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By N. S. Stoloff, R. C. Ku, R. G. Davies

The stress-strain behavior of Fe-Co and Fe- V alloys containing up to 25 pct solute have been studied in the temperature range 25° to - 196°C. The microyield stress is independent of temperature for all alloys studied, while the temperature dependence of the ordinary yield stress is large and comparable to that for unalloyed iron. An alloy-softening phenomenon is observed for many alloys relative to unalloyed iron, and appears to be a consequence of removal of inter-stitials from solution and their subsequent agglomeration. The ductile to brittle transition temperature is increased markedly by both cobalt and vanadium. Transmission electron microscopy observations reveal that cross slip and cell formation are restricted with increasing solute, which can account for many aspects of yielding and fracture behavior. IRON and other metals of bcc structure slip on many planes of the (111) zone at moderate and elevated temperatures, giving rise to wavy glide. At low temperatures, however, there is a tendency for slip to be restricted to planes of only one or two crystallographic types; in the case of Fe-Si alloys for example, (110) glide predominates, giving rise to planar slip bands."' Restriction of cross slip at low temperatures in iron has been linked by Brown and Ekvall3 to increased strain hardening in the preyield microstrain region, leading to an apparently large temperature dependence of the yield stress. Support for this view has been provided by Lawley and Gaigher4 from a transmission electron microscope study of molybdenum. They concluded that dislocations at lower temperatures, by virtue of their inability to change planes readily, are unable to interact and annihilate, leading to an increase in internal stress and work-hardening capacity. Restriction of cross slip at low temperatures has also been suggested to be an important factor in determining the ductile to brittle transition of single-phase solids, including metals of bcc structure.5 It is pertinent to note that most solute elements tend to raise the ductile to brittle transition temperature of poly crystalline ferrite,6,7 although in some cases, e.g., Fe-Cr7 and Fe-Al,8 the dilute alloys may actually yield at lower stresses than unalloyed iron. It appears, therefore, that solute elements may have an effect analogous to lowering the test temperature with regard to restricting cross glide. Such an effect has indeed been observed in the ionic alloy system KCl-KBr,9 in which bromine atoms, although causing little misfit and consequently little effect on the yield stress of KC1, have a pronounced effect in restricting wavy glide and inducing brittleness. The purpose of the present investigation was to determine the effects of selected solute atoms on the yield stress and fracture behavior of iron, and to elucidate in turn how the slip character was related to these properties. Since it is known that interstitial atoms exert a strong influence on the mechanical behavior of iron, the solute elements chosen for study were vanadium, which reacts strong with interstitials,10 and cobalt, which does not form highly stable interstitial compounds." EXPERIMENTAL PROCEDURE Four-pound ingots of each of the following alloys were vacuum-melted in zirconia crucibles: Fe-1, 5, 10, 25 at. pct Co, and Fe-1, 4, 10, 20 at. pct V. An ingot of unalloyed iron from the same original stock as that used for the alloy was remelted under similar conditions to eliminate variations in interstitial content arising from differing thermal histories. Chemical analyses of the iron, cobalt, and vanadium melt stock are listed in Table I. All ingots were rolled and swaged, commencing at 850°C, to 1/4-in.-diameter bar. The bars were then annealed at 850°C for 1 hr (except that the 10 and 20 pct V alloys were heated for 2 hr) to give a uniform equiaxed grain size of about 0.05 mm. Tensile samples of 0.125 in. diameter by 0.8 in. gage length were utilized for studies of the ductile to brittle transition. A second set of tensile samples were utilized for microstrain experiments in which strain sensitivity of 1 x 10"6 was achieved by a capacitance method.3 Cylindrical compression samples 0.250 in. diameter by 0.4 in. long also were prepared to study the influence of composition on the macroscopic yield stress, and for metallographic analyses of defor-

Jan 1, 1965

By C. S. Matthews, M. J. F. Rosenbaum

The purpose of thir work wax to lcarn it~lzut infori~lation could he obtained from various typs of pilot water floods and to attempt to find the optunum pilot patter11, for a revervoir which had previously been depleted by a solution gas drive. The study was made in the laboratory with mathemetical methods a dynamic analog and a potentiotnetric analog. Results werp tested against the field llistorics of a nrrnlber of pilot water floods. At a reasonable valrre of currzulative injection, the total production rate for the one-injector five-spot should reach about 6.5 per cent of injection rate, and for a four-injector five-spot, about 9 per cent. Accurate estimates of ultimate recovery cannot be made on the basis of such snzall prorluction rates. However, with a pilot composed of nine ir1jector.s and 16 producers the production rate is approximately 50 pcr cent of injection rate at a reasonable value of camulative injection. Sonle inforn~ation for extended performance predictions might he obtained from such a large pilot. These conclusions were drawn on the basis of results obtained for unit mobility ratio, and a sturly using tlre potentiometric analog was made of the effect of other mobility ratios to determine the range of applicability of these predictions. For the four-injector, five-spot pilot with the ratio of production to injection rate (before water breakthrough) is about twice that for with it is about two-thirds; and with M0= 10, it is about one-third For high mobility ratios, it was found that the production rate increased considerably as water-cut increased. These result can be used to modify, qualitatively, the inter.pretntions based on curves for the unit rnobilit\. ratio CaSeS. It was found that the maximum ratio of production rate to injection rate obseriled in field pilot floods was of rhe scime order as that prerdicted by these methods. The time required to reach thisr maximum did not generally agree with the time predicted for a homogeti~orir reservoir. The differcrlce between predicted and observed time of response gives an indication of the permeability profile and of the condition of the producin,g wells. Pilot water floods of the pattern type are generally carried out in reservoirs which have been depleted by solution gas drive and are at low pressure. Under these conditions, oil and water can be considered incompressible. It is assumed that, as the water is injected, an oil bank forms ahead of it and that there is a distinct interface between the water zone (or bank) and the oil zone (or bank) and between the oil zone and the region ahead of the oil zone. It is further assumed that only gas is mobile in the unflooded (gas) region, only oil is mobile in the oil bank and only water is mobile in the water bank. The saturations and the mobilities associated with each zone are assumed uniform. We idealize our reservoir to be homogeneous, horizontal and of constant thickness. Effects of gravity within the producing layer are assumed negligible. If the actual time-dcpendent flow problem is approximated by a acries of steady-state problems. the potential and stream function in the oil bank and water hank satisfy Laplace&apos;s equation in two dimensions. We can therefore use a poteiitiometric analog of this system. Potentiometric models have yielded uscful results in this laboratory&apos; and clsewhere in the study of a variety of secondary recovery problems. For the case where M = I, we generally prefer to use theoretical mcthods as well as a simpler dynamic analog. Except where otherwise noted, the ratio, side of five-spot/wellbore radius. is taken to be 3,600. a figure which corrcsponds to a normal-size wellbore in a 10-acre well spacing. THEORETICAL EVALUATION OF VARIOUS PILOT PATTERNS, Mw0 = 1 <&apos;he theoretical models which we used to examine the performance of various pilots are shown in Fig. 1. Image theory was used to determine the ratio of production rate to injection rate as a function of the volumc of the flood. The ratio of production rate to injection rate was chosen because this is an easily measurable quantity which is characteristic of a pilot

