending upon the rate at which it is solidified.' At low rates of solidification (less than 2 cm per hr) the whiskers are bladelike, whereas at higher rates of solidification they are

Jan 1, 1969

By Lyle A. Hale

The subject area known as upper Dry Valley is located 15 miles due east of Soda Springs in Sections 14 and 23, Township 9 South, Range 44 East, Caribou County, Idaho. The railroad extending from Soda Springs to its terminus at El Paso's Maybe Canyon mine is 8z miles to the north in lower Dry Valley. Initial data derived from trench work in 1962 revealed a variety of econom¬ically significant alterations of the phosphatic beds related to the rather unique geomorphic development in the northern part of phosphate lease 1-012989. It was apparent that such conditions, while valid for near-surface beds in a strike direction, would be misleading if projected to the proposed depth limits of strip mining. Consequently, a subsurface mapping program was initiated in 1963 to determine: (1) the depth and horizontal extent of weathering and related phe¬nomena, (2) the depth, thickness, and quality of ore beds and intervening strata, and (3) structural geology as a guide for mining procedures. Successful use of a scintillometer in 1956 to detect the subcrop position of phosphate beds in the Smokey Canyon area of southeastern Idaho led to the conclusion that gamma radiation surveys of drill holes could be a useful aid in subsurface mapping. The objectives of this paper are: (1) briefly to describe geologic features characteristic of the phosphate lease area and (2) to demonstrate the practical application and theory behind gamma radiation logging as an effective tool in the economic evaluation of a phosphate lease.

Jan 1, 1969

By Claude H. P. Lupis, John F. Elliott

The classic Siez~erts' technique has been employed to determine the solubility of oxygen in liquid pure silver and the effect on the oxygen solubility of solute metal additions to liquid silver. The results indicate that oxygen deviates slightly from Sieverts' law in pure silver as = 3.9. Gold, platinum, md palladium decrease the solubility of oxygen in silver. First-order free energy, enthalpy, md entropy interaction coefficients are determined from the data. An important aspect in the establishment of the formalisms to be applied to represent the thermody-namic behavior of components of solutions is the accuracy of the experimentally determined thermody-namic properties. Wagner developed the first-order free energy interaction coefficient.' Recent papers2'3 extend the treatment formally to other thermodynamic properties and define the second- and higher-order interaction coefficients. A current communication4 considers in some depth the requirements and limitations imposed because of experimental error on the use of several formalisms now under active consideration in the field. This communication reports the results of an experimental study of the behavior of oxygen in liquid silver alloys that was carried out concurrently with the development of Refs. 2 and 3 with the hope of providing sufficiently precise information so that enthalpy and entropy interaction coefficients could be determined. THE EXPERIMENTS The Sieverts technique was employed using an improved design of the reaction bulb over that developed originally by Humbert5 and subsequently improved by pehlke6 and Weinstein.7 The Vycor reaction bulb as shown in Fig. 1 was air-cooled and contained a port for the thermocouple angling off to one side and a vertical port for connections to the gas supply and

