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By Arthur H. Wilson

INTRODUCTION The stratified deposits of the coal measures are strongly laminated and exhibit a high degree of anisotropy. The stronger rocks in the sequence possess joints and shear planes, the coal itself has a closely spaced cleat pattern, and the softer rocks are capable of flowage. To calculate the general distribution of stress in such a medium by analytical means based on the theories of elasticity is difficult, and has not yet been satisfactorily achieved. Nevertheless, some estimate is required to aid the design of supporting pillars and permit the correct siting of main roadways. This is important when laying out districts for longwall extraction, particularly if the results of previous experience are not available in the area to be exploited. Although elastic stress analyses, including finite element analysis, may not be very appropriate, the basic equilibrium conditions will apply. These, combined with logical deductions based on observed fact, can be used to give appropriate solutions which experience has shown to be capable of giving acceptable results in the design of pillars associated with longwall workings. Constancy of cover load is one of the fundamental equilibrium conditions. When mining below ground, the cover is not removed, therefore the average vertical load after mining must equal the initial cover load. If mining produces a local decrease in load in any particular area, it must be balanced by an equivalent increase in load nearby. Bending moments in the strata above are capable of compensating for the turning moments which this redistribution of load may produce, and the existence of a "rear abutment", much discussed between 1950 and 1960, is not an essential equilibrium requirement. If the distribution of vertical stress is plotted three-dimensionally, then the load on any small element of area 6S will be o.6S, where o is the average stress. This also represents the volume of the "stress envelope" which lies above 6s. By making the individual areas very small and summing together, it is possible to show that the total load on any particular area can be found by calculating the volume of the stress distribution envelope which lies above it. A similar consideration applies to the stress distribution in a two-dimensional situation. If the stress distribution curve is drawn, then the area below any portion will represent the load per unit depth of section. For example, Figure 1 represents the possible stress distribution across a caved waste and associated ribside. If AW is the load deficiency [ ] These loads must balance, therefore area AW = AS, and if one can be deduced, the other will then be known. Attempts have been made to measure stress distributions in the ribside and in the waste. Stress meters in soft rocks such as the coal measures have not proved very effective. Those based on the measurement of strain have experienced difficulty in strata capable of flowage, high modulus stress meters suffer from cross sensitivity, and overcoming to obtain absolute stress is almost impossible. Load measuring instruments left in the waste have also proved largely ineffective, mainly as a result of the difficulties of protecting the leads in a caving environment. Certain logical deductions, however, can be made about the conditions in the waste. CONDITIONS IN THE WASTE Over the area of the waste the surface trough which develops is remarkably consistent, despite the geological variations which occur from coalfield to coalfield. In Britain, an accuracy of 210% is claimed for subsidence prediction based on width of extraction and depth of cover (National Coal Board, 1975). The subsidence in the USA is more variable (Adamek and Jeran, 1981), particularly with respect to the point of inflexion, but the same general pattern occurs. At the shallower depths the somewhat harder roof strata involved in the caving in the USA may suffer less compaction, giving reduced values of subsidence. Subsidence at intermediate horizons below the surface

Jan 1, 1982

By Sidney G. Parker, Jack E. Pinnell

Cubic ZnSe crystals have been grown with HCl, HBr, and I, as chemical transport reagents. The growth of large, well faceted crystals is in the order HCl < HBr < I, with some produced by I, transport being 1 cm on an edge. ZnSe:I crystals showed no strain in cross polarized light and were homogeneous as determined by electron microprobe. These ZnSe:I crystals had a mobility at 25°C of about 300 sq cm per v-sec and contained 103 dislocations per sq cm; further, these crystals were pure cubic and showed both photolumi-nescence and photo conductance. Doping was attempted during crystal growth. ZnS and Zn (S,Se) crystals were also grown by I, transport. ZnSe crystals have been grown by most of the common techniques.1"6 Of these, chemical vapor transport as developed by Kaldis2 showed promise of producing high perfection, cubic ZnSe. With chemical transport, crystals can be grown far below the transition temperature for conversion of cubic to hexagonal structure. A small temperature gradient between source and growth region tends to allow near equilibrium growth, which should lead to good crystalline perfection. Because it is necessary to form volatile compounds, halogens or their compounds are extensively used as transport agents. HCl, HBr, and I, were compared as transport agents for growth of ZnSe crystals. Doping during crystal growth was attempted. ZnS and ZnSxSe1-x crystals were also grown by chemical transport. Electrical and optical properties of the crystals were examined. EXPERIMENTAL Fig. 1 is a sketch of the growth apparatus, which was a modification of Kaldis&apos;. A quartz rod which butted against the seed crystal served as a heat sink to promote growth only on the seed. Initially, crystal growth was attempted with ZnSe prepared by wet chemical methods. Because such a material contained oxides and selenates, HC1 reacted with these oxygen compounds to form H2O and no ZnSe transport occurred. Further, this ZnSe contained about 10 ppm Cu plus other impurities. High purity ZnSe, containing small amounts or no oxygen compounds, was prepared by reaction of H2Se with zinc vapors at 600° to 800°C in an atmosphere of palladium diffused H2.7 The ZnSe thus produced was usually copper free and contained only 1 ppm by weight of magnesium as determined by emission spectrographic analysis. G.E.&apos;s electronic grade ZnS, which had about 10 ppm metallic impurities, was used without further treatment. ZnS-ZnSe charges were prepared by mixing the two compounds together, then sintering 24 hr at 1100°C in an H2S ambient. The gases, HBr and HC1, were commercial grade, of 99.9 pct purity, while the I2 was 99.999 pct pure. The single crystal seeds with (111) faces for growth were mechanically held in place by sealing the outer quartz tube to the growth tube. After the charge was introduced, the system was outgassed at l0-5 torr while heated to 500°C. The desired quantities of transport reagents were then sealed off in the system, which had been cooled to 25°C. The growth tubes were inserted into a furnace with the desired temperature and thermal gradient. The system was allowed to cool for 1 to 12 hr from growth temperatures of about 850" to 25°C. The tubes remained stationary during crystal growth. HCl CHEMICAL TRANSPORT GROWTH Preliminary runs with HC1 had a temperature gradient of 100° to 200°C and no seed or heat sink. Only small crystals were obtained in these experiments as

Jan 1, 1970

By R. M. Goldhoff, J. W. Spretnak

IN connection with establishing the mechanism by which boron enhances the hardenability of heat treatable steels, this research work has been undertaken. Spretnak and Speiser1,2 indicated the need for studying high temperature effects in boron steels and, chief among these, the possible nonhomogeneous distribution of boron in iron grains. The occurrence of this effect may be of significance in explaining the mechanism of enhancement of hardenability by boron as well as in explaining some of the observed characteristics of boron steel behavior. Primarily, then, this work was undertaken a) to establish whether or not boron is adsorbed in ? solid solutions, b) to determine the nature of any such adsorption effects, i.e., whether it is positive or negative as well as its temperature coefficient, and c) to establish the magnitude of any such effect. While past literature on this specific subject is rather sparse, a number of authors have postulated that the observed temporary loss of hardenability as well as the occurrence of the characteristic boron constituent in these steels is due to the nonuniform distribution of boron in austenite.3-0 Experimental Techniques Attempts to obtain direct evidence of grain boundary effects in boron steels have been unsuccessful, both by using the technique of Chalmers&apos; in which small concentrations of solute made radioactive by irradiation are detected by autoradiographic means, and by means of studying cleavage fractures with the electron microscope.8 The present study attempts the design of experiments to measure the effect of boron on properties which might be subject to variation because of grain boundary effects. A study of the theoretical aspects of grain growth indicates that such studies may be pertinent. Another valid type of experiment involves the measurement in polycrystalline materials of properties whose values depend on the bulk of the grain, being negligibly influenced by grain boundaries. One such property is the lattice parameter measured by X-ray diffraction. The value of the lattice parameter reflects the average conditions which obtain over a relatively large number of atoms in a fixed crystalline lattice, and is therefore mainly dependent on bulk grain material. Measurement of lattice parameter variation over the austenite range of temperature in iron with and without boron should give evidence of concentration variations in the bulk grain material if adsorption effects are significant. Finally, use is made of the Grange and Garvey3 metallographic test for boron in which a characteristic boron constituent can be developed in austenite grain boundaries. The very occurrence of this phenomenon suggests grain boundary enrichment of boron and a study of the occurrence of this constituent and its varation with austenitizing temperature should help to detect grain boundary effects. Materials One lb ingots of pure iron, an Fe-B alloy, an Fe-C alloy, and an Fe-C-B alloy were prepared. The melting technique included an initial melting of electrolytic iron under vacuum followed by remelting under hydrogen and, finally, by melting under argon with the addition of alloying elements. Each ingot was surface machined between meltings. A quantitative spectrographic analysis was obtained on the pure ingot and, in addition, oxygen, nitrogen, and carbon were determined by the vacuum fusion method. The results of these analyses are given in Table I. Semiquantitative spectrographic analyses were performed on the alloy ingots, while quantitative determinations of the alloy additions were obtained. These analyses are shown in Table 11. The cast ingots were subjected to the following sequence of fabrication treatments: forging to 5/8 in. bars, swaging to 0.300 in. rounds, drawing to 0.025 and 0.010 in. wire. Portions of each ingot were retained in the swaged condition for experimental use. For certain portions of the work typical commercial steels were used. These materials were supplied by the Republic Steel Corp., Canton, Ohio, and correspond to AISI 8640 and AISI 86B40 compositions.