By J. W. Graham

For many years the author has been cognizant of the difficulty encountered by some in treating with the water influx formulas for unsteady-state fluid flow as pertain to the material balance equation. This has particularly applied in establishing reservoir performance and identifying reservoir pressure, which to the practicing engineer has entailed a trial-and-error procedure, and for others has necessitated resorting to computing devices and reiteration processes. In retrospect this difficulty stems from the fact that reservoir pressure in the material balance formulas, as well as associated with the water influx equations, is an inexplicit term, and the work reported in the past is irrefutable. However, what will be presented in this paper is another approach to the problem, whereby the entire material balance equation will be treated by the Laplace transformation, and reservoir pressure which hereto has been inexplicit, can now be isolated by mathematical procedure to relate that parameter with all the factors contributing to its change. This is the simplification entailed, that treats first with an undersaturated oil reservoir as an integrated effect from the inception of production. The second phase pertains to saturated oil reservoirs that encompass a survey traverse. Although both methods of approach are necessarily different in aspect, the most interesting fact is that the mathematics so deduced are identical. Both the linear and radial water-drive systems are incorporated. for which an illustrated factual example is offered for the latter, treating with a saturated oil reservoir. INTRODUCTIO N What is performed in this work is the simplification of an involved computation by advanced analysis. Although such may be construed as a contradiction when one treats with higher mathematics; nevertheless, when direction is given to such an undertaking the results car. be most revealing. Likewise, it is to be mentioned that the bases for these mathematics have been developed on the expediency of the occasion. This is not to be inferred as a qualification of this work, but rather the demands frequently placed upon the author in his private prac- tice in meeting a time limit. A situation, instead of being fraught with hazards, often has given emphasis to creative thought. What will be entailed in this work is the simplification of the material balance formulas by the Laplace Transformation., Although this reveals entirely new horizons that will be given expression in a forthcoming tract, it suffices in the present instance to limit our attention to this phase of the development that treats both with an undersaturated and saturated oil reservoir. To orient the reader&apos;s thoughts as to what is involved in this simplification is the recognition that reservoir pressure, as such, is an inexplicit term in the material balance equation. This is the independent parameter that defines the total history of performance in the author&apos;s&apos; unsteady-state water influx formulas, as well as the basis for the physical dependency of fluid behavior within the formation as prescribed in the Schil-thuis&apos; material balance equation. Therefore, to isolate reservoir pressure, which is the most essential factor in any reservoir study, is rather a cumbersome procedure entailing either a trial-and-error calculation for the engineer; or as some prefer, a reiteration process performed on a computing device. However, once such an equation can be transcribed as a Laplace transformation, this inexplicitness so expressed can be alleviated to identify reservoir pressure as an explicit function of all the factors contributing to its change. This is the simplification encompassed, that will treat first with an undersaturated oil reservoir as an integrated effect from the inception of production, and secondly, with a saturated oil reservoir as a survey traverse. Although the two approaches are necessarily different because of the uhvsics involved. it is an interesting commentary that the mathematics are identical, showing the interdependency of the two methods. In order to acquaint the reader with this development, the simplest case will be treated first; namely, an under-saturated oil reservoir subject to a linear water drive. However, what may be construed for this example as an idealistic case is actually a most practical application in certain parts of the world, where the size of the fields are so large that radial water-drive approaches the configuration of a linear drive. Further, to avoid the repetition of much symbolism, frequent references will be made to the work of the author and an associate on Laplace Transformations3,

By A. Brown

RAPIDLY rising world demand for mineral products has accelerated depletion of the more readily accessible ores, particularly those of premium grade. Operations must proceed at a faster rate to deeper horizons, where there are problems of ground control that restrict economic recovery of the mineral and introduce new hazards to mine personnel. For some of the new Canadian mining fields severe problems of ground stress are still in the future, but much of Canada&apos;s mineral output comes from well established mines that have reached considerable depths. It must also be anticipated that the depletion of premium grade ores will eventually necessitate mining low grade material at competitive cost, and unsolved problems of ground control can materially increase costs. Studies of ground stress phenomena in underground workings are therefore considered a present-day necessity, especially since these investigations must be a long-term effort owing to the highly complex nature of the problem and the difficulty of making full-scale observations. In recent years the Mines Branch of the Department of Mines and Technical Surveys in Canada has conducted such an investigation. This report of the work is primarily concerned with stress problems in some Canadian coal mines and, in particular, with mine bumps. Mines Branch investigations of this and related problems are carried out by a small team of mining engineers and physicists who, with assistance from geologists, pool their special skills in an integrated program. These Canadian investigations combine a field and laboratory approach. Since data obtained under contrasting mining conditions allow useful comparisons of ground behavior under stress, this article will present data gathered under a wide range of Canadian coal mining conditions. Two contrasting longwalls in eastern Canada will be discussed and two dissimilar pillar extraction operations in western Canada. Locale of Observations In eastern Canada observations are being made in the collieries at Springhill, Nova Scotia. The district&apos;s No. 2 mine, which has a history of bump occurrences dating back to 1917, is currently being worked at a depth of 4200 ft. The mining method is longwall retreating along the strike and the practice is to retreat three walls in line, each about 350 ft long. There is no machine cutting or shooting—the coal is hand-picked and hand-loaded onto face conveyors. There are three rows of hardwood chock block supports parallel to the coal face. These supports are built during the two daily coal loading shifts, and the rear line is withdrawn during the midnight shift. The goaves are partially packed by stone midwalls 12 ft wide which are built forward daily in step with the face advance. The seam dips at 15° and averages 9 ft of strong, well cleated bituminous coal enclosed in competent beds of shales, sandy shales, and sandstones of Carboniferous age. The bumps rarely disturb the retreating longwall faces but manifest themselves as violent upthrusts of pavement in the levels leading to the walls. Observations have also been made in Springhill&apos;s No. 6 mine, which operated in a 5-ft seam of coal at a depth of about 2500 ft. Although No. 6 mine was