Jan 1, 1969

By R. H. Tien

The accuracy of the method of steady-state approximation applied to the problems of heat transfer involving phase change (London and Seban's solution) is improved by defining a "modified heat of fusion" which accounts for the effect of specific heat. An analytical expression for this modified heat of fusion is derived in terms of the actual heat of fusion, specific heat, and surface temperature. Numerical solution for the freezing of iron indicates that the ratio of the modified heat of fusion to the actual heat of fusion increases from 1.04 to 1.4 as the surface temperature decreases from 2700° to 1600°F. The heat transfer process accompanying solidification is complicated owing to the moving solid-liquid interface where the latent heat of fusion is released. Exact analytical solution is available only for a few special cases of freezing problems such as Stefan's1 problem. In a commonly used steady-state approximation method, London and seban's2 solution, the effect of specific heat is neglected. This approximation, however, may introduce some degree of error in mathematical analysis when the temperature of the solid surface is much lower than the freezing temperature, as in the case of freezing metals. In a recent work by Robertson and Schenck,3 the problem of freezing a semi-infinite region with finite surface conductance was programed in a digital computer through the finite difference method. A family of curves for the correction of the London-Seban solution was given in a dimensionless plot for different ratios of heat of fusion and specific heat effect; it was shown that the London-Seban solution when applied to the freezing of a mild steel slab under some particular conditions gave results in error by about 10 pct in the solidification rate. Although the Robertson-Schenck computer result has improved the London-Seban solution to a great extent, lack of generality and the tedious computing procedure have restricted its application. In this paper a "modified heat of fusion" which accounts for the effect of specific heat is defined, and is used instead of the actual heat of fusion in the London-Seban solution. An analytical expression of this modified heat of fusion in terms of the specific heat, surface temperature, and actual heat of fusion is derived by comparing the solutions of Stefan and London-Seban for the case of freezing of a semi-infinite region with constant surface temperature. It can also be extended to the case with finite surface conductance, and the results show good agreement with the Robertson-Schenck computer solution. The expression of the modified heat of fusion, the accuracy of the London-Seban solution, and the temperature distribution within the solid are presented graphically in dimensionless form. Numerical solution for the freezing of iron indicates that the ratio of the modified heat of fusion to the actual heat of fusion increases from 1.04 to 1.40 as the surface temperature decreases from 2700° to 1600°F.

Jan 1, 1969

By Thomas R. Bur

The order of identification and in same cases the magnitude of the elastic constants of an anisotropic material depends on the orientation of the cartesian coordinate axes with respect to a set of reference coordinate axes within the material; thus confusion will result unless standard orientations are used. In this paper the relationship between the cause (the internal fabric) and the effect (the elastic properties in this case) is discussed for single crystals and for polycrystalline and amorphous materials. While reference axes based on the cause are used in the IRE (Institute of Radio Engineers) standard for piezoelectric crystals) it is shown that a reference coordinate system that would be suitable and practical for all anisotropic polycrystalline and amorphous materials must be based directly on a three-dimensional expression of the effect. The conventions offered are similar to the IRE standards for piezoelectric crystals) but use the elastic coordinates of the wave surface which can be quite readily established experimentally as the reference coordinates.

Jan 1, 1969

By Wolfgang Pitsch

INVESTIGATIONS on the above topic have recently been published by Shapiro and Kraussl and Jana and wayman in this journal and by Kessler and Pitsch.- Parts of the results in these papers are in good agreement with each other but there are also some results which are substantially different. The main points of these differences shall be briefly discussed in this communication. Shapiro and Krauss' measured single-surface traces of the habit planes of reversed austenite plates formed within the martensite crystals and deduced from these measurements two distinct habit planes A = (0.174; 0.309; 0.935) and B = (0.375; 0.545; 0.749) within 3 deg. Kessler and pitsch4 found instead by two-surface analysis7 one habit plane n = {0.23; 0.62: 0.75) with a real scatter of 6 deg. The latter observation of a single habit plane apart from a certain scatter is in agreement with most of the investigations of martensite transformations. The differences between these two results are so great that they cannot be explained by experimental error. The purpose of this communication is to show that the A- and B-poles of Shapiro and Krauss are due to an erroneous interpretation of a single-surface trace analysis. The difficulties in the interpretation of such single-surface trace analyses are due to the high symmetry of cubic lattices, from which it follows that there are in general twenty-four equivalent possibilities of plotting a single-surface trace in a pole figure. All these possibilities must be taken into account, when putting different traces from different plates together in order to construct the habit plane. Alternatively the poles of all the traces may be plotted in a unit triangle. This is done in Fig. 1 with twenty-nine traces of different reversed austenite plates, all of this were measured by Shapiro and Krauss in the same plane of a single martensite ther traces taken from Fig. 13 in the Shapiro and Krauss paper' which were determined by electron diffraction. The traces in Figs. 1 and 2 have to be compared with the habits A, B, and n which are under discussion. Therefore the great circles of the poles A, B, and n are plotted in Figs. 3, 4, and 5 together with a 3-deg scatter region for poles A, B and a 6-deg scatter region for pole n. Comparing Figs. 1 and 2 with Figs. 3, 4, and 5 one finds the statements which