Jan 1, 1958

By T. F. Mueller, P. A. Witherspoon

For the case of an infinite radial system operating at constant terminal rate, the reservoir engineer often uses the "point source" solution of the diffiusivity equation to study pressure interference effects. At early times and at short distances from the inner boundary these solutions are invalid. The amount of error is often not precisely defined because of mathematical difficulties. Work presented here shows that, if dimensionless time is defined appropriately, previous solutions of the pressure equation can be displayed .as a family of curves on one chart. These solutions include the point source solution (referred to in the field of hydrology as the Theis solution) and other solutions obtained with digital computer methods. With these curves, an exact evaluation of the pressure drop within a reservoir or an aquifer can be made by the engineer. Examples of field problem solutions are presented. In most reservoirs the error involved when the Theis solution is employed is often negligible; whereas, in the calculation of interference effects in an aquifer, a substantial error can occur through such an approach. INTRODUCTION Flow equations are used in petroleum engineering to study the behavior of individual wells and reservoirs. In the case of wells, the pressure response at the wellbore face is the major point of interest; whereas, in the case of reservoirs, the pressure response at the interface of the aquifer boundary is sought. To aid in such studies, the flow equations have been solved in terms of the behavior at these two inner boundaries. Only limited work has been published in regard to the pressure conditions away from these points, i.e., within the reservoir or aquifer. Theis and Mortada are among the few who have reported on this problem. The Theis approach employs the exponential integral and is valid for pressure conditions that occur some distance away from the flow disturbance. It is derived from the concept of a point source, as opposed to a flow across some finite area. The Mortada results, on the other hand, are valid at all points within the reservoir or aquifer. They are presented in terms of dimension less ratios of the radius where the pressure is desired to the radius where the flow rate is measured. Their main use, in the past, has been in aquifer studies. The published results are presented in the form of graphs that are limited to a maximum radius ratio of 64. These graphical results are cumbersome to interpolate at non-integral radius ratios, so that one may be forced to utilize a rather involved analytical expression presented by Mortada. BASIC EQUATIONS The solutions of Mortada and Theis are both based on the diffusivity equation as applied to the case of an infinite radial system subject to a constant terminal rate. The equation is obtained by combining the material balance equation with Darcy&apos;s flow equation. The assumptions implicit in the use of this equation are as follows: (1) a single fluid is present that occupies the entire pore volume; (2) the reservoir is horizontal, homogeneous, uniform in thickness, and of infinite radial extent; (3) compressibility and viscosity of the fluid remain constant at all pressures; and (4) fluid density obeys the equation Using the diffusivity equation in situations where the above conditions do not hold will result in errors. These errors (not discussed here) but only the errors which arise in the solution of the equation itself. The diffusivity equation for the homogeneous reservoir conditions cited above can be written in cylindrical coordinates, as To obtain a dimensionless equation, so a single solution can be used for applications of different porosity, permeability and fluid properties, the following transformations are usually made: After these transformations are made, Eq. 3 .can be written in dimensionless form, as MORTADA SOLUTION One solution of Eq. 6 has been given by Mortada.

Jan 1, 1966

By M. Prats

The effect of a sand-filled vertical fracture of limited radial extent and finite capacity (fracture capacity is the product of the permeability and width of the fracture) on the flow behavior of a cylindrical reservoir producing an incompressible fluid through a centrally located well has been investigated mathematically. The shape of the lines of equal pressure near the fracture is essentially independent of the size of the reservoir, provided that the field radius is of the order of the fracture length or larger. For reasonable values of production rates and of fluid, reservoir and fracture properties, the total pressure drop between the end of the fracture and the well is gelrerally negligible compared with the pressure drop in the reservoir. With regard to production response, the effect of vertical fractures can be represented by the production response of an equivalent or effective well radius. For a high-capacity fracture, the effective well radius is a quarter of the total fracture length, decreasing with the fracture capacity. When invasion effects are simulated by decreasing the width of the damaged zone with distance from the well, the effect of formation damage around a fracture on the production response is not so seriolls as indicated by the literature. This suggests that frac fluids with a conventional filter-loss response are better than high-spurt-loss frac fluids, provided the effective permeability of the damaged zone is the same. INTRODUCTION This paper considers the effect of the fracture capacity, as well as the formation damage which can result from fracture treatments, on the productive capacity of vertically fractured wells. Other publications, notably those of van Poollen,l,2 consider these same effects. In addition to providing more general results for vertical fractures than are available from the liter- ature, the present paper gives the equivalent well radius of fractures having different lengths and capacities and, also, includes pressure distributions in and around the fractures. The effect of a damaged zone around a fracture on the production response was not found to be so great as that reported by van Poollen. 2 This difference probably stems from the fact that we consider a damaged zone which is widest (but is still small) near the well and thins out toward the extremities of the fracture, whereas van Poollen considers a damaged zone having a uniform width for the entire fracture length. Simple, but adequate, equations which describe the effect of these variables on production response are presented (in Appendixes A and B). Thus, results can easily be extended to values of the variables not specifically considered here. IDEALIZATION AND DESCRIPTION OF THE FRACTURED SYSTEM It is assumed that a horizontal oil-producing layer of constant thickness and of uniform porosity and permeability is bounded above and below by impermeable strata. The liquid is incompressible. It is assumed that, after the well is fractured, the cylindrical outer "boundary" is at a uniform potential, provided that it is not too near the fracture. The fracture system is represented by a single, plane, vertical fracture of limited radial extent, bounded by the impermeable matrix above and below the producing layer (reservoir).3 Fig. 1 indicates the general three-dimensional geometry of the fractured reservoir described above. If gravity effects are neglected, the flaw behavior in the reservoir will be independent of the vertical position ill the oil sand. This means that the flow behavior in the fractured reservoir can be described by the two-dimensional flow behavior shown in the horizontal cross section of the reservoir, Fig. 2. PARAMETERS The effect of a fracture on the pressure distribution in the fracture itself and in an otherwise undamaged (no skin) reservoir indicates that the pressure distribution is a function of three parameters.

