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By W. A. Griffith

Fractional replication of factorial design, a general method for planning experimentation and for analysis of data obtained, is described as applied to a flotation investigation. This method leads to determination of optimum process conditions with minimum experimental effort. Its advantages over simple factorial design are demonstrated. A METHOD for planning experimentation and for analyzing the data secured will be demonstrated. This method, termed fractional replication of factorial design, employs a relatively small number of individual experiments to determine which of a large number of process variables are controlling, to determine which combination of levels of these variables is most likely to produce optimum results, and also to predict what results will be obtained with a particular combination of conditions not already tested. Although the general method is not new, having been developed by Finney in 1945,' the extent to which it can improve the effectiveness of applied research generally has not been recognized by metallurgists. The fractional replication procedure is particularly useful in flotation experimentation and an example from such an investigation will be used in the paper. However, it has equal value in any investigation in which similar experimental difficulties are encountered. In developing a flotation process for a particular mineral separation, the investigator is inevitably confronted with the following difficulties: 1—There are a large number of potentially important process variables. 2—Results of individual experiments are not highly reproducible, due in part to the difficulty in precisely controlling all the variables. 3—Considerable effort is expended in conducting individual experiments. 4—There are practical limits on the number of individual experiments which can be made. In situations of just such a type, modern statistical methods of planning experimentation and analyzing data have their greatest value. Applications of one such technique, called factorial design, to problems of this type have been described by Dorenfeld and others.'-' The simple factorial design is an efficient procedure when the investigator hopes to provide a comprehensive understanding of the effects and interrelationships of a small number of variables over a limited range. In applied research, this is seldom the main objective. Rather, the investigator usually wishes to determine which of the many potentially important variables are in fact controlling, which levels of the controlling variables will provide opti- mum metallurgical results, and what these results will be at optimum conditions. Interest in detailed trends is limited to the controlling variables and to levels in the region of optimum conditions. Simple factorial design has serious deficiencies for such objectives and is not the most efficient method of experimental design. Deficiencies of Factorial Design In a simple factorial design, an experiment must be made at every possible combination of each level of every variable, once these have been chosen and the levels of each to be included have been decided upon. As the number of variables or levels of each increases, the experimental program quickly reaches prohibitive size. For example, an investigation of only four variables, each at four levels, requires 256 individual experiments. Often upon completion of such an extensive program, it is found that one or more of the variables has metallurgically unimportant effects or that a poor estimate has been made as to the appropriate range of levels to be investigated. The result is that only a small proportion of the data obtained falls in the range of real metallurgical interest. Indeed, it frequently can be anticipated that certain combinations of levels of variables will not produce results of interest, but they still must be included so that the essential balance, or orthogonality, of the design will be retained. It may be true that factorial design will provide the greatest amount of information from a given number of experiments, but it does not necessarily follow that it will lead to the desired information with a minimum number of experiments. Much of the information provided may be of little value. Advantages of Fractional Replication The disadvantages of simple factorial design are overcome to a great extent by a modification known as fractional replication. This is a technique for sampling systematically the potential data of a full factorial experiment, that is, the data which would have been obtained if the complete factorially designed program had been completed. Only a fraction of the total array of experiments is made, but the experiments are chosen in such a way that the important advantages of factorial design and the accompanying analysis of variance are retained. The data obtained from the first group of experiments are used to determine which of several variables are controlling and which levels of these variables are most likely to produce the desired result. Unimportant variables and levels of variables then may be