Jan 1, 1969

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

By Prakash C. Kapur

A principal first order and a minor summation term contribute to the solution of the discretized batch grinding equation when formulated in cumulative retained mode. Depending on the interrelationships between the selection and breakage parameters, the minor term may be advantageously modified in a number of ways. The reduced grinding equations thus obtained are solved by iterations to give relatively simple solutions which are tested against experimental data. The implications and advantages of the reduced grinding equations are briefly discussed.

Jan 1, 1969

By P. C. J. Gallagher

A number of recmt determinations for the ratio of extrinsic to intrinsic stacking fault energy in fcc solid solutions are examined. Some of these arise from incomplete analyses which can yield only approxi?nate values for the ratio. Reliable results, on the other hand, obtained using extrinsic-intrinsic fault pairs, show that the extrinsic and intrinsic fault energies are essentially equal in several materials. There is some reason to believe that this finding is of general applicability to fcc elements and alloys. A wide range of values has been obtained for the relative magnitudes of the extrinsic and intrinsic stacking fault energies (yext and yint, respectively) in recently published studies in a variety of materials. In contrast, Hirth and Lothe' using a central force model have shown that out to tenth nearest-neighbor interactions the perturbation in energy caused by both types of fault is the same. Although the model used is not completely valid in metals, there is nevertheless some indication that marked variations of yext/nnt should not be observed from one material to another. In early work in Cu-A1, Cu-Ge, Ni-Co, and stainless steel all the deformation faults observed in the electron microscope were found to be intrinsic in nature, which led to an attitude that the extrinsic fault energy must be considerably greater than the intrinsic. Extrinsic faulting arising from deformation has, however, more recently been directly observed in Au-4.8 at. pct n;~ Ag-6 at. pct Sn and Ag-8 at. pct sn; Ag-7.5 at. pct In and Ag-11.8 at. pct 1n;"' pure silwer and Ag-0.5 at. pct ~n;' and Cu-22 at. pct Zn, Cu-30 at. pct Zn, and Cu-7.5 at. pct ~1.l' Multilayer loops containing extrinsic faulting have also been observed in quenched aluminum." While peak asymmetries in X-ray faulting probability studies were generally attributed to the presence of twins,Lelel2 has recently reinterpreted earlier X-ray data in Ag-Sb alloysU in terms of the presence of extrinsic faulting. The determinations of yeXt/yint made from the above studies are shown in Table I, with a brief description of the techniques employed. A number of the methods utilized are deficient in one or more respects, and the reliability of the values listed will be discussed. ~ele'~ recognizes that his approximate determinations of yext/yint assumes equal numbers of extrin-sically and intrinsically faulted dislocations. It is well-known, however, that such an assumption is not at all justified since extrinsic faulting has but rarely been observed in samples studied in the electron microscope. The only conclusion that should be drawn from the X-ray results at present is that the total intrinsic scattering cross section (i.e., the product of the width of the intrinsically faulted dislocations with their density) is approximately ten times greater than for extrinsic faulting in these particular samples. An important point is that the relative magnitudes of the energies cannot be inferred from results of this type, unless the intrinsic and extrinsic faults form with equal ease. One must recognize that, although a formation barrier may restrict the amount of extrinsic faulting which occurs, this in no way implies that the extrinsic and intrinsic energies should be different. It is unlikely that a worthwhile estimate of the relative densities of extrinsically and intrinsically faulted dislocations can be made at the high deformations present in X-ray samples. ~oretto,'~ from a statistical argument applied to the nonobservation of extrinsically faulted tetrahedra out of a large sample, concluded that yeXt/yint could not be less than -4.5. However, the present author feels that a high-energy formation barrier as just supposed also explains this finding satisfactorily and that no conclusion can possibly be drawn concerning the actual extrinsic stacking fault energy. The same argument also serves to explain the fact that extrinsic faulting has been relatively little observed in the electron microscope. Extrinsic-intrinsic node pairs and isolated extrinsic nodes were first reported by Loretto~ and subsequently by Ives and Ruff,' Gallaher,' and Gallagher and Wash-burn.' Ives and Ruff' found a wide spread in the ratio of extrinsically to intrinsically faulted area in the node pairs they observed, and drew the very tentative conclusion that yeXt/yint 2 2. They recognized that a straightforward comparison of the size of the faulted areas could provide no more than a qualitative result without a theoretical analysis of the dislocation geometry associated with extrinsic faulting. A theoretical