By K. Mukherjee

Instantaneous resistance change during martensitic transformation in Fe-30 at. pct Ni alloy has been studied using a low-noise electronic system. The smallest signals recorded in this investigation were of the order of 10 pv. These small signals did not show the initial increase reported by earlier investigators to support a double shear mechanism.&apos; A variety of pulse shapes and sizes was observed during "burst" transformations, and these signals were neither a linear function of the size of martensite plates nor of the volume fraction transformed. Even the smallest signals, presumably from single plates, showed complications resulting from elastic and/or plastic deformation, shock wave propagation, and so forth, which are inherent in the growth process of a martensite plate. The time of formation and interface velocity determined froni this experiment agree very well with the pioneering work of Bunshalz and Mehl.&apos; AN Fe-30 at. pct Ni (c0.005 pct C) alloy was used to study the time of formation of martensite plates. Martensitic transformations, unlike the nucleation and growth processes, are usually characterized by an extremely fast reaction rate. During the transformation, the crystal structure changes and this change is propagated through a finite volume of the parent crystal lattice within a very short time interval. The interface between the two phases probably consists of moving dislocations, and the time of formation of the plate depends on how fast this dislocation interface can move. Knapp and Dehlin~er or Cottrell and Bilby mechanisms, or similar dislocation models, can be used to calculate the time of formation of a martensite plate of a given size. In the past, conventional photographic technique475 as well as electrical resistivity techniques"~-" have been used to measure the time of formation of a martensite plate. The specific resistance of the martensitic phase in Fe-30 at. pct Ni alloy is lower than that of the austenite phase. Therefore if a current is passed through a small austenite sample in series with a large external resistance, then one would observe a voltage change across the sample as martensite is formed. Such dc measurements are shown in Fig. 1. The initial large voltage drop in Fig. 1, at the M, temperature, is due to a "burst" transformation where a large number of plates are formed in a cataclysmic manner within a very short interval of time. Even during the later stages of transformation as shown in Fig. 1, one can observe discontinuous voltage changes due to small bursts. In order to resolve the time scale of such discontinuous stages, the voltage signals are amplified and fed into a highspeed oscilloscope. In this investigation a low-noise amplifier was used for the first stage of amplification. The signal to noise ratio was further improved by the design of a pulse transformer. This transformer was capable of amplifying the signal by a factor of six. Voltage signals were studied over a wide time scale ranging from 2 sec to 0.1 psec. I) EXPERIMENTAL PROCEDURE A) Specimen Preparation. Specimens were cut from induction-melted Fe-30 at. pct Ni (<0.005C) alloy and cold-rolled to 0.2 by 1 mm cross section and an average length of 5 cm. During mechanical shaping, the specimens were strain-annealed at 950°C for 24 hr in vacuum. Finally the finished samples were vacuum-annealed at 1000°C for 6 hr and water-quenched to room temperature. The average grain diameter was 0.02 cm. B) Cooling System. The M, temperature of the alloy was -55°C. Fig. 2 shows the arrangement which was used to cool the specimen at a slow rate. The specimens were mounted inside a i -in.-diam hole in the 2-in.-long section of the copper specimen holder. This cavity was filled with silica gel. A dummy specimen was used under identical conditions for

Jan 1, 1969

By H. J. McQueen, G. C. Kuczynski

ThE useful properties of k6-Alfenol and the thermenol alloys (summarized by J. E. Nachman and W. J. Buehler&apos;) have encouraged research into those alloys which, having compositions near 25 at. pct Al, 75 at. pct Fe, undergo an ordering transformation between 500° and 550°C. The equilibrium diagram of the iron-rich iron-aluminum alloys was first determined by Bradley and Jay.2,3 They distinguished three structures: the disordered, which is bcc; FeAl, which is simple cubic with one Fe atom and one Al atom per lattice site; and Fe3Al, which is fcc with three Fe atoms and one Al atom per lattice site. This last structure may be conceived as eight body-centered cubes with Al atoms at the centers of alternate ones, so that Al atoms have only Fe as first and second nearest neighbors. Later, Osawa and Murata4 determined the boundaries of the different superlattice regions in the iron-rich Fe-Al solid solution by dilatometric and X-ray methods. Two of the six phases, which they found between 0 and 50 at. pct Al, were never identified by other workers. A. Taylor and R. M. ones,&apos; concurrently with and independently of this research, redetermined this diagram by measuring lattice parameters at temperature. Further reference will be made to their results. EQUILIBRIUM DIAGRAM A) Experimental Procedure—The alloys were prepared from NRC gas-free iron (99.9 pct Fe) and 99.99 pct Al. They were melted in alumina&apos; crucubles under vacuum in an induction furnace. If the ingots were unsound or showed more than a 3 pct weight loss, they were rejected. The ingots were homogenized at 1100°C for 24 hr before hot-rolling at 700" to 900°C from 1 in. to 0.25 in. thick. It is interesting to note that alloys containing more than 28 at. pct Al were able to take an 80 pct reduction of area in the ordered FeAl region. The dilatometer specimens and specimens for chemical analysis were cut from these plates. A Leitz dilatometer was used to measure the coefficient of linear expansion as a function of temperature. The specimens were slowly cooled from 900" to 300°C where they were annealed for 10 hr before slowly cooling to room temperature. The expansion was recorded photographically as the alloys were heated and cooled at 1.5oC per min between 100" and 1000°C. The magnetic measurements determining the Curie points were performed on the dilatometer specimens in the dilatometer, by using direct current in the furnace windings both to heat the specimen at 1.5°C per min and to serve as the primary coil. The regular specimen holder was replaced by a thin alundum tube on which was wound, as a secondary, a closely spaced coil of fine copper wire. A reversal of current in the furnace windings produced, in the secondary, an emf which was proportional to the induction in the specimen, and which could be detected on a galvanometer. In this way, it was possible to determine the Curie points of alloys to within * 5°C. B) Results and Discussion—The coefficients of linear expansion, as obtained from the dilatometer curves, are plotted as a function of temperature and composition in Fig. 1. Since in many cases the heating and cooling curves were superimposed, it was decided to measure slopes of heating curves only. Definite high peaks, due to the transformations, were observed on each curve between 400" and 520°C, and, for alloys containing more than 23 at. pct Al, a second set of smaller peaks at temperatures above 660°C. The sharpness of the peaks indicates that ordering to Fe3Al is a first-order reaction. The compositions and the temperatures of these peaks are listed in Table I. When these temperatures are plotted as a function of the composition, the result is the constitution diagram presented in

Jan 1, 1960

By J. Nutting, D. H. Kirkwood

The oxidation of lead sulfide in air between 200° and 350°C has been investigated by electron diffraction from thick sulfide films and from galena surfnces. It has been demonstrated that sulfate is the stable reaction product up to 570°C. Sulfate is HAGIHARA has investigated&apos; single crystals of galena roasted in air by the reflection electron-diffraction technique, which owing to the very limited penetration of the beam into the crystal gives information of the nature of the surface only. He has shown that up to 280°C the first oxidation product is lead sulfate, followed by lead mono-oxysulfate (PbO . PbS04). At longer times and higher temperatures more complex patterns appeared which could not be analyzed. All of these patterns were of streaks or spots arising from crystals oriented on the galena surface, and it is probable that these crystals are lead compounds whose structures have not been determined, such as the other oxysulfates (2Pb0 • PbS04 and 4Pb0 . PbS04) or a number of oxides. Certain lead sulfide films, formed chemically, give ring patterns in transmission electron diffraction2 because they are polycrystalline, and should also give ring patterns of the products after oxidation. It was thought that a diffraction study would reveal the sequence of phases produced in the reactions at different temperatures, since X-ray powder patterns are available for many lead compounds. PREPARATION OF FILMS The films were prepared by passing H2S over a saturated solution of lead nitrate in water. Once a silvery film had formed on the solution surface, no further thickening was apparent. The films were transferred by a gauze to a bath of distilled water for washing and pieces of film were caught on small discs on which they were dried. The discs were formed initially on galena up to temperatures of 300°C, followed by oxide and oxysulfates in turn at longer times. The appearance of- these phases is believed to result from an inadequate rate of supply of sulfur to the top surface 01. the crystal. standard Siemens mounts, made of platinum alloy, and had seven 20-p apertures drilled through them. The parts of the film which had dried onto the disc surface were light blue in color, which is the interference color of a film about 600A in thickness. A strong pattern of lead sulfide was obtained in transmission electron diffraction through the apertures but slight broadening indicated a crystallite size of around 200A. Tilting a sulfide film in the beam produced arcing of the rings, increasing the intensities of the (Ill), (3111, and (222) rings and reducing (200) and (220). This arises from preferred orientation in the film, a [loo] direction of the crystallites being normal to the plane of the film. These specimens were oxidized in an oven maintained at the required temperature. The reported times include that taken to heat the film to the reaction temperature. STABLE PHASES FORMED IN OXIDATION The conditions in which various oxidation products of lead sulfide are stable have been considered by the authors in a previous paper.3 It was shown that in a normal atmosphere, taken as containing lo-&apos; atm of SOs, lead sulfate would be stable up lo about 570°C. This was confirmed by oxidizing thin films of sulfide for several days, and the analysis of the transmission-diffraction pattern is given in Table 1. The fit with the patt$rn from X-rays is good, except for the missing 3.62A ring. Some disagreement in intensities of reflections given by X-rays and electrons is to be expected. Up to 570°C a spotty pattern of sulfate was still obtained, indicating grain growth, but above this temperature the film disintegrated. Probably this is associated with the decomposition to PbO . PbS04. It needs to be emphasized that the atmosphere