Jan 1, 1959

By P. Gordon

An isothermal jacket microcalorimeter, supplemented by metallographic, microhardness, and X-ray measurements has been used to study the isothermal annealing of high purity copper after room temperature tensile deformation. The amount of stored energy released during annealing has been measured as a function of deformation in the range 10.8 to 39.5 pct elongation. The data have shown the major heat effect to be associated with recrystallization and have allowed an analysis of the recrystal-lization kinetics and the calculation of activation energies of recrystallization. WHEN a metal is deformed plastically, some of the energy expended is dissipated as heat during the working process, while the remainder is stored within the metal in the form of lattice distortions and imperfections. During subsequent heating of the metal, the distortions and imperfections can be largely annealed out and the associated stored energy released as heat. It is apparent that measurements of the evolution of stored energy during such annealing may produce important information concerning the nature of the annealing mechanisms and the imperfections involved. Some excellent studies of this type have been made in the past, notably those of Taylor and Quinney,&apos; Suzuki,2 Bever and Ticknor,3 Borelius, Berglund, and Sjöberg,4 and Clarebrough et al.5,6 None of this work, however, employed isothermal techniques, with the exception of the Borelius studies&apos; in which only the early annealing stages were investigated. Since isothermal measurements, as compared with heating or cooling curve, have the merits that 1—they reveal the kinetics of a process more clearly, 2—the results obtained are more easily applied to theory, and 3—most fundamental investigations of annealing using techniques other than calorimetry have been carried out isothermally, it was considered important to apply calorimetry to the study of the isothermal annealing of metals. Accordingly, an isothermal jacket calorimeter of the Borelius type,&apos; supplemented by metallographic, hardness, and X-ray measurements, has been used to study the annealing of high purity copper after room temperature tensile deformation. Experimental The microcalorimeter has been described fully elsewhere." Briefly, the specimen to be studied is placed in a constant temperature environment of virtually infinite heat capacity achieved, as shown in the drawing of Fig. 1, by means of a vapor thermostat. A high thermal resistance is provided between the sample and the environment and a sensitive differential thermopile (see Figs. 2 and 3) arranged with half its junctions in contact with, and thus at the constant temperature of, the environment, and the other half in contact with the sample. A reaction in the sample develops a small difference in temperature, AT, across the thermopile, which is followed by a recorder-galvanometer set-up as a function of time, t, and is converted to reaction heat per unit time, P, by the use of the equation AT P=a?T + b AT dt The constants, a and b, in Eq. 1 are determined by a simple calibration, making use of the Peltier heat developed by a small current run through the junction of a thermocouple located in an axial hole in the specimen (Fig. 2). In its present form, the limit of sensitivity of the calorimeter is a heat flow of 0.003 cal per hr. The copper used was the spectroscopically pure metal supplied by the American Smelting and Refining Co. in the form of 3/8 in. diam continuously cast rod, reported to be 99.999+ pct Cu. A small amount of the copper was available at the start of this work and is referred to hereafter as lot A. A second batch, lot B, was obtained later, most of the results described subsequently being for this lot. As will be seen, there is some indication that lot A was somewhat purer than lot B, but it is not known whether this difference was present in the as-received metal or arose during subsequent handling. The two lots of copper were remelted and cast into two 1½ in. diam ingots in vacuo, using high purity graphite crucibles and molds. The ingots were upset several times to break up the large cast grains, and then rolled and swaged to rods 0.391 in. in diameter, using several intermediate anneals with about 40 pct reduction in area between anneals. The penultimate anneal was 2 hr at 350°C. X-ray examination showed no marked general preferred orientation in the resulting rods. The grain structure typical of the two rods is shown in the micrograph of Fig. 4." It was found to be virtually im- possible to get an unambiguous measure of the absolute grain size in the two annealed rods because of the profusion of annealing twins and the lack of regularity of the grain boundaries. However, counts of the number of boundaries intersected per unit length along a random line on a polished section, making a correction for the proportion of boundaries (about half) estimated to be twin boundaries, gave a figure of about 0.015 mm for the average grain diameter. The grain size of the rod from lot A was about 5 pct smaller than that from lot B. The rods were cut into 1 ft long bars and these deformed in tension at room temperature to various total elongations in the range 10.8 to 39.5 pct. A strain rate of 1 pct per min was used. The deformed bars were then stored in a dry ice chest until such time as samples were to be cut from them. Five bars deformed as indicated in Table I were used for the subsequent tests. In all cases, all the calorimeter.

Jan 1, 1956

By Klaus-Peter M. Hanke

INTRODUCTION In early 1979 Jim Walter Resources, Inc. (JWR) of Brookwood, Alabama approached TMCI Construction, Inc (TMCI) to make a proposal on a program that involved the sinking of up to 10 ventilation shafts of approximately 6.7 m (22 ft) diameter and ranging in depth from 500 to 700 m (1650 to 2300 ft) for the JWR coal mines in Alabama. At this time TMCI was already constructing the first spiral underground bunker (capacity 2000 tons) in North America for the JWR organization at their No. 4 mine in Alabama. The TMCI proposal was based on the use of the mos modern large diameter shaft boring machine rather than sinking the shafts using the conventional drill blast-muck technique. The proposal was made based o: the experiences by the parent company, Thyssen Schachtbau, which has been using this type of machin in Germany for shaft boring since 1971. As a result of the TMCI proposal JWR issued a purchase order to TMCI for the construction of four 6.7 m (22 ft) diameter, concrete lined, unfurnished ventilation shafts ranging in depth from 500 to 700 (1650 to 2300 ft). An order was thus placed with WIRTH Machinen- and Bohrgeraete Fabrik GmbH, in Germany for the manufacture of a model 650/850 E/Sch "Schachtbohrmaschine" (Vertical Shaft Borer = V-mole which arrived on site in Alabama in early 1981. The first V-mole GSB 450/500 was introduced in Germany in 1971 and was capable of enlarging in one step a pre-drilled 1.2 m (4 ft) pilot hole to 4.5 - 5.0 m (14.7 - 16.4 ft). This machine has sunk 9 staple shafts and deepened one surface shaft for a total of 2360 m (7740 ft) of shafts. On the last shaft boring operation in 1978 the machine was converted as an experiment to drill without a pilot hol using a hydraulic pumping system to remove the cutting debris. A second generation machine, the SB VI 500/650, was introduced in 1977 for enlarging the pilot hole to a range of 5.0 - 6.5 m (16.4 - 21.3 ft) diameter. This machine is still in operation and has already drilled well over 2000 m (6500 ft) of shaft. The third generation of V-mole, the SB VII 650/85( for diameters from 6.5 to 8.5 m (21.3 to 27.9 ft) was: commissioned in May 1980 and has been used for two surface shaft deepenings totalling 606 m (1990 ft) with another scheduled for 1982. The main advantages favouring the use of such V-moles were identified as: 1) A reduction in manpower to the crew required in a conventional shaft sinking operation. 2) A considerable reduction in time to complete a shaft compared to conventional techniques. 3) The use of the V-mole eliminates many of the hazards encountered in conventional sinking. Based on the successful performance of the first three V-moles in Germany, Thyssen Schachtbau decided to employ this principle abroad. In 1980 a second machine of the third generation was built and is now operated by TMCI Construction, Inc. in Alabama. The first shaft was completed at the end of 1981 and this paper describes the method of operation including some unique aspects not attempted on prior V-mole operations and some of the statistics arising out of the experiences during the first shaft boring operation. THE NO. 7 MINE FAN SHAFT SITE Jim Walter Resources, Inc. was formed in 1970 to exploit the coal field in Alabama on the southern tip of the Appalachian coal field. The coal reserves amount to around 650 million tons of mainly good quality coking coal of which about 350 million tons are to be extracted over the next 30 years. Shaft sinking and preparatory work began in 1972, and at present 6 mines are producing around 5.4 million t.p.a. Annual production is to expand to 10 million t.p.a. as soon as possible, and the ventilation shafts to be sunk by TMCI play a vital role towards attaining this goal. The first shaft site is located at the No.7 mine, near Brookwood, Alabama. The actual location of the shaft relative to the production shafts is shown on the mine plan (Fig. 1), which also shows the room-and-pillar extraction system used at present. The mine plan further shows the conveyor route used for the muck removal. The geological survey showed that the strata consisted of horizontal layers of mainly sandstone, sandy shale and shale interspersed with several coal seams. The seam being extracted at the No. 7 mine is a combined seam made up of the Blue Creek and Mary Lee seams at a depth of 513 m (1682 ft) and having an average seam thickness of about 2 m (6 ft). At the beginning of September 1980 the surface site preparation and pre-grouting work was completed by JWR, and TMCI was able to commence with Stage I of the shaft sinking program - the drilling of the pilot hole.