Jan 1, 1956

By T. M. Allen, W. H. White

THE Greenwood-Grand Forks area of southern central British Columbia, known as the Boundary District, has a long history of mining exploration and production. At the turn of the century this was the premier copper mining camp in the British Empire, its total production amounting to some 20 million tons. Most of this ore came from the great Granby mines at Phoenix, but the Motherlode mine at Deadwood camp, 6 miles to the west, and several mines in Summit camp, 5 miles north of Phoenix, made important contributions. The large deposits were exhausted in 1918 and the district since has seen only desultory exploration and salvage operations. The orebodies are mineralized skarn zones in limestone members of a thick series of Upper Paleozoic sedimentary and volcanic strata. Chalcopyrite is the primary ore-mineral. Copper carbonates and silicates occur sparingly in outcrops, but the oxidized zone generally is very shallow. Much of the surface is mantled by glacial drift which in most places ranges in thickness from 2 to 15 ft. In some of the hanging valleys, however, the glacial drift may be as much as 100 ft thick and may assume drumlin-like forms. In 1951 an ambitious program aimed at the discovery of new orebodies and important extensions of abandoned deposits was launched by Attwood Copper Mines, Ltd. In this district so thoroughly searched by an earlier generation of prospectors, any orebody which had remained undiscovered must have little or no surface indication. Consequently, in addition to the basic detailed geological work, the program of exploration included magnetometer and self-potential surveys. Geological bets and geophysical anomalies were tested further, prior to diamond drilling, by a study of copper distribution in tree twigs and/or in the soil. The soil sampling and analytical methods used and some of the results seem of sufficient importance to warrant this paper. The authors had done some plant sampling in this and other districts, using the dithizone neutral-color-end-point method (Warren and Delavault, 1948, 1949; White, 1950),1-3 but they were unfamiliar with its soil application. Finally, after much experimenting in the field, they adopted the methods described here. These methods are not entirely original or defensible on theoretical grounds, but under field conditions of rapid sampling and analysis the results are reliable enough to be of use. Fig. 1, which shows the results of duplicate analyses of duplicate soil samples taken at 50-ft intervals across an anomalous zone, indicates the relative dependability both of the sampling and analytical methods. Sampling and Analytical Equipment A 2-ft piece of 1-in. solid drill steel, one end sharpened to a broad, conical point. The steel is marked at 1 ft from the point. A 2-ft piece of ½-in. black iron pipe, one end filed to a bevelled cutting edge. The pipe is marked at 1 ft 3 in. from the cutting end. A 3-lb hammer. A plastic or rubberized sheet about 18 in. square. Moisture-proof assay pulp envelopes. A 10-mesh seive made from window screen with the paint burnt off. A small assay spatula. A pan balance sensitive to 10 mg. Two ignition trays about 4 in. square, made of sheet iron turned up along the edges. A Coleman two-burner gasoline stove. An asbestos board about 5x8 in., used as a hot plate on the gasoline stove. A circular aluminum rack to hold 8 test tubes while refluxing (design of Almond and Morris). Pyrex Glassware Large refluxing test tubes, 25x200 mm, marked at 40 ml volume. Breakers, 20 ml. Pipettes, 1, 5, and 10-ml capacity. Graduate, 50 ml. Shaking cylinders, 100 ml, glass stoppers. Burette, 25 or 50-ml capacity, with holder. Chemical Supplies 1 N sulphuric acid. Hydroxylamine hydrochloride, solid crystals. Fisher Alkacid test paper. Copper standard solution. Dithizone standard solution 60 mg per liter. Water reasonably free of metals. Soil Sampling Method: The problem of how to take a soil sample is extremely crucial. The method outlined below, adopted after a number of tests, has the advantages of uniform pattern, uniform depth, and uniform size of sample. The area to be tested was marked off by chain and compass lines 100 ft apart, normal to the strike of possible ore deposits. Numbered stakes were set at 50-ft intervals along these lines and a soil sample was taken at each stake in the following manner. The drill steel was driven into the ground normal to the slope of the surface to the marked depth of 1 ft, moved slightly from side to side, then carefully withdrawn. The iron pipe was inserted to the bottom of this hole, tapped down to the marked depth of 1 ft 3 in. and withdrawn; the 3-in. soil plug in the