Jan 1, 1965

By Charles E. Mann, Douglas J. Lootens, Rufino B. Bomasang

INTRODUCTION The economy of the Philippines, like that of many other developing nations, has been severely strained by the rapid escalation of imported crude oil prices over the past decade. In an effort to reduce its dependence on imported crude, significantly increased emphasis, both in the public and private sectors, is being placed on the rapid development of Philippine coal resources. This paper is designed to present an overview of the Philippine coal industry, its historical development, present status, and future potential. COAL RESOURCES AND RESERVES In 1977, a British consulting firm collated all available data on Philippine coal resources and estimated the total coals potential at about 0.9 to 1.4 billion metric tons (mt). In 1981, using more recent data the Philippine Bureau of Energy Development (BED) estimated the potential at 1.7 billion mt. The BED estimated the proven coal reserves at 257 million mt. These coal resources are scattered throughout the major islands comprising the Philippine archipelago. However, about 52 percent of the currently proven reserves are located in the tiny island of Semirara between the islands of Mindoro and Panay. About 25 percent is located in the Cagayan Valley in northeastern Luzon while 13 percent is located in Mindanao. The remaining 10 percent is scattered in the islands of Cebu, Samar, Mindoro, Negros, Polillo, Batan, and Catanduanes. The bulk of Philippine coal is sub-bituminous in rank. Some bituminous coal with coking properties has been reported in Malangas, Zamboanga del Sur in western Mindanao, and in Catanduanes, but the exact tonnages have not been accurately established. It is believed, however, to be at most 5 million tons. A little semi-anthracite coal exists in Malangas with the remaining unmined reserves estimated at a little more than one million tons. Table 1 shows the quality ranges of Philippine coal deposits.. Figure 1 shows the distribution of known Philippine coal resources PHILIPPINE COAL PRODUCTION In 1981, total coal production was 330,720 mt. Though modest by world standards, this was the highest production figure in Philippine coal mining history. This came from 25 mines, mainly small scale underground mines of capacities varying from 10 to 100 tons per day (tpd). The actual production capability was about 800,000 mt in 1981, but the producers had to scale down production to the level of local demand. Even then, some 50,000 tons of coal remained unused by year-end. The 1981 production came from the following areas: Cebu 224,751 mt (68%) Zamboanga del Sur 57,095 mt (17%) Semirara 13,222 mt (4%) Polillo 17,132 mt (5%) Cebu has always been the main source of Philippine coal production. Coal mining has been carried out in Cebu for the last 50 years, although it has been characterized by a very crude mining technology. Due to the limited size of coal deposits and complicated geology, however, Cebu&apos;s share of the total national production is expected to go down to only 10 percent by 1985. Except for Semirara&apos;s open-pit production, the balance of Philippine coal production comes from underground mines. These underground mines generally use room-and-pillar methods, except for those at Zamboanga del Sur and Polillo which use modified longwall methods patterned after those used in Taiwan. Due to the much higher mining recovery, most underground mines are now planning on switching to longwall. At Semirara, an open pit mine is now being developed for a one million ton per year capacity by 1984, and will then be the largest Philippine coal mine. While present earthmoving work is done with bulldozers, loaders, and trucks, the main coal extraction equipment will be bucket wheel excavators imported from Austria. PRESENT COAL UTILIZATION Existing coal production is sold mainly to coal- fired cement plants and power plants. The balance is sold to a sugar central, a coconut oil mill, a food processing plant, and two plants producing carbide and ferro-silicon alloys.

Jan 1, 1982

By A. W. D. Hills, M. R. Moore

An apparatus has been developed in which metals can bc solidified under closely controlled unidirectional heat flow conditions. The metals are cooled by a multiple-air jet system, designed so that the heat transfer coefficient is uniformly distributed over the cooled surface. They are contained in a special furnace system of low thermal mass which enables unidirectional heat flow conditions to be rigorously maintained for certain specific cooling rates. This apparatus has been used to study the solidijication of pure lead and pure tin at zero superheat, solid metal thicknesses being determined by thermal analysis, and by dipstick readings. Detailed thermal balances have been drawn up on the experiments in order to determzne the cooling conditions that most rigorously correspond to unidirectional heat flow. Solid metal thicknesses, measured experimentally for these conditions, have beetz shown to agree closely with the theoretical wedictzons of different integml-profile methods. lt is concluded that any errors inherent in the integval-profile method are no greater than the errors inherent in experimental investigations of solidification. A knowledge of the influence of heat transfer rates on the solidification of metals is essential to the understanding and control of industrial casting processes. Since very few formal methods are available for solving the heat conduction equation under solidification conditions several authors have developed approximate techniques for doing so. One of the most promising is the integral-profile technique that has been used by Goodman,1 Hills,2,3 Tien4 and Hills and ~oore&apos; to predict solidification rates under certain specific heat transfer coniditions. In the first of this present series of papers6 Hills has further generalized the method and developed a universal integral-profile technique that can be used to predict solidification rates under a wide variety of unidirectional heat flow conditions. Since the method is approximate it is necessary to investigate the accuracy with which it predicts actual solidification rates. A review of the literature7 shows that solidification rates have seldom been measured under accurately known heat transfer conditions and it was therefore decided to develop experimental techniques that would enable this to be done. Results obtained would then be available as a check on the approximate solutions already developed, and in the development of further solutions that would be applicable under more complicated conditions. The initial work in this experimental program which is described here, is concerned with the solidification of pure metals at zero superheat under unidirectional heat flow conditions. Subsequent experiments have been concerned with the solidification of pure metals at appreciable superheats, under varying unidirectional heat flow conditions and under two dimensional heat flow conditions. In a series of experiments recently initiated, the solidification of binary alloys is also being investigated. The results of these subsequent experiments, together with relevant theory, will be described in later papers. The solidifying metal has been cooled in all the experiments, by a multiple air jet system designed so that the heat transfer coefficient to the cooled surface is constant and is uniformly distributed over the surface. This type of system has been chosen since only one parameter is needed to specify the heat transfer conditions and since these conditions are analogous to those met in certain continuous casting processes.&apos; Air cooling was chosen in preference to water cooling, however, since it offers a wider range of heat transfer conditions, and since it can be investigated by analogous mass transfer techniques. The first part of this paper discusses the existing integral-profile solutions that correspond to the heat transfer conditions used in the experiments, and describes the development and use of the experimental apparatus. In subsequent sections the heat transfer and solidification results are presented, and the various theoretical predictions are compared with them, and with one another.