Jan 1, 1969

By Michael Epstein, Daniel E. Rosner

Fume nucleation sufficiently close to vaporizing suvfaces can augment net vaporization rates into cooler environments. Environmental conditions favoring large vaporization rate enhancements are briefly discussed and a previous theoretical treatment of this nucleation phenomenon is generalized to account for the self-regulating effect of condensalion-heat release within the boundary layer. Despite kinetic limitations on homogeneous nucleation, and latent heat release, non-diffusive condensate removal processes appear to make possible large enhancements in steady-state vaporization rates, provided surface temperatures are well below the boiling point. When condensed phases vaporize (or dissolve) into cooler media, the diffusion-limited mass loss rate can be strongly influenced by the process of nucleation/con-densation (or precipitation) within the thermal boundary layer. This condensation process (which typically leads to mists or fumes in the case of evaporation into cooler gases) has the effect of steepening the vapor pressure profiles near the evaporating surface, since the condensation zone acts as a vapor sink. However. the resulting enhancement in the diffusion-limited evaporation rate can be estimated (as first done by Turkdogan1 for the case of molten iron/nickel alloys evaporating into helium) only if one has independent knowledge of the critical supersaturation, sCrit(T), required to homogeneously nucleate the vapor.* In a recent reformulation and generalization of the theoretical model of Ref. 1 it has been shown that, when log sCrit is approximately linear in reciprocal temperature, rather simple expressions can be derived4 for the ratio of the actual rate of vaporization j" to either the minimum (no condensation) rate j"min, or the maximum (equilibrium condensation) rate j"max In the present communication we wish to briefly report on further developments and implications of the formulation of Ref. 4, with emphasis on i) environmental conditions favoring large enhancements in vaporization rate, and ii) the self-regulatory influence of condensation heat release (neglected in Refs. 1 to 4) on predicted vaporization rates. Additionally, we take this opportunity to correct several misprints appear- ing in Ref. 4, and comment on Elenbaas's recent criticism5 of Ref. 1. MAXIMUM POSSIBLE VAPORIZATION RATE IN PRESENCE OF CONDENSATION A nonequilibrium theory is of interest because of the very large difference between the minimum (no condensation) and maximum (equilibrium condensation) vaporization rate. The magnitude of this maximum possible enhancement can be shown quite clearly by combining a result of Refs. 3 and 4 with the fact that for most liquids there is a simple relationship between the molar heat of evaporation, A, and its boiling point, i.e., A/(RTBp) = C, where the constant C, often called the Trouton ratio, takes on values not very different from 11.* More generally, for any substance (including The Trouton ratio (which for water is 13, for methane, 10, and so forth) will be recognized as the ratio of the molar entropy change upon vaporization (at TBP or Ttransf) to the unlversal gas constant R. Its near constancy reflects the fact that the change in atomic order upon vaporization depends only weakly on the kinds of molecules involved. those that sublime under ordinary conditions) we can define a characteristic transformation temperature. Ttransf, by a relation of the form Ttransf =A/(CR), and then examine the maximum possible evaporation rates as a function of how far removed from Ttransf are the surface temperature, Tw, and ambient temperature, T. Subject to the assumptions: 1) equilibrium vapor pressure, pv,eq, everywhere small compared to prevailing total pressure, p, and 2) negligible effect of condensation heat on temperature profile, the maximum enhancement ratio was found (Eq. [17], Ref. 4) to be: where, for most vapors, Nu/NuD (the ratio of heat transfer coefficient to mass transfer coefficient for the same configuration) is a number near unity.* Ex- *An alternative derivation of the Nu = NuD special case of this equation. revealing its validity for arbitrary velocity/temperature profiles in a laminar boundary layer, is given in Ref. 3. amining this result for a "Trouton substance", one obtains the results shown in Fig. 1, constructed for C = 11. Since we are concerned with vaporization enhancements (j'max/J"min > 1) at surface temperatures below Ttransf, this area of interest is shown unshaded. One notes that at a fixed ambient temperature (hence, T/TtranSf) there is a unique surface temperature, 2T , at which j"max/j"min attains its peak value; moreover, the peak enhancement ratio, see dashed locus. Fig. 1, is: (NuA/NuD)(C/4)(Ttransf/T,). Hence, if Nu = NuD, when the ambient temperature is less than 1/4 of TtranSf the peak enhancement exceeds the Trouton

