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By A. Timur

Fluid flow properties of porous media have long been of interest in such varied disciplines as geology, geophysics, soil mechanics, and chemical, civil, and mechanical engineering. This interest has resulted in numerous models of porous media that have been proposed, tested, and found to be useful under, at best, only special circumstances. A critical review of most of these models is given by Scheidegger. 1 The application of each new tool to the study of porous media has helped to test some of the existing theories and to form new ideas based on the new parameters being measured. In the application of nuclear magnetic resonance (NMR) techniques to the study of the properties of fluids in porous media, the theoretical studies of Korringa et al.2 resulted in a model for the relaxation of spin polarization of protons in a hydrogenous fluid in a pore of a solid. Seevers3,4 verified this model, established a method for measuring the surface-to-volume-ratio distribution in a porous medium, and proposed a technique for determining specific permeability in sandstones. In the present investigation, the uses of NMR methods are extended and a simple model of porous media is developed from an analysis of pulsed NMR measurements. In this model, the pore spaces of a porous medium are divided into three groups on the basis of their surface-to-volume ratios. To evaluate predictions of the NMR model, laboratory measurements of spin-lattice relaxation time, porosity, permeability, and residual (irreducible) water saturation were conducted on more than 150 sandstone samples obtained from four oil fields in North America. Applications are discussed for estimating the volume of movable fluid, ?p, and the specific permeability, k, of sandstone samples. The former parameter, which can be considered as producible porosity, is expressed by ?p = [1 -- (Swr/100)]? , .... (1) where + is porosity in percent of bulk volume and Swr is the residual (irreducible) water saturation in percent of pore volume at a capillary pressure of 50 Psi. Fast, nondestructive laboratory methods are described for determining porosity, movable fluid, and permeability of sandstone samples from measurements with a pulsed NMR (spin-echo) apparatus. Procedures are given for adapting these methods to samples of irregular shape and small size. Theory General In the Korringa, Seevers, and Torrey2 (KST) model the observed decrease in the spin-lattice relaxation time, T1, of protons of a hydrogenous liquid contained in the pore spaces of a porous solid is attributed to an increase in the correlation time for the random motion of the water molecules and to the presence of paramagnetic centers at the liquid-solid interface. This KST model predicts the observed relaxation time of a hydrogenous liquid in a pore of a solid through

Jan 1, 1970

By D. S. Pye, J. P. Gallus

Successful hydraulic pressure treatment of oil and gas wells that have long producing intervals, multiple pay zones, fluid thief zones, or natural or induced fractures has long been a serious problem plaguing the petroleum industry. High fluid-injection rates, straddle packers, ball sealers, and either liquid or solid additives to the treating fluids are being used to cope with this difficult and costly problem.l-6 The use of ball sealers and straddle packers is limited, in practice, to wells that have been completed with perforated cemented casings or liners. Well stimulation with ball sealers and straddle packers is usually successful as long as the cement remains competent. The other techniques of diverting are used with all types of completions. However, there are two significant disadvantages of the high rate method: excessive horsepower requirements, and the need of large treating-fluid volume. Consequently, most well stimulation techniques that involve diverting depend upon ball sealers or granular materials. Liquid diverting agents, and some of the solid ones in use today, frequently will cause formation damage. On the other hand, the most popular particulate diverting agents often are so soluble in the treating fluid that they become largely ineffective; their particle size is severely reduced as they dissolve while being transported through thousands of feet of pipe to the formation face down hole. In our attempts to deal with the shortcomings of these diverting agents, we experimented with a large variety of potentially suitable deformable materials the solubility of which could be controlled. Following are the criteria for the diverting agent sought: 1. The material must be effective in reducing fluid loss to thief zones, including existing fractures and very high permeability layers in the formation to be pressure treated. 2. The material must have enough strength to bridge under the treating pressure. 3. The material must be insoluble or slowly soluble in the treating fluids so that the particles retain sufficient size to be effective after they reach the formation face. 4. The material must be completely soluble in the produced oil or condensate liquid so that it can be removed readily; it must not cause formation damage. A number of products consisting of various polymers blended with waxes and other solid hydrocarbons were examined. All these materials satisfied the criteria for a diverting agent and also exhibited some degree of plastic deformability. On the basis of initial tests of strength and hardness, several blends of wax and polymer were selected for extensive testing in the laboratory and the field. These compounds have congealing temperatures ranging from 140 to 190F; they are insoluble in water and soluble in oil. They conformed, therefore, to the criteria specified for a theoretically superior diverting agent. Laboratory and field tests were conducted using these wax-polymer materials to demonstrate that the use of a deformable diverting agent can significantly improve fluid diverting performance. Data in this