Jan 1, 1970

By C. J. Bechtoldt, H. C. Vacher

Quenched alloys, prepared by powder metallurgical techniques, were examined by microscopic and X-ray diffraction methods. The compositions and heat treatments were chosen so that the chromium and nickel solvuses could be determined and a range of composition and temperature, in which a eutectoid had been reported, could be explored in small intervals. The results showed no evidence of eutectoid reactions having taken place. ALLOYS containing iron, chromium, molybdenum, and nickel are extensively used in high-temperature applications. In order to provide basic information on the solid-state reactions that occur in such alloys, the National Bureau of Standards is engaged in an extensive study of the equilibrium phases in the binary, ternary, and quaternary systems involving these four metals. Attention was directed to the chromium-nickel system because a review of the literature showed conflicting data. A recent compendium1 of the constitution of binary alloys gives two diagrams for the chromium-nickel system, one a simple eutectic and the second a diagram showing a eutectoid and a eutectic. The eutectoid was the result of an allotropic transformation in a high-temperature solid-solution form of a chromium-rich phase called 0. The approximate temperature and composition of the eutectoid was 1200°C and 30 at. pct Ni. In the preliminary study, at the Bureau, no transformation was indicated in the chromium-rich phase of ternary and quaternary alloys in which chromium and nickel were major components. Similar results have been reported from time to time in the literature,2-8 In consequence of this situation, a systematic study was made of the constitution of heat-treated chromium-nickel alloys using metallographic and X-ray diffraction methods. The compositions of the alloys were selected so as to determine the boundaries of the chromium-rich and the nickel-rich phases and to explore in small intervals the ranges in composition and temperature in which the eutectoid had been reported. The results of this study are reported and discussed in the present paper. EXPERIMENTAL PROCEDURES Materials, Alloys, and Heat Treatments—The alloys were prepared by a powder metallurgy technique similar to that used in earlier work.9 Analyses of the materials used are given in Table I. Powders were mixed using a vibrator in 30-g batches of predetermined composition; 2-g pellets were made from the mixture by compacting at room temperature in a 1/2-in. diam mold under 60,000 lb per sq in. pressure. The pellets were sintered in dry hydrogen for 10 days at 1300°C. At the end of the sintering treatment the specimens were quenched in water, which caused a pale green film to form on the chromium-rich alloys and thin black scale to form on the nickel-rich alloys. The pellets after sintering were approximately 1/2 in. diam by 3/32 in. thick. The purification train9 was modified by inserting a tube of titanium turnings, heated at 700°C to increase the efficiency of the removal of oxgen and nitrogen. It was found in the earlier work that the sintering treatment lowered the carbon, oxygen, and nitrogen contents of chromium-rich alloys to 0.01, 0.01, and 0.004 wt pct, respectively, and that there was a loss of chromium. In order to ascertain the extent of this loss, the chromium contents of certain alloys were determined chemically. They included those alloys used to determine the parameter-composition curves and those of critical composition, used to determine the chromium-solvus microscopically; these analyses were made on samples after the final heat treatments. The mixed powder values for the chromium content of those alloys that were not analyzed were adjusted to conform to a smooth curve based on the chemically analyzed values for

Jan 1, 1962

By J. Kostuik, M. J. de Bastiani

The method of mining the uranium orebody at Denison mine in the Elliot Lake district of Ontario is discussed. Details of the development of haulage-ways and rooms are giuen, as well as methods of ore haulage. The milling and beneficiation stages are noted briefly. Located in the Elliot Lake mining district of Canada, the Denison mine lies between Sudbury to the east and Sault Ste. Marie to the west, Fig. 1. This area is overlain by Huronian sediments filling a basin in the Keewatin basement complex. Subsequent folding of these sediments developed a synclinal structure, known locally as the Quirke Lake Trough, which forms the northern portion of the now famous big Z structure, the geological trademark of this region. Plunging to the west and extending nine miles from the granite outcropping in the north to the Keewatin lava contact to the south, the syncline has dips of 10" to 45" on the north limb and 10" to 20" on the south limb, Fig. 2. The Denison orebody, located on the north limb of the syncline, lies between 800 and 3000 ft below the surface. The main ore zone is within 50 ft of the Missisagi-Keewatin contact (see Fig. 3), and it varies in thickness from 6 to 32 ft. This ore zone has a composite dip of 19" to the south and is composed primarily of two pyritized conglomerate beds separated by a band of pebbly quartzite stratum. The upper conglomerate bed of the main zone varies from 2 to 15 ft in thickness, while the lower conglomerate varies from 2 to 12 ft. Over extended areas, mining is carried out over the entire section comprising the two conglomerate layers and intercalated quartzite; in other areas, the conglomerates are selectively mined, depending on the thickness of the quartz-ite. The ore zone contains approximately 6 pct sulfides and 80 pct silica. The predominant uranium-bear ing minerals are brannerite, uraninite, and an unidentified mineral (probably thucolite). Some of the uneconomic metallic minerals identified to date are pyrite, pyrrhotite, and chalcopyrite. MINE LAYOUT Shafts: Underground exploration and development (Fig. 4) were performed through two shafts 1/2 mile apart. The No. 1 shaft, sunk to a depth of 1856 ft with the main station established at the 1600-ft ore level, is a 250-sq ft, 5-compartment shaft capable of handling 4500 tpd. Two 5x5-1/2-ft compartments serviced by a 12-ft diam double-drum hoist, are used for hoisting 190-cu-ft bottom-dump skips in balance. A 30-man cage, offset by a counterbalance, operates within a 5-1/2x11-1/2-ft compartment. The fifth compartment is used as a manway, pipe, and cable-way. This shaft is also provided with an intermediate pumping station used during the initial mining phase as well as loading-pocket and spill-pocket installations and pumping facilities. The 480-sq ft No. 2 shaft, located down-dip from No. 1 shaft, has a 2776-ft depth. Serving as the main hoisting shaft with a maximum capacity of 9000 tpd, it has eight compartments, four of which are used for hoisting ore in 10-ton capacity bottom-dump skips. These four compartments, measuring 5x6-ft in section, are serviced by two 12-ft diam double-drum semi-automatic hoists. A 50-man cage is operated in a 15x8-ft compartment, and it is counterbalanced by a 12-ton weight. Two compartments are used for ventilation, manway, electric cables, and pipes. A station was constructed at the 1325-ft horizon of the No. 2 shaft for relay pumping. The main sta-

Jan 1, 1961

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

Hydrogen forms a beta-stabilized system with titanium, with a beta eutectoid at about 300°C and 44 atomic pct H2. &apos;The solid solubility of hydrogen in alpha decreases from about 8 to about 0.1 atomic pct from 300°C to room temperature. Hydrogen has little effect on tensile properties, but decreases notch-bar toughness to a large degree. This latter effect appears to be the result of increased notch sensitivity. PRIOR to this investigation, only a small amount of information was available on the effect of hydrogen on the mechanical properties of titanium. The effects of the other interstitially soluble elements, carbon, oxygen, and nitrogen, had received detailed study. Jaffee and Campbell1 indicated that hydrogen up to 1 atomic pct did not affect tensile properties deleteriously. Pitler&apos; indicated that 1 atomic pct H, in titanium reduced the impact strength appreciably, but his alloys contained appreciable amounts of oxygen, and it was difficult to attribute the embrittlement entirely to hydrogen. The high temperature portion of the equilibrium diagram for the Ti-H system was established by McQuillan," and his data generally corresponded with the results of Kirschfeld and Sieverts," Gibb and Kruschwitz," Bevington, Martin, and Mathews," and other investigators. The lower concentration limit of the hydride phase varied considerably among investigators, and Gibb and Kruschwitz9 ad shown that small amounts of contaminants in either titanium or hydrogen caused considerable variation in this lower limit. In view of this pronounced effect of contaminants, the extrapolated value of McQuillan&apos;s, about 48 atomic pct at the 325°C eutectoid, appeared the most reasonable. McQuillan&apos;s lowest experimental value was 54 atomic pct at a temperature of 450 °C. The density of titanium had been shown to decrease with increasing hydrogen content, but discrepancies were noted among the various investigations. The best values indicated that the density was decreased from 4.56 grams per cc at 0.27 atomic pctl to 3.84 grams per cc at 61.3 atomic pct? This investigation was conducted to determine the effects of hydrogen on a titanium, both in high purity and commercially pure metals, and on high purity a titanium alloys. Material and Fabrication The literature indicated that impurities in either the hydrogen or the titanium must be kept to a minimum. For this reason, the initial studies were made with high purity iodide-refined titanium. The vendor&apos;s analysis of the iodide titanium and the hydrogen content of the as-fabricated Y4 in. diameter rods are shown in Table I. Two 1 lb ingots were prepared by arc melting under argon in a water-cooled crucible, using a water,cooled tungsten electrode. This equipment has been described.&apos; As-cast Brine11 hardness numbers of 88 and 58 for these ingots were low enough to insure that the high purity of the metal was maintained during arc melting. The ingots were hot forged to % in. diameter rods at 800°C, cleaned by grit blasting, and then cold swaged to Yz in. diameter rods. The rod was then air annealed at 725 "C, ground to remove scale, and cold swaged to Y4 in. diameter (75 pct reduction in area). The material was then annealed for 1 hr in argon at 800°C to develop an equiaxed a grain size of about 0.05 mm. Micro tensile specimens and microimpact specimens were machined from this rod prior to treatment in the Sieverts-type absorption apparatus. Two lots of commercially pure RC-55 titanium were also used in this investigation to determine the effects of hydrogen and the normal impurities on mechanical properties. The commercially pure RC-55 alloy was obtained in the form of % in. diameter rod. The analysis of this material is also given in Table I. The % in. diameter rods were hot swaged