Jan 1, 1982

By K. Brack, G. H. Schwuttke

Annealing properties of subszerface amorphous lavers produced through high-energy ion implantation in silicon are studied. The buried layers are produced through the implantation of ions (nitrogen), ranging in energy from 1.5 to 2 mev. X-ray interference patterns, transmission electron microscopy, and resistivity profiling are used to study the annealing characteristics of the ion damage. The annealing experiments indicate a low temperature (below 700°C) and a high temperature (above 700°C) region. Significant changes occur in the amorphous layer during the high-temperature anneal. Such changes are corre-lated with the re crystallization of the amorphous silicon and the formation of subsurface (buried) silicon-nitride films. TODAY&apos;S main problems in the field of ion implantation are related to the accurate determination and prediction of 1) the distribution profiles of implanted ions, 2) the lattice sites occupied by the implanted ions, 3) the lattice damage produced through ion implantation, and 4) the annealing characteristics of damage centers in the lattice. This paper reports investigations concerned with the problems listed under 3) and 4). EXPERIMENTAL Our investigations cover the energy range of incident ions from 100 to 300 mev and from 1 to 2.5 mev. The emphasis of this study is on the energy range from 1.5 to 2 mev. The experiments are conducted with single charged nitrogen ions. To implant the ions a van de Graaff generator is used as described by Roosild et al.1 Accordingly, a gas containing the desired ion specie is passed through a thermome-chanical leak into a radio frequency activated source. The positive ions are driven into the van de Graaff with the help of a variable voltage probe. Emerging from the accelerator the ions drift into a magnetic analyzing system and here the desired ion specie is bent 90 deg into the exit port. The ion beam leaving the analyzer is defocused and drifts down a 4-ft long tube to hit the silicon target. At this position the 20 pamp ion beam has a circular cross-section of 2.1 cm. N2 is used as a source gas for nitrogen ions. The implantation target is silicon with zero dislocation density, 2 ohm-cm resistivity, (111) orientation, mechanically-chemically polished, and 1 mm thick. The target is mounted on a water-cooled heat sink and kept at room temperature. A fluence of 1015 to 1016 ions per sq cm is used. RESULTS 1) Silicon Perfection after Bombardment. High-energy ion bombardment of silicon has some striking effects on lattice perfection. Some results were reported in detail previously at the Santa Fe conference2 and are here briefly summarized for the benefit of the experiments described in the following. 1.1) Identification of Surface Films on Silicon. After bombardment all samples are found to be coated with surface films. The films on the silicon surface vary in thickness and color; they can be transparent, slightly brown, or opaque. The films are thicker and darker in the high-intensity area of the beam and they delineate the bombarded surface area of the crystal. The films produce electron diffraction patterns characteristic of carbon and of SiO2. Carbon is predominant. The presence of carbon in these films was confirmed by use of the electron microprobe. Formation of the films occurs independently of the ions used and is attributed to a contaminated vacuum of the high-voltage machine. The carbon is most likely the product of the pump oil which is cracked and polymerized under ion impact. The films stick tenaciously to the silicon surface and burn off in a low-temperature Bunsen flame. 1.2) Mechanical Perfection of the Silicon Surface. The mechanical perfection of the bombarded silicon surface was investigated through optical microscopy, electron microscopy in which the replica technique is used, and optical interferometry. No mechanical damage of the surface was visible after bombardment. However, if a bombarded sample is soaked for several minutes in hydrofluoric acid (HF), gas bubbles may develop in certain spots of the silicon surface. It is also noted that in these areas the surface film starts to peel off. Relatively large patches of film come off if the sample is soaked in HF during ultrasonic agitation. After HF treatment, pits may be present on the silicon surface. The pit dimensions are estimated to be as large as 50 µ. The pits appear in the region of most intense irradiation. 1.3) Lattice Perfection After Bombardment. No lattice damage is found on the silicon surface. Electron transmission micrographs and selected area diffraction patterns of the surface show no difference before and after bombardment. Measured approximately 2 µm down from the surface, the silicon lattice throughout this depth is of good perfection. Well-defined Laue spots and Kikuchi lines are obtained from the surface as well as from the indicated area below the surface. However, some radiation damage is dispersed in this top layer. A sharp boundary line separates this surface layer from a highly damaged layer which extends further downward into the silicon. Typical of this

Jan 1, 1970

By P. Greenfield, C. C. Smith, A. M. Taylor

The Mg-Zr alloy ZA and Mg-Mn alloy AM503(S) are shown to have a markedly improved resistance to creep deformation after suitable heat treatments. This improvement makes them suitable for certain stress-bearing fuel element components in nuclear reactors. The extent of strengthening is described and an explanation of the behavior of both materials is given, based on a combination of strain-aging and grain growth. The increase in operating temperatures of fuel element components in Calder Hall type nuclear reactors has necessitated the development of magnesium base alloys with a very high resistance to creep at temperatures up to 500°C. Such alloys are not required for fuel element cans, which require high-creep ductility rather than strength, but for can supporting and stabilizing components, which are needed to support the imposed loads without deforming more than about 1 pct in times of up to 40,000 hr. The amount and type of alloying addition made to magnesium for these parts is limited by the necessity of keeping the cross-section to thermal neutrons as low as possible. The alloys must also possess a high resistance to oxidation in CO2. Alloys which have been developed for this application include ZA, an alloy of magnesium with 0.5 to 0.7 pct Zr and AM503(S), an alloy of magnesium with 0.5 to 0.75 pct Mn. In the as-extruded condition these alloys are very weak and ductile in creep but it has been found that they can be strengthened to a significant extent by heat treatment. This paper describes the method of developing a high-creep resistance in ZA and AM503(S), the extent of the strengthening produced and discusses the probable mechanisms of strengthening. TEST MATERIALS Specimens were taken from typical casts of ZA and AM503(S) alloys extruded into 2 1/4-in.-diam bars, supplied by Magnesium Elektron Ltd. Typical analyses of the bars were as follows: The as-extruded mean grain diameter was 0.001 to 0.002 in. for the ZA alloy and 0.003 in. for the AM503(S) alloy. EXPERIMENTAL METHODS Extruded bars of ZA alloy, 2 1/4 in. in diameter and 9 in. long, were heat treated in electrical resistance furnaces in an atmosphere of flowing CO2 containing 50 to 300 ppm water, thereby reducing the extent of oxidation compared with that which would have occurred in air. Heat treatments were carried out at 600oc for times of 8, 24, 48, 72, and 96 hr and material was subsequently both furnace cooled and water quenched. In order to measure the effect of time of heat treatment, specimens were creep tested at 400°C and 336 psi for about 1000 hr. Subsequently, the behavior of material heat treated for 96 hr at 600°C and furnace cooled was tested at a variety of stresses from 200° to 500°C. Tests were also conducted at 200o and 400°C on material in the as-extruded condition for comparative purposes. With the AM503(S) alloy, only the effect of heat treatment at 565°C for 4 hr was examined. It has been shown1 that such a heat treatment produces marked strengthening in this alloy. Tests on this material were conducted at a variety of stresses at 200°, 300°, and 400oc with comparative tests on as-extruded material at 200o and 400°C. The creep tests were carried out on machines using dead-weight loading and direct micrometer strain measurements on specimens 5 in. long and 0.357 in. diameter. At temperatures of 400° C and below, the creep tests were conducted in air, but at higher temperatures an atmosphere of CO2 was used. Grain size measurements were made on ZA in the extruded and heat treated states and on each specimen after creep testing. This was done by a line count of a minimum of 20 grains in two or three random fields in the longitudinal and transverse directions. The same method was used for measuring the grain size of as-extruded AM503(S), but the grain size of the heat treated material was so large that this method could not be employed. For heat-treated AM503(S) the large grained characteristics (between 0.1 and 1 in.) were confirmed by the measurement of individual grains. In the case of the ZA alloy, specimens taken from various stages in the program were analysed for hydrogen by a combustion method. Material in various states was also analysed for the soluble and insoluble zirconium content by dissolving in dilute hydrochloric acid. This technique has been useda for the determination of amounts of zirconium present