Jan 1, 1970

By C. F. Weinaug, P. M. Blair

Many difference equations used to approximate reservoir flow problems treat the phase pressures implicitly but not the mobility-density coefficients. Such difference equations are neither wholly explicit nor implicit, but might be described as mixed. Mixed equations are relatively easy to apply. But the associated time truncation error is relatively large, and when used to solve problems characterized by high flow rates, these equations may be unstable for practical size time steps. This paper outlines the development of a completely implicit difference analogue for reservoir simulation, along with a Newtonian iterative method for solving the resulting nonlinear set of algebraic equations that arise at each time step. While this implicit equation requires two to three times more work than does the mixed equation, it is shown to markedly decrease the time truncation error and to yield a stable solution for much larger time steps than does the mixed equation. INTRODUCTION Calculation of multiphase, multidimensional flow in porous media is generally accomplished by numerical methods that involve approximating systems of partial differential equations by systems of partial difference equations. The early development of difference equation techniques was directed toward the solution of linear differential systems. However, the equations of multiphase fluid flow through porous media are highly nonlinear in that mobility and density often are strong functions of pressure and saturation. Thus, solution of the flow problems by difference equations involves solving sets of algebraic equations whose coefficients change from step to step of the calculations. Current practice is to evaluate most coefficients at the beginning of a time step and then to apply difference methods well suited for solving linear problems. At least two major difficulties arise from the use of this practice. First, evaluation of coefficients at the old time level and evaluation of pressures at the new time level results in larger time truncation errors near displacement fronts than if all quantities in the distance derivative were evaluated at the same time level. Second, evaluation of mobility coefficients at old time levels results in an unstable difference equation in regions of high flow rate. The first of these difficulties often results in optimistic recovery behind the displacement front, and the second requires the use of small time steps or special techniques in solving coning problems1 or problems of gas percolation.2 Evaluation of all quantities in the distance differences at the new time level results in a completely implicit difference system. Such a difference system has a lower time truncation error than equations in which mobilities are evaluated at the old level and pressures evaluated at the new level. The algebraic equations resulting from the fully implicit difference equation are, in this case, nonlinear and require some iterative method for their solution. This paper develops fully implicit difference equations for two-phase flow in porous media, describes their solution by Newtonian iteration, and gives examples of problems more easily solved by the new method than by previous methods. EVOLUTION OF DIFFERENCE EQUATIONS FOR NONLINEAR PROCESSES The completely implicit difference equation used in these calculations results from evolution beginning with explicit difference equations, proceeding through what we will call "mixed" equations, and arriving now at a completely implicit equation. Let us illustrate the evolution by considering different analogs of the nonlinear equation

Jan 1, 1970

By Jacques B. Wertz

Recurring movements remotely connected with the Murray fracture zone and the San Andreas fault complex, together with the slow northwestward drift affecting the Baja California peninsula, could progressively have accentuated the tensional situation already connected with the anticlinorium in southern Arizona. From the fragmentary data gathered on the Texas lineament, it appears that a very mild curvature, concave to the northeast, may be present along this belt throughout Arizona. Those localities where the successive changes in direc¬tion of the strands of the lineament belt seem to occur do generally coincide with intersections of both north-northwestern and northeastern breaks. It is along the outward, southern fringe of the belt (at such structural centers like Bisbee, Baboquivari, Ajo) that the greatest impact of regional movements could be expected to have occurred through tangential-torsional stresses. Although it si accepted that the north-northwestern and more particu¬larly the northeastern fractures in Southeast Arizona are propitious to or partially responsible for mineralization, it seems undeniable that the Texas lineament belt must have greatly increased the potentialities for ore throughout the Arizona copper province. While intrusive bodies occur near major intersections, with the Texas lineament belt as a common denominator, it seems, the ore deposits are to be found close to one of the intrusive stocks, varying in distance from contiguity (Bisbee) to one or two miles away (Silver Bell orebodies).