Jan 1, 1955

By John C. Sawyer

A brief review is given to show that catastrophic oxidation of stainless steel in the presence of lead oxide is similar in many respects to catastrophic oxidation as caused by MoO3 and V2O5, Experimental data are presented to show that lead oxide accelerates the normal oxidation process of stainless steel by chemically altering the normally protective oxide film formed on the base metal. Data are given to show that similar reactions occur during oxidation of stainless steel in the presence of MOO3,and V2O5. THE mechanism by which pure metals oxidize at high temperatures has been the subject of intensive research for many years and much has been accomplished towards understanding the processes involved. The mechanisms by which alloys oxidize have also been investigated, but due partly to the fewer number of investigations and partly to the complexity of the oxide systems present, available knowledge is not as extensive as with pure metals. When oxidation processes are further complicated by atmospheres contaminated with sulfide, halide, or oxide vapors, the knowledge of fundamentals becomes meager or altogether lacking. Thus, it is not surprising to find that the catastrophic oxidation of stainless steels in metal oxide vapors of MOO, and V2O5 is not a well understood phenomenon despite the fact that a number of investigations have been undertaken. The literature in dealing with the subject of catastrophic oxidation is primarily concerned with the effects of MOO3 and V2O5, but does mention that other metal oxide vapors, one of which is lead oxide, appear to promote a similar type of accelerated oxidation. While this latter effect is virtually unknown, the deleterious effect of lead oxide is of considerable commercial importance, as it is believed to be one of the fundamental reasons for exhaust-valve failure in gasoline engines. For this reason studies have been in progress for many years attempting to better understand the mechanism involved. Modern exhaust-valve alloys"2containing 20 to 25 pct Cr plus nickel and/or manganese are in effect high-grade austenitic stainless steels exhibiting ex- cellent oxidation resistance in air at exhaust valve operating temperatures of 1100° to 1700°F; yet these same alloys are prone to corrode during engine service because of the conditions attending their operation. These conditions are such that the valves become coated with deposits of complex lead compounds mainly derived from gasoline additives of tetraethyllead, ethylene dibromide, and ethylene dichloride. Literature searches3-7 and discussions with various investigators show that considerable difference of opinion exists as to the nature of the lead-bearing deposits found on the surface of exhaust valves and the atmospheres to which they are subjected; yet, all seem to generally agree that corrosion, a gradual transformation of alloy to nonmetallic products of corrosion, is a consequence of the presence of lead compounds. This majority opinion seems to be substantiated by laboratory engine tests which show that corrosion does not occur to any appreciable extent when lead-free fuels are used. The first observations of catastrophic oxidation reported in the literature were probably made by pfeil,8 but it was Leslie and Fontana9 who undertook the first detailed study of the phenomenon. Their work was chiefly centered on the acceleration of oxidation which took place when stainless steels containing more than 3 pct Mo were heated in air with restricted circulation. These investigators reported that the presence of other oxides near the surface would further accelerate the rapid oxidation which occurred. While they recognized that the effect was attributable to the presence of molybdenum, it was Rathenau and Meijering" who emphasized the fact that the presence of molybdenum in the alloy was incidental to the presence of MOO3 vapor in the atmosphere surrounding the specimens. Evans,11 as well as Cunningham and Brasunas 12 studied similar

Jan 1, 1962

By Bernard G. Carbajal

The dielectric properties and thermal stability of glow-discharge polytnerized films of styrene, chloro-benzene, and other organics and photoresist filrns are presented. Variations in the glow-discharge polymerization procedure are related to thermal stability. Thermal treatwzents to improve the dielectric properties of both positive (A2 340) and negative (KMER) photoresists are given. THIS study of the dielectric properties of thin organic polymer films is part of a program to investigate the electronic applications of organic materials. Thin organic polymer films have been produced in an ac glow discharge,13 with a low-energy electron-beam process,4 and in an rf dicharge. A process has been developed during the course of this program for forming thin organic polymer films in a dc glow discharge. These glow-discharge polymerized (GDP) films exhibit some useful dielectric and insulative properties. Variations in the properties of the GDP films can be induced by changes in the source material (monomer) andor in the conditions of the glow discharge. Thin organic polymer films can also be produced from typical positive and negative photoresists. Some variations in the properties of the photoresist films can be induced by suitable post-application treatments such as thermal crosslinking. The properties of interest in this study are dielectric constant, dielectric strength, resistivity, and thermal stability. POLYMER FILM PREPARATION I) GDP Films. The GDP films were prepared in a dc glow discharge in an atmosphere of organic monomer vapor. The details of the glow-discharge procedure have been presented previously.6 Briefly, under the influence of a dc glow discharge organic vapors can be polymerized in the vapor phase and the resultant polymer (GDP film) deposits on and in the vicinity of the cathode. Substrates placed behind a screen cathode can be uniformly coated over all exposed areas. Pattern definition can be achieved using normal mask stencil techniques. Table I presents the pertinent parameters in the preparation of GDP styrene. Conditions of Forrrzation of GDP Styrene. The rate of deposition for GDP films was monitored using a current-time integrator. The thickness of the deposited film for a given set of experimental conditions was a function of the current-time integral. The fifth row in Table I is a compilation of the deposition rate of GDP styrene films. Other organic monomers behave in a similar fashion. With the exception of the highly halogenated saturated hydrocarbons, all organics subjected to the conditions of the glow discharge form GDP films. 11) Photoresist Films. Photoresists are normally recognized to exist in two forms, a low molecular weight, soluble polymer form (A) and a high molecular weight, crosslinked insoluble form (B). Typical negative photoresists are applied in the low molecular weight form A and converted to the high molecular weight form B by the action of light. (Positive photoresists are applied in form B and converted to form A by the action of light.) Eastman Kodak Metal Etch Resist (KMER) has been chosen as a typical negative photoresist. Polymer film samples were prepared in the same configuration used for GDP films. The KMER was applied in the usual fashion using a 120°C drying step (infrared-lamp heating) and a 180°C post-bake. Care must be taken to completely remove the solvent in the drying step and to properly develop and postbake to exposed photoresist. If the photoresist film is not properly dried and postbaked, severe blistering and peeling will occur during subsequent elevated-temperature exposure. Thickness can be controlled by varying the viscosity of the form A photoresist and the spin rate at application. AZ 340 was chosen as a typical positive photore-