Jan 1, 1962

By R. D. Schoone, J. T. Michalak

Recovery, recrystallization, and texture development of a cold-rolled aluminum-killed steel have been studied during simulated box annealing. Two different initial conditions existed prior to cold rolling: 1) essentially all of the nitrogen in solid solution and 2) most of the nitrogen precipitated as AlN. The combined effect of nitrogen and aluminum in solid solution before annealing was to inhibit recovery and sub-grain growth at temperatures above about 1000°F and to raise the recrystallization temperature range on continuous heating at 40°F per hr from 1000"-1050°F to 1065"-1085°F. For the material with nitrogen and aluminum initially in solution there was an inhibition in the nucleation of the (001) [110] texture component and an enhancement of the (111) [110] texture component. The differences in annealing behavior mzd texture development are attributed to preprecipitation clustering of aluminum and nitrogen at subboundary sites developed by prior cold working. THE annealing of cold-worked aluminum-killed steels has been the subject of numerous investigations.&apos;-&apos;2 These studies have been concerned with kinetics of recrystallization, with microstructure and texture development, and with the individual and combined effects of composition, thermal history prior to cold rolling, and heating rates during subsequent annealing. It has been shown that the inhibition of recrystallization, and the development of the pancake-shaped grain and recrystallization texture characteristic of aluminum-killed steels, can be associated with the precipitation of A1N particles during a recrystallization anneal involving heating rates in the range 20" to 80°F per hr. If the AIN is precipitated before cold rolling or if more rapid heating rates are employed, the cold-rolled steels recrystallize more rapidly to an equiaxed grain structure and texture comparable to that of rimmed low-carbon steel. The retardation of recrystallization, the development of the elongated grain structure, and the pronounced (111) texture have been attributed to: 1) precipitation of A1N at prior cold-worked grain boundaries to form a mechanical barrier to grain boundary migration;&apos; 2) precipitation on the boundaries of the growing recrystal-lizing grains as well as on cold-worked grain boundaries;&apos;" and 3) preprecipitation clustering or precipitation on subboundaries to retard recovery, nucleation, and growth. The present study was undertaken to study in more detail recrystallization and texture development during commercial box annealing of cold-rolled aluminum-killed steels. Comparison of the annealing be- havior after cold rolling, for two different conditions prior to cold rolling, was made in an attempt to define more clearly the role of aluminum and nitrogen in forming the recrystallization texture. A) MATERIAL AND PROCEDURE The material used in this investigation was a commercial low-carbon aluminum-killed steel which was hot-rolled with a finishing temperature of about 1565"F, then coiled at about 1020°F. The composition, in wt pct, was: 0.050 C, 0.30 Mn, 0.007 P, 0.019 Si, 0.03 Cu, 0.02 Ni, 0.02 Cr, 0.045 Al, and 0.004 N. Two 4.5 by 13 by 0.078 in. sections were cut from the center section of a hot-rolled panel and one of these was reheated to provide two different conditions prior to cold rolling: low AlN: as commercially hot-rolled, with aluminum and nitrogen in solid solution; and high AlN: as commercially hot-rolled, then reheated at 1300°F for 3.5 hr to precipitate most of the nitrogen as AlN. ~etallc&a~hic examination indicated that the reheating did not change grain size nor carbide distribution (some spheroidization of pearlite was noted). Texture analysis at half-thickness level showed that both sections had the same substantially random as-hot-rolled texture. The results of check chemical analysis of each sample are given in Table I. Both sections were cold-reduced 65 pct on a laboratory rolling mill to a final thickness of 0.027 in. Cold rolling, in one direction only, was in the direction of the prior hot rolling. Specimens 1.0 by 1.25 in. were cut from the cold-rolled sheets and given a simulated box anneal in an atmosphere of 2 pct HZ-98 pct He. Specimens were heated at a constant rate of 40°F per hr from room temperature to various temperatures in the range 750" to 1300°F and cooled immediately by withdrawal to the water-cooled end of a tube furnace. The temperature in the 6-in. uniform hot zone of the furnace was controlled within 3"F. Selection of the individual specimens was made to give a random distribution of annealing temperatures with respect to location in the cold-rolled sheet. At least two specimens of each condition were annealed to the same temperature and smaller specimens for light microscopy, transmission electron microscopy, and X-ray studies were prepared from each of these. Rolling-plane sections for each of these studies were taken at half thickness. Light microscopy and transmission electron micro-

Jan 1, 1969

By C. D. Williams, C. E. Ells

The susceptibility of quenched and aged Zr-2.5 wt pct Nb alloy to embritt2ement during irradiation has been examined for a number of solution temperatures and aging times. Material quenched from temperatures approximately 40°C below the transus has high tensile ductility, and this ductility is insensitive to aging at 500°C or to irradiation. If, however, the material is quenched from temperatures above the transus it becomes highly susceptible to loss of ductility either from aging at 500 or from irradiation. Inter granular failure is characteristic of the materials having low ductility. The distribution of the equilibrium phase is found to control the susceptibility to embrittlement by restricting 6 grain growth during heat treatment and thus influencing crack propagation. IN zirconium, as in titanium, -stabilizing alloy additions are used to obtain high strengths via quench and age heat treatments, and the Zr-2.5 pct Nb alloy has been developed1 because of its strength advantage over the Zircaloys. Early in the development of the Zr-2.5 pct Nb alloy the problem of 13 embrittlement was appreciated, and for this reason the solution temperature was chosen below the p transus.&apos; In the course of irradiation studies on quenched and aged Zr-2.5 wt pct Nb alloy it was found&apos; that irradiation introduced an important aspect of p embrittlement, riz., material quenched from the phase and aged 24 hr at 500°C was severely embrittled by moderate doses of neutron irradiation. This effect had not been studied in titanium alloys. In titanium the metallurgical features leading to 0 ernbrittlement were found to be structures with: a) coarse a platelets at the grain bondaries, b) finely dispersed a uniformly distributed throughout the (0) matrix,6 c) Widmanstatten a-13 with more than 50 pct P, d) the presence of some metastable p transformation products,3 and e) large prior -phase grain size.5 Alternatively, the presence of a uniform distribution of coarse a was conducive to high ductility and a structure largely of equiaxed a was very dctile. The detailed mechanisms of the embrittlement have not been worked out for all of these conditions, although weakness at either a-matrix boundaries or prior p grain boundaries have been prominent in the eculation. It was proposed that acicular a might act as a mild notch, and low ductility has been associated with easy fracture along its boundary.&apos; There have been two opposing suggestions for the source of the high ductility associated with equiaxed a phase. JaffeeB proposed that this a would accept a large por- tion of the oxygen, thus increasing the ductility of the matrix, whereas after study of a Zr-Nb-Cu alloy Weinstein and oltz proposed that the a phase, softer than the martensitic matrix, acted to blunt cracks formed in the matrix. In the present work we have studied the effect of neutron irradiation on the ductility, particularly the P embrittlement, of the Zr-2.5 wt pct Nb alloy. By a variation of solution temperature and aging time a variety of metallurgical conditions have been examined, and a range of resultant ductilities obtained. The ductility has been related to the material microstructure and mode of fracture. EXPERIMENTAL The alloy used in the present work came from two separate ingots fabricated into rod of 3/8 or i in. diam, Table I. For both batches the P transus temperature was approximately 890° C. Most of the heat treatments were done directly on lengths of the j} in. diam rod, after which the tensile test specimens were machined. Quenching was achieved by dropping rods from a dynamic vacuum into water, the cooling rate estimated to be 2 100°C per sec. For aging the rods were encapsulated in evacuated silica tubes. Round tensile test specimens, with gage diam and length 0.160 and 1.0 in., respectively, were used throughout and pulled at room temperature or 300°C on Instron tensile machines, at a crosshead speed of 0.05 ipm. Specimens were irradiated in the NRX and NRU reactors, in facilities described in previous publications.&apos;0 The metallurgical conditions examined have been: All tensile test specimens were machined with axes in the axial direction of the swaged rod. Although the specimen had a degree of preferred crystallo-graphic orientation with basal plane normals both parallel with and perpendicular to the tensile axis, the material was comparatively isotropic." The techniques of thin foil examination in the electron micro-