Jan 1, 1970

By L. B. Davidson

The petroleum literature contains many reports on the relative permeability properties of porous media. However, only recently have studies of relative permeability at elevated temperatures been made.1 -5 Each of these studies presents relative permeability data on water-oil systems in linear sandpacks or sandstone cores under isothermal conditions. The results of these investigations are dissimilar. Edmondsonl found that in Berea sandstone a temperature-dependent effect was present, while Shilobod,2 using the same material, found no temperature dependence after normalizing for initial water saturation. Workers at Texas A&M U.3-5 found that the ratio kw/ko was temperature dependent in an unconsolidated system. The differences in results of these studies are probably a consequence of differences in the material employed, in the experimental procedures followed, and in the properties of the porous systems used. This paper describes an experimental investigation of permeability ratio temperature dependence, conducted to clarify some of the results obtained by previous workers. Each experiment described in this paper involved the isothermal displacement of Chevron No. 15 white oil by either nitrogen, steam, or distilled water and displacement of water by nitrogen. All permeability ratios were calculated using the Welge procedure. Values of the water-oil permeability ratio were obtained over the temperature range 75OF to 540°F. Results indicate the ratio is temperature dependent at low water saturations, probably due to interfacial effects. However, as the saturation is increased, temperature dependence decreases until, above some minimum saturation, the ratio becomes insensitive to temperature. Previously published work indicates that the dependence reappears at very high water saturations, a region of the ratio curve not completely examined in the present study. It appears that water-oil permeability ratios are temperature dependent at the extremes of the ratio curve where changes in interfacial tension with temperature induce variations in residual saturations. Between the extremes, there is a region in which the permeability ratio is insensitive to temperature. The size and location of this region is probably a function of the characteristics of the porous system. Gas-oil permeability ratios calculated from nitrogen-white oil displacement experiments indicate a definite temperature dependence over the range 75OF to 500°F and over the entire gas saturation range studied. Evidence discussed in this report indicates that this dependence is a consequence of molecular slippage in the gas phase. This is an extension of the Klinkenberg effect6 to two-phase systems at high temperatures (the existence of slippage in two-phase systems at room temperature has been demonstrated7). Evidence for a similar source of temperature dependence in superheated steam-white oil experiments

Jan 1, 1970

By Burt C. Mariacher

The Minerals Beneficiation Division meets each year at the Annual Meeting of AIME. All members are invited and encouraged to attend. For the information of those who did not attend the meeting in Denver last February, this column presents a summary of the reports given and topics discussed. Technical Committee Coordination Consolidation of technical programs having common interest to MBD and the Extractive Metallurgy Division is proving a considerable success, both on the technical committee level-through the efforts of the MBD-EMD Coordinating Committee-and in special symposia. MBD Chairman, R. S. Shoemaker, noted that J. D. Prater will be serving as Chairman of both the MBD Chemical Processing Committee and the EMD Hydrometallurgy Committee for 1970-71. R. P. Ehrlich commented on the cooperative effort of both divisions in organizing the Copper Metallurgy Symposium held at the Denver Meeting. This effort, he said, was important to the success of the Symposium. H. R. Spedden discussed inter-Division coordination activities on the SME level. The forthcoming MBD-M&E-EMD Joint Lead-Zinc Symposium is yet another example of progress in this direction.

Jan 1, 1970

By John E. Young

United States Steel Corporation's Winifrede Mine is operated by Lynch District in the mountainous region of Eastern Kentucky. This region is characterized by narrow mountain ridges and precipitous slows which present both an opportunity and challenge in the design and selection of coal handling facilities for the movement of coal from the section belts to the railroad cars. The narrow finger ridges precluded use of underground haulage and, thereby, presented the opportunity to use high capacity equipment on the outside bench. The precipitous mountain slopes, steepest at the Winifrede seam horizon, presented a challenge to select a solution for lowering the coal approximately 1000 feet from the seam level to the valley floor railroad load-out point. It was evident from the start of planning that these two factors predominated; namely, rail haulage and coal lowering, and solutions to these would determine the final design of the Winifrede Mine coal handling facilities.

Jan 1, 1970

By R. Stefanko, Y. J. Wang, H. R. Hardy, R. Y. Kim

Since 1964, the Dept. of Mining at The Pennsylvania State University has been carrying out extensive studies associated with the phenomena of microseismic activity and inelastic behavior in geologic materials. Briefly, the program to date has involved the following stages 1) Study of the microseismic noise and energy rates for selected geologic materials under incremental, uniaxial tension.1,2 2) Investigation of the frequency spectra of microseismic activity of selected geologic materials under incremental, uniaxial tension.3,4 3) Investigation of the time-dependent inelastic deformation of geologic materials and the analysis of such deformation in terms of mechanical models.5, 6 4) Simultaneous study of microseismic activity and time-dependent inelastic deformation in geologic materials under incremental, uniaxial compression.7,8 Details of the research involved in stage 4 of the program constitute the subject of this chapter. It should be noted that the majority of the experimental data quoted in this chapter forms part of a thesis to be presented by one of the authors (Kim) in partial fulfillment of the requirements for the Ph.D. degree in mining engineering at The Pennsylvania State University. During the last two or three years, a number of important papers have been published which deal primarily with the fundamental structure and mechanical behavior of geologic materials. Recent papers 9,10 have provided research workers in the rock mechanics field with a meaningful overall picture of rock as a structural material. The concept that many