Jan 1, 1967

By R. R. Boucher, O. J. C. Runnalls

A pronounced thermal effect has been observed on heating or cooling a1wninum-rich Al-U and Al-Pu alloys. From microscopic and X-ray diffractionstudies, the effectl has been attributed to trnsfor)nations in the inlemetallic phases UAl, and PuAl , involuing rearrangement or cluslering of vacancies The transformation obsrved in Al-20 wi oct U alloys occurred near the a Al-UAl4 eutectic tem-perature of 646°C making it difjicult to detect from heating curves. When cooling, howeoer, thermal mad X-ray analyses indicnted that the high-temperati~re phase labeled p UAL, precipitated initially during euitectic solidification. As solidification continued and after an induction period o-f 5 lo 20 tnin the nu-cleatiorz and growth of the low- twmperature phase, a UAl4 produced an euolution of energy which raised the observed alloy temperature by 1° to 2°C. in Al-Pu alloys the transformation occurred at 645°C, 5 deg below the eutectic solidification temperccture. The eslimated latent heat of transformation was 25 +5 cnl per g PuAl,. The high-tetnpevcl-ture forms of UAl, and PuAl, were easily 9-etccined by chill casting Al-U and Al-Pu alloys and on reheating the alloys the trcltzsforrnation to the a phase was sluggish even above 600°C. Separated single cryslals o-f UAl4, joy example, showed no evidence Of transformalion after heating for 16 hr at 620°C. The transformation rates increased yapidly enough with increasing temperature, however, that a a spontaneous liberation of energy lens observed on occasion when bealing cast Al-20 wt pet U to neal- the RECENT phase studies on A1-Pu alloys have indicated that earlier reported equilibrium diagrams should be modified to take account of several poly- morphic transformations in the intermetallic compound PuAl,.&apos; During the course of the latter work an unexpected heat evolution was observed while cooling a solid alloy consisting of a mixture of a aluminum and PuA1,. The evolution occurred at 645°C, y below the a A1-Pu A1, eutectic solidification temperature. Subsequent thermal-analysis experiments with A1-U alloys showed that heat was evolved there also at a temperature nearly coincident with the a A1-UA1, eutectic solidification temperature of 646°. A search of the literature revealed that similar thermal effects had been observed before for both A1-U and A1-Pu but had never been fully explained.2,3 The purpose of the present paper is to describe thermal-analysis and X-ray diffraction experiments which have led to the conclusion that the thermal effects are due to transformations which involve the rearrangement of vacancies in the intermetallic compounds UA1, and PuA1,. EXPERIMENTAL PROCEDURE The A1-U alloys were prepared by heating super-pure aluminum (99.99 pct +) obtained from the Aluminum Co. of Canada in a graphite crucible surrounded by an induction coil. At 1000°C high-purity uranium metal produced by the Eldorado Mining and Refining Co., Ltd. was dropped into the liquid aluminum and was dissolved completely within 15 min. The impurities in the uranium were A1—4 ppm, Ca-4, C-70, Cr-3, Cu-6, Fe-30, Mg-2, Mn-10, Ni-25, Si-25, and Zn-2. The A1-Pu alloys were prepared by reacting plutonium dioxide with liquid aluminum under cryolite (3 NaF . AlF,) for 10 min at 1100°C in graphite crucibles exposed to the air. The plutonium was 99.8 pct pure, containing trace impurities of Ca, Cu, Fe, Pb, Si, and Zn. The liquid alloys were usually poured into water-cooled molds to provide castings of uniform composition from which samples could be cut for heat treatment and thermal-analysis experiments.

Jan 1, 1965

By Seymour G. Epstein

Using a modified capillary-reservoir technique, electromigration of dilute solutions of silver in liquid bismuth has been measured with relatively good precision. The effects of experiment duration, temperature. current density, and silver concentration have been investigated. Chemical diffusion coefficients of silver in liquid bismuth were also measured at temperatures ranging from 300°to 600°C. The effective valence of silver in bismuth was calculated as a function of temperature from a comparison of electric mobilities and diffusion coefficients. In an alloy containing 1 wt pct Ag, the electric mobility of silver increased from 1.65 x X sq cm per v-sec at 300°C to 2.38 x 10-4at 600°C; the diffusion coefficient in-creased from 3.0 to 17.5 x 10-5 sq cm per sec over the same temperature range. Calculated values of effective valence decreased from 0.28 at 300°C to 0.10 at 600°c. ALTHOUGH there has been considerable progress in the theoretical treatment of electron-transport properties in liquid metals, the mechanisms of mass-transport phenomena in liquid metals are still not clearly understood. This is especially true for the case of electro migration, alternatively termed elec-trotransport or electrodiffusion, which is mass transport induced by an applied electric field. A thorough knowledge of the mechanisms governing electromigration will considerably aid in understanding the electronic state of an impurity atom in a liquid metal. Electromigration has been long observed and studied in liquid metals and alloys. However, no satisfactory theory to explain the observed effects has been developed. The disparity in the present theoretical treatments, summarized by Verhoeven,1 has been attributed to the difficulty in describing the momentum transfer between electrons and ions and to the lack of precise measurements in liquid metals, especially at elevated temperatures. Prior to the last decade most of the electromigration studies were qualitative, in that only the direction of migration of alloy constituents was determined with any degree of reliability. These results have been summarized by schwarz,2 who was able to measure the electric mobility of several elements in mercury. More recently electromigration in liquid metals has been measured by a variety of techniques, with a varying degree of success. Mangelsdorf3,4 made precise measurements on dilute amalgams at room temperature, using a technique relating changes in composition to changes in alloy resistivity, but was unable to make measurements at elevated temperatures. Using a modification of this technique, Verhoeven and Hucke5 measured electromigration and resistivities in liquid Bi-Sn alloys. However, the resistivity technique is not sensitive to small composition changes and is impractical for very dilute alloys. Verhoeven and Hucke6 also measured electromigration of several solutes in liquid bismuth by adapting the capillary-reservoir method for determining diffusion coefficients in liquids. The reported precision of these measurements was poor, however, primarily due to the large uncertainties in the chemical analyses to determine concentration changes. Belashchenko7 has summarized the recent Russian investigations of electromigration, many of which, however, are of questionable accuracy. The present study was initiated to develop an experimental technique which would be both versatile and sufficiently sensitive to yield precise measurements of electromigration of solutes in dilute metal alloys at elevated temperatures. Using this technique, a comprehensive study of silver in liquid bismuth was made to determine the effects of experimental variables on the apparent electric mobilities. Chemical diffusion coefficients of silver in liquid bismuth were also measured over the same temperature range for comparison with the electromigration data. EXPERIMENTAL TECHNIQUE Electromigration Measurements. Electromigration of silver in liquid bismuth was measured by the capillary-reservoir technique, similar to that used by Verhoeven and Hucke,6 but modified to yield more