Jan 1, 1970

By J. Paone, S. Tandanand

This paper studies the behavior of rock at the initial state of crater formation resulting from stresses created under a drill bit. The purpose of this study is to determine which mechanical properties of rock are important in rock fragmentation by drilling. Although a definite relation between the drilling strength and relevant mechanical properties has not been established, maximum yield strength or hardness of rock is apparently a parameter of drillability of rock. The strengths of rock were considered from the Mohr-Coulomb criterion from which the surface of failure was constructed. The results from previous triaxial tests on Solenhofen limestone were adopted in establishing a limit of failure. Inelastic behavior of Solenhofen limestone was observed under a low velocity impact of a hemispherical bit and under static indentation with a similar bit. Permanent set at low applied loads in the indented area was measured with an interferometric technique. A quantitative determination of strengths of the rock was made under static indentation. The maximum yield strength estimated from the average stress over the contact area for plastic deformation was used as the crushing strength of rock under a drill bit. Much research has been done on energy requirements and mechanisms of energy dissipation to perfect rock fragmentation by a drilling process. But more needs to be done. More needs to be known about the mechanisms of energy dissipation or failure criteria of rocks in the drilling process in order to evaluate the efficiency of energy requirements in specific rock fragmentation. This paper examines some published studies on rock failure and energy dissipation and presents some findings in that phase of research concerned with rock fragmentation by drilling. This work is specifically concerned with rock behavior at an early stage of failure induced by a concentrated load. Consideration is limited to the primary phase of the crater formation under drill bit, i.e., before chipping takes place. Failure Phenomena of Rocks: Failure of rocks can be classified into two types, fracture and plastic flow. Both involve separation of material to form new surfaces with complete or partial loss of cohesion. Fracture is further classified as extension (or cleavage) fracture and shear fracture. Extension fracture involves separation in a plane without shear stress component, while shear fracture involves slippage along a plane as a result of combined stresses. Then, shear fracture inclines to the axes of the principal stresses. Plastic flow occurs under combined stresses, especially at high confining pressure and temperature, and denotes macroscopically irrecoverable deformation of rocks. Flow mechanisms have been classified as in-tergranular failure, intragranular gliding, and re-crystallization of mineral constituents.6 Failure phenomena in rocks are complicated because they include fractures and plastic flow as well as a friction process developed intrinsically as the internal stresses increase. All can occur in one rupture process, depending on the varying stress conditions. Both fracture and plastic flow are encountered in rock drilling. Rock failure under a drill bit as observed in drop tests simulating a single blow of a percussion drill, consists of two types, crushing and chipping. Crushing is considered as a separation of material particles by many fractures resulting from the application of high compressive stresses exceeding the strength of rock at the contact area. Chipping results from subsurface fractures extended to the face surface; this phase is preceded by crushing or surface deformation. The state of stress under the drill bit and the strength of rock create and control these two types of failure. The state of stress under the bit and in the vicinity of the contact area depend on the bit configuration and the magnitude of applied force. The strength of rock, characterized by its ability to resist penetration, depends on its composition and structure. However, the term "strength" quantitatively defined, is still ambiguous and may or may not correspond to the tensile, compressive and shear strength obtained from simple tests. Rock Failure Criterion: Rocks are weak in tension, their tensile strength being many times less than their compressive strength. This characteristic excludes

Jan 1, 1967

By I. M. Roberts

THE war emergency has affected every phase of industry. The gas and coke-oven companies have sought faithfully to discharge their responsibility in this critical period and have willingly modified their operations where possible to meet the ever increasing demands made upon them. Our company made commitments for blast-furnace coke for war purposes which necessitated a reduction in coking time in order to produce the amount required to. meet the new demands. At the same time there were certain customers of long standing, who had been supplied with foundry and egg-sized coke produced on fairly long coking periods, who also were engaged in war work and whose patronage we desired to retain. Coke produced on short coking rates from the coal mixture we were then using would not have been satisfactory for these customers. The average width of our ovens is 19 ¾ in., which is a little wider than the more modern ovens of the present day. They were originally designed to give somewhat cool tops in order to produce a rich gas. This necessitates carrying the heats a little on the warm side so that the tops will be fully carbonized. A reduction in coking time, as is generally known, is accompanied by a reduction in the average size of the coke produced. This is due to the greater shrinkage that takes place at the higher temperatures required to carbonize the charges in a shorter time. The net result is that the coke is more cross fractured and longitudinally fractured and breaks up into small sizes on handling. The cokes produced from the better coking coals seem to be more susceptible to fracture at high temperatures than those from poorer coking coals. A coal mixture that produces a beautiful foundry-sized coke at 30 to 36 hr. may yield a product at 18 hr. that would be so badly fractured as to be unsatisfactory for foundry practice. COKING CHARACTERISTICS OF COALS Our problem was to find some economical innovation and develop a method that would enable us to reduce the coking time and still produce a coke satisfactory to our foundry trade. However, before discussing the results of our present operations, it might be well to present a few observations on the coking characteristics of coals in general. Most coke-oven operators carbonize a blended mixture of coals. It may consist of a single high-volatile coal with a single low-volatile coal, or of a combination of several high-volatile and low-volatile coals. Medium-volatile coals of the Eagle seam are used for the production of high-grade foundry coke. Medium and high-volatile coals are often blended with one or more low-volatile coals. The possibilities are almost infinite, but the combinations are limited by such factors as cost and facilities for handling multicoal mixtures, and by other practical considerations. Every coal has characteristics that make it blend better with a particular coal or coals in preference to others. This property has