Jan 1, 1970

By William F. Lawrence

Within ten to fifteen years, coal-fired power generating stations will be producing over 40 million tons of coal-ash annually in the United States. The largest part of this ash will be emitted from the boilers, entrained in the off-gas stream and trapped as flyash. However, about 15 percent (six million tons) will he removed from furnace bottoms as bottom ash or molten coal-ash slag. In current practice, the molten coal-ash slap is generally water quenched and then transported either as a slurry or in granular form to storage or disposal areas. Although a small amount of this slag is marketed as abrasive grit or as roofing granules, most of it is considered a waste material which must be disposed of at considerable cost to the power companies and therefore to the public. The accom¬panying economic loss in terms of unused raw materials and displaced land is not as obvious but is just as real. The Coal Research Bureau at West Virginia University under the sponsorship of the U. S. Bureau of Mines has been examining the possible utilization of both coal-ash slag and flyash in the mineral wool industry as a method of partially alleviating the growing national problem of solid waste disposal. The potential marketing situation for mineral wool manufactured from coal-ash is illustrated in Figure 1. This bar graph depicts the growth in value of mineral wool shipments1 from 1949 through 1966. In this 17-year period, the value in¬creased by over 350 percent, more than 20 percent per year, despite a decrease in unit cost of mineral wool. It therefore appears likely that coal-ash could find a steady market as a supplement to existing sources of raw materials for mineral wool production.

Jan 1, 1970

By James H. Williams

More than 100,000 residents of Springfield and surrounding communities live on karst (sinkhole) terrain on the Springfield Plateau in southwestern Missouri. The city occupier much of the headwaters area of Wilson Creek basin, which is underlain by the Burlington Limestone (Mississippian), a cavernous, massively bedded formation averaging 150 feet in thickness. Sinkholes, some as deep as 75 feet, pock-mark the uplands. Stony red residual clay mantles the pinnacled limestone bedrock. Surface water lost to sinkholes and losing reaches of upstream areas resurges in springs and estevellas (reversible sinkholes) in the lower reaches of Wilson Creek. The Springfield Southwest Treatment Plant, an activated sludge process sewage treatment facility, situated about mid-basin at the confluence of Wilson Creek and a tributary, South Creek, serves the entire city. Effluent from the treatment plant together with industrial, street-wash and other waste from the-headwaters of the basin have degraded both surface and ground water quality in much of the Wilson Creek watershed. The area affected includes Wilson's Creek Battlefield National Park and recreational reaches of James River below the mouth of Wilson Creek.

Jan 1, 1970

By H. C. Gatos, J. T. A. Pollock, V. Sadagopan

PREVIOUS investigations on the effect of neutron irradiation on the superconducting properties of bulk transition metals indicated that little or no change occurred in poly crystalline disordered materials, particularly if cold-worked prior to irradiation. Only the superconducting properties of ordered intermetal-lic A15 compounds were found to be sensitive to irradiation, and the observed reduction in Tc and increased magnetic hysteresis or critical current densities were attributed to the introduction of flux pinning vacancy clusters and disorder in the lattice. Since the former would also be expected to be present after irradiation in disordered alloys, the general conclusion was that the disordering effect of the irradiation was the primary reason for the changes observed. The present note reports some unusual effects of neutron irradiation on cold worked Nb(Cb)-Ti-V alloys. Specimens with nominal composition as given in Table I were prepared by repeated arc melting, taking the usual precautions, and homogenized at 1000°C for 24 hr prior to a reduction of 15:l by cold rolling. Samples of size 1 by 1 by 25 mm were sliced from the rolled strips. The sarmples chosen for irradiating were sealed in a cadmium tube (wall thickness 1 mm) prior to exposure in a fast neutron flux of 3.7 x 1019 neutrons per sq cm in the swimming pool reactor of Union Carbide Corporation&apos;s Sterling Forest Reactor. During irradiation the temperature of the samples was maintained below 70°C. The irradiated samples were stored at room temperature for approximately 1 year allowing the radiation levels to reach a safe handling value. Tc measurements were made employing a self-inductance coil technique. Jc data at 4.2"Kwere obtained using a four lead resistivity method. The latter measurements were made at the Francis Bitter National Magnet Laboratory by setting the perpendicularly applied field and increasing the direct current through the sample until a potential of about 10-6 v was detected. Tc values for the nonirradiated samples are listed in Table I together with the change in Tc after irradiation. A decrease in Tc of 0.25 or 0.3"K was measured for three of the four samples, the exception being the Nb-30 at. pct V-20 at. pct Ti alloy which showed a decrease of 0.5K. Jc vs applied field data are plotted in Fig. 1 for the Nb-20 at. pct V-30 at. pct Ti alloy. These curves are typical of the four alloys and surprisingly indicate that a degradation occurred in all the samples after irradiation. Hc2 values, obtained by extrapolation to zero current, are 8 to 15 pct lower than those measured for the nonirradiated specimens. The reasons for the degradation of Tc and jc ob-served in the alloys on exposure to neutron irradiation are not immediately apparent. The temperature at which the samples were maintained during bombardment (<70°C) and stored (20°C) make it highly unlikely that any significant change in the dislocation density of the materials through thermally activated migration and annihilation would occur. The explanation must lie in the type of damage produced by the bombardment. McEvoy et a1. reported no change in superconduct-