Jan 1, 1967

By R. G. Garlick, H. B. Probst

Tungsten single-crystal specimens of various orientations were deformed in tension at room temperature. Slip traces indicated both (112)(111) and (110) (111) slip; however, about 10 pct plastic dejormation was required bejore these traces could he seen. Resolzled shear-stress considerations indicated that at least some of the particular systems observed were not those on which slip initiated hut were secondary systems. This is highly probable, considering the high plastic strains involved. Analysis of the stress data with respect to possible slip systems indicated that slip must have been initiated at stresses below the proportional-limit stresses measured. ALTHOUGH there is general agreement that slip deformation in fcc and hep metals takes place on the plane of close packing and in the direction of close packing, there is no such agreement for slip in bcc metals. It is generally agreed that the close-packed direction (111) is the slip direction, but investigations have led to conflicting descriptions of the slip plane. As Hoke and Maddin1 point out, there are essentially four points of view. 1) Deformation in bcc metals is composite shear on (112) and (110) planes or on nonparallel (110) planes, and any apparent slip on other planes can be accounted for completely by slip on these planes. Chen and Maddin have reported this to be the possible case for molybdenum." 2) Slip occurs in the (111) direction and is limited to {110), {112), and (123) planes (the three closest packed planes of the lattice). 3) Slip occurs in a (111) direction, but not necessarily on planes of close packing (banal slip). 4) Slip occurs in those directions and on those planes for which ß, the ratio of Burgers vector to interplanar spacing, is a minimum. The slip systems of the bcc metal tungsten have never been fully determined, although several investigators have reported pertinent results.3"7 The present work was initiated to determine the active slip systems in tungsten at room temperature, the critical resolved shear stresses associ- ated with these systems, and the orientation dependency of operative systems. These features of tungsten deformation at room temperature have never been reported in the literature. The authors find this somewhat surprising, particularly in view of the availability of tungsten single crystals since the advent of electron-beam zone-melting techniques and the widespread interest in refractory metals. It would seem apparent that such work has been attempted but the results have not been reported, possibly due to the conflict with deformation theory. The results of the present work conflict with any straightforward description of deformation based on the proposed explanations of slip in bcc metals. Although these conflicts have not been resolved, a presentation of the problem seems in order and should be of value to others working in this field. MATERIALS AND PROCEDURE Single-crystal tungsten rods of 1/8-in. diameter were grown from undoped commercial rod by one-pass electron-beam zone melting in apparatus previously described by witzke.8 Representative analyses of the rod before and after melting are given in Table I. There was no detectable zoning of impurities during melting. Buttonhead tensile specimens, as shown in Fig. 1, were machined from single crystals. Two flats 90 deg apart were ground in the gage length of each specimen. These flat surfaces facilitated the analysis of slip traces. No attempt was made to position these flats with respect to the crystal orientation. The worked surface layer of the machined specimens was removed by electrolytic polishing in a NaOH solution. Tensile-axis orientations were determined by standard Laue back-reflection techniques. The sharpness of the Laue spots indicated that the crystals were free of strain.

Jan 1, 1964

By A. R. Elsea, E. E. Fletcher

Cast X-40 alloy with the lowest nitrogen content studied had a 100-hr rupture stress at 1500°F about equal to the reported value for the commercial alloy. Increases in nitrogen content progressively decreased the rupture strength, and with about 0.1 to 0.2 pct N a minimum strength was reached, but there was no accompanying change in microstructure. Further increases in nitrogen resulted in the fomzation of progressively increasing amounts of a lamellar, pearlitic-type structure at the grain boundaries, with accompanying increases in rupture strength, and above about 0.25 to 0.33 pct N, the rupture strength exceeded the normally reported values. Two series of melts representing different melting stocks exhibited minimum rupture strengths at different nitrogen contents. This suggests that some unidentwed trace element not removed by vacuum melting has a strong influence on the response of this alloy to variations in nitrogen content. In a series of melts with manganese contents ranging from 0.6 to 3.2 pct, the material with the lowest manganese content had the highest 100-hr rupture strength at 1500°F. The manganese variations had no appreciable effect on the microstructure. CAST cobalt-base alloys such as X-40* exhibit high strengths at elevated temperatures (1500°F and above), but they also show considerable scatter in high-temperature properties. Since the design of parts for critical applications must be based on the minimum expected properties, this broad scatter appreciably lowers the design strength of the alloy. If the relatively poor properties exhibited by a few test parts from any given group could be improved, the spread in properties would be narrowed, and the design stress could more closely approach the average expected properties. The purpose of this research investigation was to learn what were the causes of these erratic properties and, if possible, to find methods for eliminating them. Earlier unpublished work showed that vacuum melting markedly influenced the high-temperature strength of cast X-40 alloy. There were indications that this behavior may have been the result of changes in the nitrogen or manganese content of the castings. Consequently, in the current investigation, the influence of variations in nitrogen and manganese content on the structure and high-temperature properties of cast X-40 alloy was studied. In this program, X-40 melting stock was vacuum melted to produce a base material that was very low in nitrogen content and in volatile trace elements. Additions were then made to this base material to produce alloys of the desired composition. The metal was cast into investment molds producing coupons which were machined into stress-rupture bars. These bars were subjected to stress-rupture tests and me-tallographic study to determine the influence of changes in analyses (nitrogen and manganese content) on the structure and properties. Material—The melting stock used for these experi-ments was in the form of shot from two master heats of commercial X-40 alloy. Only one master heat was used in a given series of melts. Thus, any differences in structure or properties that showed up in the specimens from a given series would be the result only of the intended variations in composition. The certified analyses of the master heats were as follows: C Mn Si Cr Ni Lot No. 2 0.50 0.71 0.66 25.44 10.53 Lot No. 3 0.54 0.73 0.70 25.95 10.00 W Fe Co P S Lot No. 2 7.45 1.34 Bal. 0.011 0.013 Lot No. 3 7.58 1.53 Bal. 0.005 0.016

Jan 1, 1960

By J. G. Early, F. V. Lenel, G. S. Ansell

The isothermal shrinkage rates of copper-powder compacts were determined in the temperature range from 760o to 1060oC. The rates for compacts fabricated from a pure spherical copper powder were compared, on the one hand, with those fabricated from a spherical powder containing a dispersion of aluminum oxide in the copper matrix and, on the other hand, with those fabricated from a pure copper powder having irregularly shaped particles. The irregular copper-powder compacts shrank much faster than the spherical copper-powder compacts and these, in turn, shrank faster than dispersion -strengthened copper -powder compacts. The experiments were run under a small external load. By varying this load, the stress dependence of the isothermal shrinkage rate could be measured for compacts from spherical-copper powders. This stress dependence was found to be approximately proportional to the 4th (dispersion-strengthened alloys) or 4.5th (pure metals) power of the stress. It is concluded that the material-trans port mechanism is due to dislocation climb rather than to Herring-Naharro creep. In this investigation the isothermal shrinkage rates of compacts made of copper powder with an average particle size of 70 g in the temperature range from 780o to 1060°C were studied. The aim of the investigation was to determine the mechanism of material transport responsible for the shrinkage of these compacts. Since the phenomenon observed in this investigation was shrinkage of compacts at high temperatures, it will be necessary to consider all the material-transport mechanisms possible in sintering. It is unlikely that evaporation and condensation, surface diffusion, or even volume diffusion of vacancies, in which surfaces of small radius of curvature are vacancy sources and those of larger radius of curvature vacancy sinks, will materially contribute to a sintering process involving shrinkage, i.e., one in which the centers of adjacent particles move towards each other. The two principal mechanisms which were considered were the so-called Nabarro-Herring mechanism and a plastic deformation mechanism by dislocation movement. Both of these mechanisms were originally conceived to explain creep, i.e., the plastic deformation of metals at elevated temperatures under a constant applied stress. The shrinking of metal-powder compacts which was studied in this investigation can be readily treated as a creep process. This means that the shrinkage rates observed are considered as creep rates under the influence of an applied stress. It is true that the stresses in sintering experiments are generally not constant but decrease continually with time, but, by considering creep rates or shrinkage rates over a relatively short time interval, the small changes in stress during this time interval can generally be neglected. Nabarro-Herring microcreep is a high-temperature deformation mechanism which is caused by a diffusional flow of vacancies from boundaries under a tensile stress towards those under a compres-sive stress. Herring1 has shown that in this type of microcreep the strain rate e is proportional to the applied stress and follows an equation of the form ma, aexp(-Q/RT) [l| where <j is applied stress, Q is the activation energy for self-diffusion, R is the gas constant, and T is the absolute temperature This type of creep can explain the shrinkage of a porous compact. The surface of the pores are subjected to the tensile stress of surface tension, while the grain boundaries are under a compressive stress also due to surface tension. Vacancies diffuse from the pore surface through the lattice to the grain boundaries, where they are eliminated. In order to maintain vacancy equilibrium at the pore surface the vacancies leaving the region of the pore surface are replenished from the volume of the pore, which means that the pores shrink.

Jan 1, 1964