Jan 1, 1969

By J. Szekely, Robert G. Lee

Calculations are presented for the prediction of the combined radiative-convective heat loss from molten steel held in a ladle, covered by initially molten slag. A mathematical formulation is given and numerical solutions are presented of the resultant partial differential equation. It is shown that a slag layer of about 2 to 3 in. thick would prevent any significant heat loss from the top metal surface for Periods of up to 1 hr. For thinner slag layers (or in the absence of the protective slag) appreciable heat losses would occur; plots given in the paper allow the quantitative evaluation of the fall in the metal temperature due to this heat loss. The ironmaking-steel processing operation involves several intermediate steps where the molten metal is held or transfered in ladles. The quantitative assessment of the heat losses occurring under these conditions is of considerable importance in process design considerations since the temperature of the metal may have to meet rigid specifications in any given part of the processing sequence. While the metal is held in a ladle, heat is lost by two mechanisms: i) by conduction into the ladle walls; ii) by radiation and convection from the top surface. Calculations relating to the conductive heat loss, are readily made and information may be found in the literature both on data pertaining to metallurgical situations and on the techniques that are available for performing additional computations.'-3 The evaluation of the combined convective-radiative heat loss is less straightforward, especially when there exists a protective slag layer covering the metal. In this latter case, as the top slag surface loses heat partial solidification may occur and the latent heat thus given up by the slag may represent an effective barrier to the heat loss from the metal. A semiquantitative assessment of the role played by the slag in preventing heat loss from the metal has been made in a previous paper,4 where it was shown that a slag layer 6 in. thick would act as a near-perfect insulator for periods of up to 2 hr. However, this first paper reported on an essentially preliminary investigation that considered only one slag layer thickness; furthermore, the boundary conditions used for the calculations were somewhat restrictive since no allowance was made for changes in the metal temperature. The purpose of this second paper is to extend the scope of the preliminary investigation previously reported by: i) considering several slag layer thicknesses; ii) allowing for variations in the metal temperature; and finally iii) by performing calculations on the net loss from the metal rather than from the slag surface. FORMULATION Consider a slag phase extending from y = 0 to y = L1, covering a metal phase that occupies the region extending from y = Ll to y = L, as illustrated in Fig. 1. Denote the slag and metal temperatures by TS and Tm and assume that initially both slag and metal are molten, having a uniform temperature Ti. At time = zero the surface represented by the y = 0 plane (top slag surface) is brought into contact with cold air, the temperature of which is given as T Thus for time > zero, heat will be transfered from the slag to the air by natural convection and thermal radiation; as a result of this heat loss the slag temperature will fall and after some time a solid phase is formed and a solidification boundary (more realistically described as a zone) will move progressively from y = 0 toward y = L1. Once the region of temperature gradients, moving ahead of the solidification zone, reach the slag-metal interface (y = L1) there will be a net transfer of heat from the metal through the slag to the cold air, across the y = 0 plane. In the formulation of moving boundary problems, involving phase changes that require computer solution, it is convenient to represent both phases by a single equation, making allowance for the latent heat of solidification by assigning an appropriate temperature dependence to the specific heat content. Thus the energy equation for the whole of the slag may be written as follows:

Jan 1, 1969

By R. E. Robbins, H. R. Brager

THIS note describes an unusual result obtained in an electron microscope investigation of cavities produced in commercial type 304 stainless steel irradiated in a thermal reactor (ETR) at 290°C to a high neutron flu-ence, 6 x loz1 n per sq cm. The analysis of the steel used is given in Table I. The unusual result is that the calculated quantity of helium gas produced by transmutation during the irradiation, 12 ppm, is less than one-tenth the amount of gas necessary to balance the surface tension of the observed cavities produced in the steel during ETR irradiation. Therefore, the cavities would be expected to behave like voids; however, they behave like "gas filled" bubbles. The maximum quantity of helium produced in the steel by B" transmutation was 8 ppm. In addition, the amount of helium formed by (n, (1) fast neutron reactions with the major alloy constituents and nitrogen was calculated to be 4 ppm based on the tabulated differential or effective fission-averaged cross sections of elements in type 304 stainless steel irradiated in typical thermal reactors.', In previous investigations concerning commercial austenitic stainless steel irradiated in a thermal reactor, the amount of helium gas calculated to be produced by transmutation has always been significantly greater than the amount calculated on the basis that the bubbles were gas filled, PPs= 2y/R. The balance of the gas was assumed to be in bubbles smaller than could be detected on the electron micrographs. Accordingly, the bubbles were attributed to helium produced from transmutation of impurity boron by thermal neutrons. These bubbles were not uniformly dispersed in the matrix but were located principally at grain boundaries, or were radially positioned around a few precipitates located in the matrix and at the grain bundaries., 4 Voids have also been observed in austenitic stainless steel irradiated at high temperature to high neutron fluences in the EBR-I1 and Dounreay Fast Reactors. The voids were uniformly distributed throughout the matrix. The amounts of helium gas produced by transmutation during these irradiations were less than one-tenth the amounts needed to balance the surface tension of the voids formed by the fast reactor irradiation. The fast reactor results are quite analogous to those reported here for the ETR irradiated steel. Electron microscope examination of the fast reactor irradiated material after a 1 hr postirradiation annealing at 900°C disclosed that essentially all the voids had been eliminated. The authors stated that the voids had developed due to the high concentration of vacancies produced during irradiatin., 6, ' The microstructure of the ETR irradiated material as-tested at 75O°C, Fig. 1, contained about 2 X lot5 cavities per cm3 with an average diameter of 110A. With the Van der Waals b correction and y = 1500 ergs per cm2, 300 ppm He would balance the surface tension of the observed cavities. Stereoscopic examination of the electron micrographs showed that the cavities were neither preferentially located near the grain boundaries nor highly concentrated at specific regions or precipitates. The cavities were nearly uniformly distributed throughout the matrix, on dislocations and at grain boundaries. These observations imply that the cavities were not the sole results of B'O