Jan 1, 1970

This report was limited to a search of available literature on under- ground methods to combat acid water pollution. From this review it is evident that very little work has been done in this specific area. It is also evident that there are specific areas of mining engineering and mining related hydrology and geology that need further research efforts to solve the many water problems. They are: (A) Composition, variation and availability for oxidation of sulfur in strata. (B) Rate of oxidation of sulfuritic materials. (C) In situ limestone and its influence on underground acid drainage. (D) Structural, stratigraphic and hydrologic character of old mining areas as a basis to make decisions about adjacent new mining areas. (E) Operational changes in mining methods to prevent pollution. (F) Sealants for underground coating to exclude water from contact with pyrite to inhibit formation of the contaminants. Such a program has been initiated on refuse piles. The prime purpose of this report is to investigate those practices which have been used to regulate or control water accumulation and prevent harmful mine drainage. A supplemental purpose is to indicate those areas which need further research to prevent underground mine water pollution.

Jan 1, 1970

By Alder KF

Nuclear power stations to be installed in Australia will be fuelled from Australian resources of raw materials. This will require the establishment of new manufacturing industries and the eventual expansion of established activities, especially in uranium mining and the preparation of precision metal products. This paper presents some predictions of the possible growth of nuclear power installations in Australia. These might amount to 4000 MWE by 1985 and 11,500 MWE by 1990 and towards the end of the century, about 50% of new generating plant might be nuclear. Predictions are given of the demands for materials (uranium and zirconium) and fuel manufacturing services for four reactor systems which might be considered in the programme. - The availability of raw materials and technical capability place Australia in a particularly good position to undertake the manufacture of nuclear fuel&apos;; in addition to satisfying the domestic demand we should actively seek export markets for these products.

Jan 1, 1970

By Guillermo Krstulovich

Pillar strength is a fundamental variable in the design of room and pillar mining. A number of researchers have investigated the strength of mine pillars by loading cubical, cylindrical and rectangular model pillars to failure in a compression testing machine (1). Several of these researchers have observed an increase in the compressive strength of model pillar with an increase in friction at the platen-specimen interface (2, 3, 4, 5). It has been postulated that the friction prevents lateral expansion of the specimen, thereby exerting a confining pressure at the interface. Seldenrath and Gramberg in their work with cylindrical specimens of limestone and marble noted that the effect of clamping the ends of the specimens, i.e., to restrict lateral movement of the specimen face, was to increase the compressive strength about 10% for marble and from 50-75% for the limestone, as compared to the same type of specimens when tested with the end planes free (6). No attempt was made to determine the confining pressure exerted by the clamps. In recent years, Bureau of Mines has conducted an extensive study, similar to Seldenrath and Gramberg&apos;s, with dog bone specimens. The confining pressure exerted by the clamps was determined and an increase in the compressive strength with increasing confining pressure noted (7, 8).

Jan 1, 1970

By P. O. Metz, E. L. Wiehe, J. S. Foster

BASED on their analyses of growth kinetics, ibbs&apos; and Harris et al.&apos; have recently proposed that the rate of subcritical graphitization of steel is controlled by the rate of diffusion of carbon in ferrite. illert has concluded that this is the rate controlling growth mechanism when the growing graphite particles are relatively large. Harris et al.&apos; also propose that the matrix surrounding a growing graphite particle is plastically deformed to make room for the growing particle. If this plastic deformation does occur, then preferred recrystallization may be observed around the larger particles. If diffusion of carbon in ferrite is rate controlling, then a graphite particle growing in a matrix of, say, tempered martensite or pearlite, should be surrounded by a carbide depleted zone. Thus, the simple metallographic experiments reported here are sufficient to determine whether or not diffusion of carbon in ferrite is the dominant mechanism for the growth of graphite in steel. The present investigation considers graphitization in five alloys. The compositions are given in Table I. Graphitization was carried out at three temperatures: 900°K (627"C), 950°K (677"C), and 990°K (&apos;717°C). Samples were reacted in both the martensitic and the pearlitic initial conditions. In the hypoeutectoid steels, Sets 7 and 8, .and in the hypereutectoid Fe-C binary, Set 6, graphitization was very limited after 1000 hr at temperature. In these samples graphite particles observed were less than 10 p in diam. In the hypereutectoid commercial steels, Sets 1 and 3, large graphite particles (100 p) did not appear until after 250 hr at temperature. The limited number of graphite particles observed and the range of sizes obtained prohibited measurement of growth rates in this investigation. However, in all samples showing graphitization, neithe a carbide depleted zone nor recrystallization was observed. illert&apos;s model predicts that diffusion of carbon in ferrite should become dominant for graphite particles larger than about 300 p in diam. The largest graphite particle observed in this investigation was approximately 450 p in diam. No evidence of carbide depletion was noted. Fig. 1 shows a typical graphite particle. This nodule is from an initially pearlitic sample from Set 3 after