Jan 1, 1955

By P. A. Witherspoon, S. P. Neuman

Evaluating the permeability of a caprock overlying a potential gas storage reservoir is a very critical problem. Pumping water from the reservoir can be used as an evaluation tool in analyzing this problem. Fluid level changes that occur in the aquifer us well as in the caprock can be measured with appropriately placed wells. If the leakage of water from the caprock into the aquifer is considerable, the effects will be apparent in the aquifer. If the leakage is slight, however, it will not be possible to detect it with certainty from observations in the aquifer alone. Fluid level measurements in the caprock must be relied upon. and improved methods of analyzing such effects have been developed which are based on a theoretical analysis of fluid flow through a caprock of infinite thickness. An example applying these methods to field data is discussed. INTRODUCTION One of the most critical problems in evaluating an aquifer gas storage project is determining the tightness of the caprock overlying the formation to be used as the storage reservoir. A formation that has previously held oil or gas obviously has a suitable caprock, but an aquifer that contains only water gives no such assurance. A number of aquifer projects in the United States have been troubled by gas leaking out of the intended storage zone, and the ensuing difficulties have led to the development of new evaluation methods. One of these new methods is pump testing wherein water is removed from the aquifer at some controlled rate prior to injection of gas. This fluid withdrawal causes a pressure drop to move out through the aquifer for considerable distances in a matter of days or weeks. Depending on the properties of the caprock, a pressure transient can also pass upward (as well as downward) through the caprock layers adjacent to the aquifer. Thus, if the operator has placed observation wells at appropriate distances from the pumping well, the rapidity with which the pressure transients reach different points in the system can be used to investigate the fluid transport properties of both the aquifer and its caprock. The usefulness of pump testing has been recognized by groundwater hydrologists for many years as a means of determining the potential yield and properties of aquifers used in water supply They have introduced the term "leaky aquifer" for a system in which an aquifer is overlain (or underlain) by semipermeable caprock layers. The ease with which water leaks into the aquifer during pumping can, of course, be very beneficial in bringing additional water to the pumped well. Hydrologists have therefore devoted considerable attention to this prob-lem. From the gas storage standpoint, however, the tighter the caprock layers that overlie the intended storage reservoir, the better are the conditions for minimizing or eliminating any vertical migration of gas. Thus, after a suitable geologic structure has been found, the emphasis in aquifer storage projects is in determining that the caprock is tight. Attention has recently been focused on the use of pump testing as one approach to solving this problem.23,24 This paper presents a further development on evaluating the permeability of a slightly leaky caprock when the caprock is of infinite thickness. From the practical standpoint, this means that the caprock layers are thick enough that pressure transients do not reach the outer boundaries of the system during the pumping test. In a subsequent paper, an analysis of the case where the caprock is of finite thickness will be presented. PREVIOUS WORK ON LEAKY AQUIFERS Jacob" developed a partial differential equation describing the flow of water in an aquifer of permeability k that is overlain by a leaky caprock of permeability k'. Fig. 1 shows a schematic cross-section of the system under consideration. One of his principle assumptions was that if k > > k', the direction of flow is essentially vertical in the caprock and horizontal in the aquifer. Neuman19 confirmed the validity of Jacob's assumption using a mathematical model. Another assumption was that a permeable source layer overlies the caprock (Fig. 1) and is able to maintain a constant hydraulic head at the upper boundary of the caprock. By neglecting the effects of compressibility within the caprock, Jacob1* developed a solution for a bounded circular aquifer. Later, Hantush and Jacobx5 used the same assumptions to solve the case of an infinite radial aquifer that is pumped at a constant rate. Their solution may be expressed in di-mensionless parameters by

By G. V. Jere, C. C. Patel

Chlorination of the various constituents of ilmenite by different chlorinating agents in presence of various reducing agents, have been considered on the basis of the standard free energy and standard enthalpy changes as a function of temperature. The standard free energy change considerations show that it is beneficial to chlorinate ilmenite by chlorine in the presence of carbon and also that iron constituent of ilmenite can be preferentially chlorinated by clzlorine, titanium tetrachloride or their mixture. These findilzgs have been corroborated from the published work. METALLURGICAL processes involving the use of titanium tetrachloride have gained in importance because of the use of the latter in the manufacture of titanium metal. Since ilmenite is more abundant in nature than any other titanium mineral, the future of the metallurgical processes depends on the utilization of ilmenite for the production of titanium tetrachloride. In these laboratories, investigations have been carried out on the chlorination of ilmenite under a variety of conditions.1'2 During these studies, it was noticed that 1) preferential chlorination of iron was effected at low temperatures (400° to 600°C) and at low carbon content (6 to 7 pct), 2) carbonyl chloride retarded the chlorination of iron oxides and titania perceptibly, while 3) carbon-tetrachloride, compounds of sulphur and some other catalysts favored the chlorination. Moles3 has found that oxides of iron are chlorinated in preference to titania at high temperatures, while wilcox4 has claimed the preferential chlorination of titania between 1200" and 1500°C. It has been shown in this paper that preferential chlorination of titania claimed by Wilcox is not likely to occur. Daubenspeck and coworkers5,6 have claimed the preferential chlorination of iron by chlorine or by a mixture of titanium tetrachloride and chlorine between 700° and 1050°C in the absence of carbon. Even when plain titanium tetrachloride is employed as the chlorinating agent, pascaud7 noticed the preferential chlorination of iron and other oxides. The purpose of this paper is to explain from thermodynamical considerations, the various chlorination reactions studied so far. ILMENITE CONSTITUENTS AND THEIR CHLORINATION PRODUCTS Although the general composition of the ilmenite mineral is represented as FeTiO,, most of the ilmenites found in nature have variable quantities of TiO2 (44.6 to 64 pct), FeO (4.7 to 36 pct) and Fe2O3 (6.9 to 28 pct).8 The higher content of ferric iron in ilmenites was attributed by Millerg to the presence of arizonite (Fe2O3.3TiO2). But the X-ray studies by Overholt, Vaw, and odd" have shown that arizonite is a mixture of haematite, ilmenite, anatase, and rutile. Except for the anatase, similar views have been advanced by Lynd, Sigurdson, North, and Anderson8 from magnetic, X-ray, and optical and electron microscope studies. The ilmenite ores can, therefore, be assumed to consist of mineral aggregates of ilmenite, rutile and haematite. From the free energy of formation of ilmenite (FeTiO3), it has been shown by Kelley, Todd, and King11 that ilmenite is stable even up to its melting point (1367°C) and would not undergo decomposition into its constituent oxides. Schomate, Naylor, and Boericke12 have found that in the presence of a reducing agent the iron constituent of ilmenite is selectively reduced. The reaction of chlorine with ilmenite in presence of a reducing agent can, therefore, be synonymous with that of the reaction of chlorine with the constituents of ilmenite, viz., TiO2, FeO, and Fe2O3. Most of the reaction products of chlorination of ilmenite in the presence of reducing agents will be in equilibrium with their dissociation products, depending on the temperature. The titanium tetrachloride is, however, quite stable up to 1500°C due to its covalent nature. The equilibrium for the ferric chloride system has been investigated by Kangro and Bernstorff, 13, schafer14 and Kangro and petersen,15 and the results are summarized in Fig. 1, curves a, b, and c respectively. From these results, it is clear that the ferric chloride disociates as follows: 324° to 700°C FeaCl6(g) ?2FeCl2(c) + Cl2(g) [1] 324°to 900°C Fe2Cl6(g) =2 Fe Cl2 Reaction [I] (curve a) occurs in the forward direction to about 6 pct at 400°C but falls off very rapidly with increase in temperature and beyond 600°C, it is practically negligible, perhaps due to the formation of the stable monomer, FeC13(g). As the temperature is further increased, the amount of FeCl,(g) in-