Jan 1, 1969

By C. T. Liu, J. Gurland

The deformation behavior in tension of spheroidized carbon steels was studied at room temperature as a function of carbon content, 0.065 to 1.46 wt Pct, and carbide particle size, 0.88 to 2.77 p. It was found that the Hall-Petch strength-grain size relation is directly applicable to the yield and flow stresses of the two lower-carbon steels , 0.065 and 0.30 pct C. The strength data for the medium- and high-carbon steels, 0.55 to 1.46 pct C, also satisfied the Hall-Petch relation, provided that these data are based upon the particle spacing. Beyond 4 pct strain, the flow stress data of all the steels studied could be represented by the same Hall-Petch relation with dinerent spacings for grain boundary and particle strengthening. The behavior of the higher-carbon steels was consistent with the postulated formation of a dislocation cell network during processing and initial deformation (up to 4 pct strain). The cell size was assumed to be equal to the planar particle spacing. The true stress at the ultimate tensile strength was also found to be a function of the particle spacing. At a given temperature and strain rate, the yield and flow stresses of carbon steels depend on the type and dimensions of the microstructure. Starting with the work of Gensamer et al. in 1942,' experimental studies on pearlitic and spheroidized carbon steels revealed that the strength of steels is a function of two main parameters: the ferrite grain size2'3 and the carbide particle spacing;1'4'5 on this basis, two different strengthening mechanisms have been developed to apply to steels of low and high carbon contents, respectively. In polycrystalline iron and mild steels the grain boundaries are regarded as the major structural barriers to slip. The relation between strength and grain size is generally represented by the Hall-Petch equation which is based on a linear proportionality between strength and the inverse square root of the average grain size.2'3y677 However, Gensamer et al.' and Roberts et related the yield strength of medium -and high-carbon steels to the carbide particle spacing alone, and they found a linear relation between the logarithm of the mean free path in the ferrite and the yield strength in both spheroidized and pearlitic steels. By means of the electron microscope, Turkalo and LOW' extended the study to finer structures; they concluded that the logarithmic relation is not valid for the entire range of microstructures unless grain boundaries are also included in the measurement of the mean free path. For the specific case of spheroidized steels, Ansell and aenel' found that the yield strength data,4'5 when plotted as a function of mean free path, fit the Hall-Petch equation; however, T'ysong found that the same data fit the 0rowanl0 relation if a planar inter-particle spacing is used. Recently Kossowsky and ~rown" studied the strength of prestrained spheroidized steels, 0.48 and 0.95 pct C, and concluded that the strength due to the carbide dispersions varies linearly with the reciprocal of the square root of the mean free path between carbide particles and dislocation networks. Such networks were first observed by Turkalo." The conclusion common to all these studies is that the available slip distance in the ferrite is the most important variable in determining strendh. Previous work on carbon steels is restricted to limited composition and strain ranges. The mechanism which governs the flow properties is not clearly understood, and, in particular, little is known about the composition dependence of the transition between grain boundary strengthening and particle hardening. The purpose of the present work is to investigate the strengthening mechanism in spheroidized steels over a wide range of carbon content, 0.065 to 1.46 wt pct, and plastic strain, yielding to necking. The spheroidized structure was chosen because of its relative simplicity and the relative ease of control and measurement of the structural parameters. The experimental work is limited to tensile testing at room temperature at constant extension rate. The effects of the carbide particles on the fracture behavior of spheroidized steels are discussed elsewhere.13 EXPERIMENTAL PROCEDURE Eight different grades of vacuum-cast carbon steels were supplied in the form of forged and rolled plate by the Applied Research Laboratory of the U.S. Steel Corp. The compositions furnished with these steels are given in Table I; the carbon content ranges from 0.065 to 1.46 wt pct, or from 1.0 to 22.3 vol pct of carbide. The steel plates were cut transversely into rods a little larger than the test specimens, 1 in. gage length, i in. diam. The rods were austenitized in air (enriched with CO by a consumable carbon-rich muffle) at 50° C above theA, orA., temperature for 2 hr and then quenched in oil with vigorous stirring. The as-quenched rods were tempered in two stages in order to obtain the desired distributions and sizes of carbide particles. The rods were first tempered at 460° C for 10 hr and then at 700" C for periods ranging from 4 hr to 3 days, in vacuum. After final machining, all specimens were vacuum-annealed again at 650°C for 1 hr in order to relieve residual stresses. The tension tests were carried out in two steps. The initial part of the load-strain curve, up to about 2 pct strain, was determined on a Riehle testing machine with an extensometer of small strain range, 4 pct strain, in order to obtain the yield and initial flow piopertiesi As soon as the first part of the test was finished, the specimen was placed in an Instron testing machine equipped with a strain gage extensometer with a maximum strain range of 50 pct. The load-strain curve to fracture was

Jan 1, 1969