Jan 1, 1970

By G. L. F. Powell

g samples of Cu-20 wt pct Ag alloy have been mdercooled to a maximum of 197°C by melting under a slag of commercial soda-lime glass in a vitreous silica crucible. No grain refinement of the primary copper was observed in samples undercooled to the maximum of 197°C. When the samples contained a small amount of oxygen, the copper dendrites were partially recrystallized at undercoolings greater than 97°C. In previous papers&apos;-3 reporting the grain structure of undercooled silver and copper, it was observed that grain refinement was dependent on both undercooling and oxygen content. Grain refinement occurred in undercooled silver when the degree of undercooling exceeded the range 153" to 175"C, while in Ag-0 alloys (0.12 wt pct) fine equiaxed grains were exhibited when undercooling was greater than 50°C. Similarly, copper samples undercooled as much as 208°C displayed fan-shaped growth from a single nucleation site, while the grain structure of Cu-O alloys (0.08 wt pct) was fine and equiaxed at undercoolings larger than 150°C. Thus the presence of oxygen greatly reduced the undercooling at which grain refinement occurred. It was also observed that the change in grain size resulted from recrystallization and was not due to an enhanced nucleation rate in the liquid-solid transformation. It is possible that the influence of oxygen on recrystallization is due primarily to its presence as a solute element. walker4,&apos; reported that, although a grain size change did not occur in pure nickel until the undercooling exceeded 150°C, small grains were observed in samples of Ni-Cu alloy solidified at small and large degrees of undercooling. Jackson et al.6 suggested that the fine grained structure of the Ni-Cu alloy resulted from the melting off of dendrite arms during recalescence. This remelting process may occur in alloys as a result of segregation during freezing which causes a variation in liquidus temperature from point to point within a dendrite. It was therefore decided to undercool copper with a metallic alloying element to ascertain whether the presence of a metallic solute would have a similar effect to oxygen in inducing grain refinement. A Cu-Ag alloy was chosen, since both metals had been shown to behave similarly on undercooling. The alloy Cu-20 wt pct Ag was selected since the eutectic constituent outlines the initial growth form of the primary copper, so that the as-frozen grain structure is not obscured if subsequent recrystallization occurs. This paper describes the results of undercooling experiments carried out with Cu-20 pct Ag samples undercooled to a maximum of 197°C and the effect of oxygen content on the grain structure of the undercooled samples. EXPERIMENTAL Melting was carried out in a small cylindrical resistance furnace using "fine" silver granulate and oxygen-free high conductivity copper. The procedure adopted was to melt the required quantity of silver in air in a clean vitreous silica crucible for approximately 15 min, freeze, and add granulated commercial soda-lime glass to form a complete surface slag cover, after which the sample was melted and frozen several times to reduce the oxygen content. The glass slag cover was approximately 3 in. thick. Pieces of copper (=50 g) were added to the crucible until the required quantity to make 350-g samples of alloy had been charged. Each piece was added quickly to the crucible which was held at a temperature slightly above the melting point of silver. The piece was quickly pushed beneath the glass to minimize oxidation and any oxide coating usually decomposed before the piece had settled down into the silver. After the full quantity of copper had been added, the melt was stirred with a silica rod to hasten homogenization and a Pt/Pt 13 pct Rh thermocouple enclosed in a vitreous silica sheath inserted for temperature measurement. Heating and cooling curves were recorded on a potentiometric chart recorder fitted with a zero suppression unit. The milli-voltage range of the recorder was adjusted so that temperatures could be read to 1°C. Heating and cooling curves were taken every hour until three consecutive readings gave the same solidus-liquidus range, consistent with the solidus-liquidus range for this alloy composition by reference to Hansen and Anderko.7 Metallographic examination of samples frozen at this stage, failed to show any variation in composition from bottom to top of the ingot. Consequently, it was considered that the melt was homogeneous at this stage and undercooling experiments were then car-

Jan 1, 1970

By T. Reed Scollon

With some uncertainty as to the type, rate and scope of adoption of air pollution control regulations, and with limited information on the availability of low-sulfur fuels, it is possible at best to make only a rough assessment of the impact of such regulations on coal. It is apparent from the following discussion that regulations of the type already effective or being considered, if adopted and enforced on a widespread basis over a short-term period and if substitute fuels were available, both quantitatively and economically, could result in a loss of more than one-half of coal&apos;s markets. Depending on the areal sequence of adoption of such regulations, some areas would be able to obtain limited amounts of low-sulfur coals. Others would not. Because of the usually greater distances from the large industrial coal consuming areas to new sources of coal supply, and because of the higher mine prices for low-sulfur coals, the delivered prices of such coals as might be available would be much higher than those for high-sulfur coals. A large and sudden demand for low-sulfur coals would exert further upward pressure on prices.