Jan 1, 1944

By H. Doi, Y. Fujiwara, K. Miyake

In order to throw light on the mechanism of plastic deformation of WC-Co alloys, compressive tests of WC-(7 to 43) vol pct Co alloys have been carried out at room temperature, and stress-micro strain relation has been investigated in detail. The analysis of the factors affecting the yield stresses reveals that the yield stresses can be predicted by modified Oro-wan&apos;s theory if one properly estimates the planar in-terfiarticle spacings. Conzpressive straining of some of the alloys by 0.066 to 0.17pct increases the decrements by a factor of as much as 3.4 to 14, whereas the corresponding increase in the electrical resistivities is less than 10 pct. The analysis of the decrement data in terms of -Gramto and Lücke theory shows that the marked increase is attributed to increased dislocation darnping itt the binder (cobalt) phase. By cornbilling the decrement data and the conzjwession duta, one obtains the relation between flow stress in shear (?t) and increase in dislocation density (p): At = const . v6 . This is interHeted to mean that the mechanism of strain hardening of CirC-Co alloys is essentially sarne as the one for dispersion strengthened alloys. The possible effect of bridge formations between the carbide particles has also been examined. OWING to the combination of hardness, strength, and other physical and chemical properties, WC-Co alloys have opened the way for unique fields of applications, the recent ones being, for instance, anvils for super-high-pressure generation apparatuses. In such applications, the alloys are frequently subjected to very high compressive stresses: these stresses may cause the alloys to deform plastically and eventually to fail. However, much remains obscure regarding the nature of the plasticity of the alloys. Evidently, the alloys owe their high strength to the hard carbide particles which frequently occupy as much as 80 to 90 pct in volume fraction, whereas the ductility required for practical applications is provided by the small amount of the binder phase between the carbide particles. When the volume fraction of the carbide phase is not very large, deformation behavior of the alloys may be described by some of the current dispersion strengthening theories. However, greatly increasing the carbide phase is thought to lead to some carbide skeleton structure or bridge formations owing to the increased chances for direct contacts between the carbide particles;1,2 this may appreciably affect the plasticity of the alloys. Regarding the effect of formation of the carbide skeleton structure, it is interesting to note the work by Ivensen et al.3 on compression tests of the alloys containing somewhat large carbide particles; they observe extensive generation of slip bands in the carbide particles after application of some preliminary compressive stresses. They interpret the results in terms of plastic deformatiot: of the carbide particles which are supposed to have formed a skeleton structure; the binder phase plays only a passive role, at least in the early stages of the deformation. That carbide crystals exhibit microplasticity at room temperature is apparent from the work of Takahashi and Freise4 and French and Thomas5 on indentation of WC single crystals. On the other hand, Dawihl and coworkers6-10 maintain that even when volume fraction of the carbide phase is very large (for instance, more than 90 pet), a very thin binder layer generally exists between the carbide particles. They interpret the results of the extensive mechanical tests in terms of the plasticity of such a layer. Gurland and Bardzil11 point out that decrease in ductility of the alloys with increase in the carbide phase is caused by the effect of plastic constraint exerted by the dispersed carbide particles. Drucker12 further develops this concept from a continuum-mechanics approach on an assumption that a continuous thin binder layer separates the carbide particles. A common feature of the studies reported so far on the plasticity of the alloys is that the information deduced is invariably qualitative in nature. Thus, very few systematic experiments for obtaining reliable and sufficiently detailed stress-strain curves of the alloys varying widely in the microstructural features have been carried out. In particular, it may be of special interest to investigate in detail the early stages of the plastic deformation of the alloys in order to shed light on the strengthening mechanism. However, such work appears to be extremely rare. Doi et al.13 recently reported a first brief account of the results of some quantitative analysis of the plasticity of the alloys in terms of dislocation theory. Their experiment was rather limited in the composition range covered (volume fraction occupied by the carbide phase: 79 to 83 pct), and thus they could not necessarily elucidate the controlling mechanism of plastic deformation of the alloys of a more general composition range. Consequently, in the present investigation, deformation behavior and some other physical properties of the alloys were investigated and discussed in more detail over a much wider composition range. SPECIMEN PREPARATION WC-Co alloys used in this experiment were prepared in cylindrical or rectangular form by sintering in vacuo compressed mixtures of tungsten carbide and cobalt

Jan 1, 1970

Jan 1, 1926

By AIME AIME

THE Seventh International Petroleum Exposition and Congress to be held in Tulsa, Okla., Oct. 4 to 11, inclusive, in true western spirit promises to be bigger and better than ever. The Exposition has become an established institution. It gives opportunity to petroleum engineers, technologists, and operators to see each year at one place what the tool makers and machinery manufacturers have to offer which is new or better. It has truly become a place "where men, methods and machinery meet." It is also a convenient focus for technical meetings of various kinds devoted to petroleum and natural gas problems. &apos;The Petroleum Division of the A. I. M. E. has for several years held its chief fall meeting at Tulsa just preceding the opening of the Es- position. This year our meeting will be on Oct. 2 and 3 and it will be held as usual at Hotel Mayo. The Mid- Continent Oil and Gas Association will, as usual, hold a meeting during the Exposition and this year the Petroleum Division of the A. S. M. E. will hold a three- day session, Oct. 6-8, in the auditorium on the Esposition grounds. In all, six technical sessions are planned by this Society, and aside from reports of committees some 20 technical papers are to be presented. Members of the Institute should attend its own meeting and stay over for as many days as possible for the other meeting at which they will hear and see much of helpful interest.

Jan 1, 1930

By AIME AIME

ABOUT 55 attended the general session of the Nonferrous Metallurgy Committee on Wednesday afternoon. In opening the proceedings the Chairman, Frank G. Breyer, served notice of his intention to make an early start this year in securing papers for his committee. He voiced the thought that more importance should be attached to the prompt publication of data on new advances in practice; the record of technical progress should be written before the sharpness of the current image becomes blurred by the veil of time. As an illustration, Mr. Breyer declared that great strides have been made in the zinc industry during the past nine years, whereby zinc ore is converted directly to the oxide in large mechanical furnaces, yet the literature is confined to patents.

Jan 1, 1933

By E. S. Tankins, G. R. Belton

A simple solution model, based upon the formation of molecular species, is developed for strongly electronegative dilute solutes in liquid binary-metallic solvents. Two approximations are considered for the relative concentrations of the species: the random and the quasi-chemical. Equations are presented for the partial molar free energy, enthalpy, and entropy of mixing of the solute. An experimental study has been made of equilibrium in the reaction H2 6) +0 (dissolved) = H2O(g))for the liquid Cu-Co alloys. The standard free energy of solution of oxygen is presented as a function of composition for the alloys at 1550°C and as a function of temperature for five of the alloys. The experimental results for these alloys and also for Cu-Ni alloys are shown to be in reasonable agreernent with the theory in the random approximation. A knowledge of the thermodynamic behavior of dilute solutes in liquid metals and alloys is of importance in understanding and designing refining and alloy-making processes. Accordingly, several attempts have been made to derive suitable solution models to forecast the effect of a third component on the activity coefficient of such a solute in a metal. Alcock and Richardson&apos; reviewed the literature prior to 1958 and also showed that a regular solution model gave a reasonable description in the case of metallic solutes but failed to account for the behavior of the more electronegative solutes sulfur and oxygen. These same authors2 later modified their model by using the quasi-chemical approximation3 to calculate the average composition of the first coordination shell surrounding each solute atom. This modified model was shown to lead to a better qualitative description of the behavior of the electronegative solutes; however, quantitative agreement with experimental data for oxygen in alloys could only be achieved by assuming a very small coordination number. The authors concluded that the major source of error in the model was the assumption that pairwise interaction energies were independent of composition. Substitutional and interstitial random solution models by Wada and saito4 are essentially similar to the first model except that the required interchange energies were derived from the modified solubility parameter equation of Mott, instead of from experimental binary data. Most recently Hoch5 has presented a statistical model for interstitial solutions and has applied the model to the Fe-C-O system. However, as the various interaction energies needed in the model had to be derived from the ternary data, the model does not promise well as a means of forecasting ternary behavior. Each of the above models carries the assumption that the strongly electronegative solutes have the same configurational environment as metallic solutes; i.e., the solute can be treated as a substitutional or interstitial atom in a quasi-crystalline lattice and is surrounded by a normal coordination shell of solvent atoms. There are, however, a number of facts which suggest that this is unlikely. First, the heats of solution are large, being more typical of molecule formation rather than alloying. For example, the heats of solution of monatomic oxygen and sulfur in liquid iron are -90 kea16,8 and -74 kea1,7, 8 respectively. These are to be compared with maximum heats of solution of metallic solutes in liquid iron of about -13 keal (silicon is an exception with -28.5 kea17). The large depression of the surface tension of liquid iron by trace amounts of the electronegative solutes oxygen, sulfur, and selenium9 suggests, by analogy with aqueous systems, the possible existence of polar molecules in the liquid. The effect of these solutes is at least three orders of magnitude greater than normal metal solutes.10 As has been pointed out by Richardson,11 the electron affinities and ionization potentials of oxygen and sulfur are such that it is likely that they exist in metallic solution as negatively charged ions. If this is so, and it is assumed that electrostatic forces play an important role in determining the configuration, it is unlikely that the stable configuration will be that of an isolated ion surrounded by a symmetrical coordination shell of solvent ions. It is more likely that the energy of the system would be lowered by the formation of solute-solvent screened dipoles. The above arguments suggest the formation of "molecular species" between solute and solvent atoms. The idea of the existence of molecular species in such solutions is not new, however&apos;, for Marshall and chipman12 have explained in a semi-quantitative manner the C-O equilibrium in liquid iron by postulating the species CO. Chen and Chip-man13 interpreted their measurements on the Cr-O equilibrium in iron in terms of the species CrO. Zapffe and sims14 have also postulated the existence of such species in liquid-iron alloys.