Jan 1, 1961

By H. T. Sumsion, A. U. Seybolt

The results of an investigation of vanadium-rich V-O solid solutions are presented, indicating the structure and lattice parameters of two solutions, a and ß, and their approximate temperature-composition existence. The a solution is the terminal body-centered cubic one, and contains up to 3.2 atomic pct 0. The ß solution has an ordered body-centered tetragonal structure, is formed at 1270°C, and exists from about 15 to 22 atomic pct 0. From the evidence available, the various phase boundaries have no appreciable temperature dependence. Evidence has been found for a polymorphic transformation in pure vanadium at 1550°C. IN an earlier investigation' dealing with the preparation of pure vanadium by calcium reduction of the oxide, it was found that small amounts of oxygen drastically reduced the ductility of the metal. Because this effect was so marked, it was decided to make a study of the solubility of oxygen in solid vanadium. This report deals principally with this solubility and the nature of the phase relationships in the vanadium-rich region, particularly at temperatures below 1300 °C. However, during the investigation enough data on the V-0 system were obtained to make it appear worthwhile to present a tentative phase diagram up to the composition VO. The only significant prior work found on this system are the contributions of Klemm and Grimm,' and Mathewson et al.3 Klemm and Grimm prepared a wide range of V-O compositions by powder techniques including the compositions VO.l, VO.2, VO.3 and VO4 (9.1, 16.8, 23, and 28.6 atomic pct 0, respectively). The first three compositions were found to consist of a body-centered tetragonal solid solution, while the last also showed lines of VO (NaCl structure). They found that the parameter c, increased and the parameter a, decreased with increasing concentration of oxygen. For their composition VO.27, or about 16.8 atomic pct O, they cite the values a, = 2.948A, c, = 3.53A, and c/a = 1.2. Klemm and Grimm made no attempt to determine the solid solubility limit nor to construct a phase diagram. They did, however, give some data on the homogeneity range of VO, and they proposed a structure for the body-centered tetragonal solid solution; these points will be taken up later. Materials and Preparation of Samples The vanadium used in this investigation was prepared in the laboratory by the method previously mentioned.' A typical analysis is as follows: Fe, 0.007 pct; Si, 0.02; Ca, 0.06; C, 0.224; O2, 0.044; N,, 0.0017; H2, 0.003; and V, 99.34 ±0.3 (assay). The vanadium assay is probably low by about the error given. The impurities total about 0.36 which, if subtracted from 100, gives a purity of about 99.6. At the time material was being prepared for this work no suitable technique was available for melting vanadium without appreciable contamination. The procedure adopted therefore was to cut the calcium-reduced regulii into slices which were then rolled to strip about 0.025 in. thick for oxygen diffusion. Pieces of rolled vanadium of approximately 0.025xY4xl in. and weighing about 0.3 g were suspended in a vertical fused-silica tube which was part of an ordinary gas absorption apparatus. The silica tube was heated by an electric resistance-tube furnace which could be raised around the silica tube or lowered away from it as desired. This apparatus had no novel features which require detailed description. Other than the silica tube and furnace, it consisted of a glass system evacuated by a liquid nitrogen trapped mercury diffusion pump, a mercury-operated gas burette, a McLeod and a Pirani gage, and a mercury manometer. It was also equipped with suitably located stopcocks for isolating various parts of the system; the vacuum ordinarily attained was between 10" and 10-6 mm of mercury. Oxygen generated by decomposing MnO2 was passed through anhydrous magnesium perchlo-rate before introducing it into the gas burette and thence to the absorption chamber.