Jan 1, 1970

By Mark J. Klein

The creep of 043 was studied over the temperature range 1650" to 3200°F and over the stress range 3000 to 44,000 psi. The steady-state creep rate over this range of stress and temperature can be expressed by the equation where A is a constant, is the stress, and is -0.8 x 103 psi-&apos;. Over a narrow range of stress variations c0 a and for this proportionality n varies from 3 to 30 in accordance with the relation n = aB. Above about 2400° F, H, the apparent activation energy for creep, is 110,000 cal per mole, a value about equal to that estimated for self-diffusion in this alloy. Below 2400°F, H increases with decreasing temperature reaching a value of -125,000 cal per mole at 1700° F. In this temperature region, H appears to be a function of the interstitial concentration of the alloy. MOST of the detailed creep studies of dispersion strengthened metals have been concerned with metals having fcc structures. However, there are a number of important refractory alloys with bcc structures that derive part of their high temperature strength from an interstitial phase and whose creep behavior has not been well defined. This paper describes the creep behavior of the bcc alloy, D43, over the temperature range 1650" to 3200°F (0.4 to 0.7 Thm) and over the stress range 3000 to 44,000 psi. In addition to colum-bium, this alloy contains 10 pct W. 1 pct Zr, and sufficient carbon (-0.1 pct) to form a carbide dispersion throughout the matrix of the alloy. The effects of variations in temperature and stress on the steady-state creep rate of this alloy are presented in this paper. EXPERIMENTAL PROCEDURES Creep tests were made in a vacuum of 106 torr under constant tensile stress conditions using a Full-man-type lever arm.&apos; Creep specimens were machined from 0.020-in. D43 sheet (grain size -5 x l0-4 in.) processed in a duplex condition (solution annealed -2900°F, 40 pct reduction in area, aged 2600°F). The specimens were tested in this condition without further heat treatment. Specimen extensions over 1-in. gage lengths were continuously recorded using a high temperature strain gage extensometer. Differential temperature and stress measurements were used to determine temperature and stress dependencies of the creep rate. Activation energies were calculated from the changes in strain rate induced by abrupt shifts in the temperature during constant stress creep tests. The 100°F temperature shifts used in most of the activation energy determinations required 15 to 90 sec depending upon the temperature at which the shift was made. The dependence of strain rate on stress was determined by measuring the change in strain rate for incremental stress reductions during constant temperature tests. It has been shown that columbium-base alloys such as D43 are susceptible to contamination by gaseous interstitial elements during vacuum heat treatments.&apos; In this regard, it is unlikely that these alloys can be heat treated without some loss or gain of interstitial elements despite the precautions taken to control the heat treating environment. However, several factors suggest that changes in interstitial concentrations of the specimens during testing did not affect the results presented in this paper. First, the dependence of the creep rate on the stress or temperature determined during the course of a single creep test showed no variations with the duration of the test. A variation would be expected if a loss or gain in interstitial concentration during the course of the test affected results. In addition, precautions taken during this investigation to minimize interstitial contamination by wrapping the gage lengths of the specimens with various foils2 (Mo, Ta, W) did not produce a detectable change in the stress and temperature dependencies relative to the unwrapped specimens. The averages of duplicate analyses for carbon and oxygen in several specimens determined before and after creep testing are listed in Table I. The combined nitrogen and hydrogen concentrations which were ordinarily less than 50 ppm did not change in a detectable way with creep testing. The analyses show that only minor changes in carbon concentration occurred during creep testing except for specimen 4. This specimen which was tested at 3100°F lost a significant amount of its carbon concentration to the vacuum environment. Specimen 1 gained 100 ppm of O, while specimens 2, 3, and 4, which were tested at progressively higher temperatures, lost increasing portions of their initial oxygen concentrations during testing. RESULTS AND DISCUSSION The Temperature Dependence of the Creep Rate. The apparent activation energy for creep, H, was de-rived from creep curves similar to that shown in Fig. 1. Steady-state creep was rapidly attained at the beginning of the test and with each change in temperature. This behavior suggests that the alloy rapidly attains a stable structure with each shift in temperature or that the structure is constant throughout the test. Since the dispersion will tend to stabilize the structure, the latter is probably the case. The activation energy was found to be independent of the direction of the temperature shift and the magnitude of the shift (50" or 100°F). Although H was approximately independent of the strain, there was a tendency for it