Jan 1, 1965

By N. D. Shutler

This paper describes a numerical mathematical model of the steamflood process that depends on fewer restrictive assumptions than models previously reported. The solution, however, is obtained economically. Example calculations are presented that, on comparison with experimental results, tend to validate the model. Results that expose certain process mechanics are discussed. The model describes the simultaneous flow of three phases — oil, water and gas — in one dimension. It includes the effects of three-phase relative permeabilities, capillary pressure, and temperature- and pressure - dependent fluid properties. Interphase mass transfer of water-steam is allowed, but the oil is assumed nonvolatile and the hydrocarbon gas insoluble in the liquid phases. The model allows heat convection in one dimension and two-dimensional heat conduction in a vertical cross-section spanning the oil sand and adjacent strata. The hydrocarbon-steam gas composition is tracked, but the effect of gas composition on water-steam phase behavior is neglected. The model is solved numerically in three separate stages. The three-phase mass balances are solved simultaneously using Newtonian iteration on nonlinearities occurring in the accumulation terms. The energy balance is solved separately by noniterative application of the alternating-direction implicit procedure. Separate solution of the composition balance is accomplished by straightforward solution of the finite difference equations. The method of effecting nonsimultaneous, stable solution of the mass and energy balances is the key to the success of the model. INTRODUCTION Mathematical tools as well as laboratory and field experiments are necessary to help us understand the complex steamflood process. A mathematical model can expose process mechanics and show the relative importance of process variables, but this ability is often limited by restrictive assumptions. Most known models of steam processes,l-5 with the exception of the model of Gottfried,6 are "simplified" in that they involve analytic approximations and require many restrictive assumptions. The primary utility of these methods lies in the routine use as an aid in engineering design. By contrast, the comprehensive model presented here is numerical and requires far fewer restrictive assumptions. It finds its primary utility as a research tool. It serves as an aid in understanding the nature of the process, in interpreting laboratory experiments and in evaluating and developing simpler mathematical models for engineering design. The major reason why previously presented models have been confined to the "simplified" class is evidenced by the one published exception. In 1965, Gottfried6 presented a numerical model for the combustion process of which the steam process is a subset. The result is a comprehensive tool (though it neglects capillarity and two-dimensional heat conduction) that is troubled with convergence problems and that requires 2 to 3 hours of IBM 7094 time to complete a calculation. Though our present model does not simulate combustion, it does consider capillarity and two-dimensional heat conduction and it overcomes the convergence and computer-time problems. MATHEMATICAL DESCRIPTION OF STEAMFLOODING FLUID FLOW The equations employed to describe three-phase fluid flow are of a familiar form. Darcy&apos;s. law provides expressions for the velocities of the three phases (oil, water and gas), which, when combined with oil, water and gas mass balances, give the partial differential equations governing flow of the

Jan 1, 1970

By B. H. Caudle, L. H. Silberberg

Reservoir depletion by natural water drive is typified by the movement of water from an aquifer into the adjacent oil-bearing formation. Prior studies of this type 01 water movement have generally neglected the resistance to flow in the aquifer and its effect on the movement of water into the oil bearing zone. A method for designing and operating scaled models of such reservoir systems is presented. Experimental data on a model of an edge-water-drive reservoir are shown and discussed. INTRODUCTION Most petroleum reservoirs derive at least a part of their productive capacity from water influx. This water may be injected from the surface or it may come from an aquifer adjacent to the oil zone. In either case, the reservoir engineer must be able to estimate the advance of the water as a function of either the elapsed time or the fluid produced. This paper describes a type of fluid flow model which includes the effect of viscous and gravitational forces in the reservoir and the surrounding aquifer. Natural water influx can be divided into three general (but widely overlapping) categories according to the direction of flow in the aquifer. These are shown schematically in Fig. 1. Fig. l(a) illustrates an edge-water-drive mechanism. In this case, water advances updip along the stratum but the movement of water is essentially horizontal and very little of the oil is actually underlain by water. The bottom-water drive (Fig. l(b)) is characterized by a thick aquifer underlying the oil zone. The water movement is generally vertical in the aquifer. The third category is illustrated in l(c). Referred to as the "thin oil column", this type of oil accumulation consists of oil over water in a relatively thin stratum. Fluid movement is horizontal in both the oil and water zones, except close to the producing well. One characteristic which all three of these types have in common is that part of the water flow takes place in the water invaded region of the oil reservoir while the remainder of the water flow occurs in the aquifer. The resistance to the flow of water usually will not be the same in these two regions. This occurs because the porous rock normally contains only water in the aquifer, while the water-invaded region always contains microscopic globules of bypassed oil (residual oil) which interfere with the flow of water through the rock. The production history of any type of a water-drive system is a function of two phenomena — where the water goes, and how it displaces the oil in the area invaded by the water. It is usually impractical to study these two phenomena at the same time. In most cases one type of analysis is used to predict the gross movement of water in the reservoir, while a different type of analysis is employed to determine the amount of oil to be recovered from the gross volume contacted by the water. The portion of the oil reservoir which is invaded by water is mainly a function of the resistances to fluid flow in the several parts of the flow system. This gross water influx in the three types of natural water drive typically results in water cusping to the production wells either from the side or from below (water coning). In 1747, Muskat described a greatly simplified mathematical model for predicting the area invaded by water in a bottom-water-drive reservoir.1 This model used the Laplace equation and suitable boundary conditions to describe the isopotentials and streamlines in the flow system. The use of this model assumes that (1) the reservoir rock is homogeneous in nature, (2) the oil and water mobilities are equal, (3) there is no oil flowing in the water invaded region, and (4) external forces — such as gravity — do not affect the flow. This method has been used for both natural water drives and water injection projects. In this, as in most models, the method of images is used to reduce the size of the model necessary to describe the reservoir. The assumption of equal viscosities and permea-

Jan 1, 1966

By William Fink

SINCE so many different curves have been published for the solid solubility of zinc in aluminum, it seems desirable to definitely establish the correct curve by two or more independent methods. The curve published in part I1 was based entirely upon X-ray measurements because the other methods employed at that time were not satisfactory. The present paper (the seventeenth of this series on high-purity aluminum alloys) describes the determination of the solid solubility of zinc in aluminum by the measurement of electrical resistivity at temperature and by microscopic examination. Since the publication of our part I in 1932, an investigation of the solubility relations in the aluminum-zinc system has been reported by Schmid and Wassermann2, who obtained their solubility results from lattice-parameter measurements on heat-treated and quenched speci-mens. The diagram that they published is shown in Fig. 1. In this investigation they also found by X-ray measurements that the parameter of the gamma phase changed continuously with zinc content and at such a rate that it would be identical with that of the beta phase at 60 atomic per cent zinc. It was concluded therefore that the beta and gamma phases, from the point of view of structural relationship, are one single phase. They also suggested a gap of immiscibility between 270° and 350° C. The complete boundary in this region could not be deter-mined satisfactorily by the method employed and therefore was not shown in their diagram.

Jan 1, 1936