Jan 1, 1970

Jan 1, 1970

By N. S. Stoloff, J. N. Mushovic

Age hardening response of a Mg-Th-Zr alloy has been studied at temperatures in the range 60° to 450°C. Transmission microscopy revealed clustering of thorium atoms at low aging temperatures, supporting a previous report of GP zone formation. Peak strengthening, which is observed at 325°C, is due to the formation of a coherent, ordered, DO19 type superlattice structure, of Hobable composition Mg3Th, as plates parallel to the matrix prism planes. These plates later reveal a Laves phase structure of composition Mg2Th. The equilibrium Mg4Th phase begins to precipitate in two different forms at an early stage, competitively with the Mg2Th plates. RECENT work on the Mg-Th system indicated that, unlike most magnesium-base alloys, complex precipitation phenomena may be occurring. The partial phase diagram of the Mg-Th system indicates that an equilibrium phase, Mg5Th, is the sole intermediate phase.&apos; sturkey,&apos; however, has reported, using X-ray and electron diffraction techniques, that a metastable fcc Laves phase, Mg2Th, precedes the formation of the equilibrium compound, which he identified as closer in composition to Mg4Th. Murakami et al.3 reported that the equilibrium phase precipitates preferentially on grain boundaries and dislocations in a Mg-1.7 wt pct Th alloy; Kent and Kelly4 aged a more dilute alloy, Mg-0.5 wt pct Th, for 4 days at 220°C and found similar results. In addition, they reported that a platelike phase with a structure close to that of the magnesium matrix forms perpendicular to the basal plane and is probably ordered. Research on a Mg-4 wt pct Th alloy by electrical resistance measurements and transmission electron microscopy has suggested that GP zones may form at low aging temperatures.3 However, the electron micrographs purporting to show this phenomenon were not conclusive. In view of the fragmentary evidence concerning the nature of the precipitation processes in the various Mg-Th alloys, an aging study was undertaken to clarify the characteristics of the various precipitates which form and to correlate the mechanical properties of the system with the direct precipitate-dislocation interactions. The latter results are presented elsewhere.&apos; The purpose of this paper is, therefore, to discuss the precipitation sequence in this system. EXPERIMENTAL PROCEDURE Sheet stock (0.060 and 0.010 in. thick) of a commercial Mg-3.93 wt pct Th-0.42 wt pct Zr alloy (designated HK3lA) similar to that studied by sturkey2 was supplied through the courtesy of Dr. S. L. Couling of Dow Metal Products Co. Zirconium does not enter into any precipitation reactions,&apos; but is present primarily as a grain refiner. The alloy was chill cast, warm rolled to 0.090 in. thick stock, and then finally reduced by a combination of hot and cold rolling. The alloy chemistry is given in Table I. This material was solution treated at 580°C for 4 hr in a dry CO2 atmosphere, and then water quenched. Material in this condition was fairly clear of precipitate particles and was fully recrystallized. Aging at temperatures less than 200°C was accomplished by immersing the alloy in a silicone oil bath; for higher temperatures, aging was done in a salt pot. Age hardening treatments were conducted at 60°, 80°, 105°, 135°, 160°, 250°, 325°, 350°, and 450°C for times ranging from 5 min to 400 hr. Hardness tests were performed on chemically polished 0.060-in.-thick blanks of solution treated material which were aged at the various temperatures for increasing lengths of time. For aging temperatures above 150°C the Rockwell Superficial 30T scale was employed, while samples hardened at temperatures below 150°C were monitored with the 45T scale. Each data point consists of at least three separate readings. Yield stresses also were measured at room temperature on both 0.060 and 0.010 in. sheet specimens aged at 325°C. The aged foils were thinned by the window method in a solution of 80 pct absolute alcohol and 20 pct concentrated perchloric acid (70 pct) maintained at 0°C. A stainless steel cathode was used and the applied voltage was 10 to 15 v. Thinned samples were rinsed in distilled water and pure methanol. After the me-thanol rinse the thin foils were quickly dried between filter paper. Foils prepared by the above method were examined in a Hitachi HU11B electron microscope operating at 100 kv. RESULTS A) Hardness. The hardness data are depicted in Figs. 1 and 2. Peak strengthening occurs at 325°C after aging about 6 min, see Fig. 1. Significant strengthening is achieved also at 350°C, but aging at 450°C produces only softening. The stepped curve at 250°C indicates that a complicated precipitation process may be occurring at that temperature. Fig. 2 suggests that at least two hardening mechanisms exist since the lowest temperature hardness peaks are displaced to the left of the peaks obtained at 135° and 105°C. A great deal of scatter is observed at long times in all cases due to magnesium surface degradation caused by the silicone oil bath. B) Identification of the Strengthening Precipitates. The structure formed atlowagingtemperatures (c10O°C) was not clearly resolvable by transmission microscopy. The only bright-field evidence for a change in structure was a mottled appearance which could be observed at extinction contours, as shown in Fig. 3(a), and the disappearance of this effect when dislocations produced under the influence of the electron beam passed through the matrix, as noted in

Jan 1, 1970