Jan 1, 1954

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'-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,' 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 L. L. Handy

Solvent floods using slugs of solvent have been found to show continuity in behavior from the vapor pressure of the solvent to the critical pressure for the two-component driving gas-solvent system. In the pressure region between the solvent vapor pressure and the critical pressure for the gas-solvent system, the gar and solvent are only partially miscible. Although complete miscibility cannot be obtained at these pressures, complete oil recovery is possible in principle. In two-phase solvent floods the solvent is propagated tllrough the reservoir, primarily, in the vapor phase. The carrier gas requirements constitute a significant factor in the economics of the process. A qualitative theory is proposed for estimating the amount of dry gas required to move the solvent through the reservoir. The theory shows that for two-phase solvent floods the total gas needed is a minimum at the vapor pressure of the solvent and at the critical pressure for the gas-solvent system, and is a maximum at some intermediate pressure. The predictions of the theory are supported by experimental studies using methane, butane and decane or methane, propane and decane in a natural sandstone core. INTRODUCTION Previously, solvent slug processes have been found effective for oil recovery in two pressure ranges. First, conventional miscible displacements are possible at pressures greater than the critical pressure for the gas-solvent system. Second, Jenks, et al,' have shown that, at pressures slightly in excess of the vapor pressure of the solvent, a solvent slug can be propagated through a reservoir by a gas essentially insoluble in the liquid solvent. The solvent bank displaces the oil ahead of it. Both of these processes, at least ideally, are capable of recovering all of the oil in the swept regions. Slug processes for which the gas and solvent are partially miscible have not been considered; that is, those systems for which the solvent and driving gas form two equilibrium phases in which the vapor phase contains a significant amount of solvent and the liquid phase an appreciable amount of the driving gas. Welge and Johnson' have shown that the gas needed to movc a solvent slug through the reservoir increases with increasing pressure above the vapor pressure of the solvent. It will be shown that solvent slug processes can, theoretically, recover all of the oil at any pressure greater than the vapor pressure of the solvent. But the amount of gas required to move the solvent through the reservoir depends very much on the pressure and temperature. In the present study a maximum in the gas requirements was both predicted theoretically and observed experimentally. This result has not been reported previously, and would not have been predicted from the Welge and Johnson model. The gas requirements are a minimum at the pressures corresponding to the vapor pressure of the solvent and again at the critical pressure for the gas-solvent system, and are a maximum at some intermediate pressure. AN APPROXIMATE THEORY FOR TWO-PHASE SOLVENT FLOODING The differences and similarities between conventional solvent floods and two-phase solvent floods are best understood by referring to concepts developed for miscible displacement in which miscibility is generated in the reservoir. In Fig. 1(A), a ternary diagram is shown for a hypothetical gas-solvent-oil system. To be rigorous the three components should each consist of a single molecular species. The pressure for Fig. 1(A) is greater than the critical pressure for the binary gas-solvent system at the specified temperature. Diagrams of this type are the ones most frequently referred to in discussions of enriched-gas drive and miscible displacement. A limiting tie line is shown tangent to the two-phase envelope and intersecting the gas-solvent line at Point A. To obtain generated miscibility with this type system, others have shown that, for an oil of Composition D, a mixture of gas and solvent must be injected which is richer in solvent than that composition indicated by A. An oil repeatedly contacted with a gas phase richer than A changes toward a composition which would be at equilibrium with the injected mixture, that is, a composition lying on a tie line which passes through the injected-gas composition. Since no such tie line exists, the oil is enriched to the point at which it becomes directly miscible with the injected mixture. At pressures lower than the critical pressure for the gas-solvent system, other types of phase diagrams are observed. The ones of interest in this paper are for pressures greater than the vapor pressure of the solvent, but less than the critical pressure of the gas-solvent system. Such a ternary diagram is shown on Fig. 1(B). In this case, two-phase behavior is observed not only for gas-oil mixtures, but also for certain compositions in the gas-solvent system. If a gas of Composition A (a dew-point vapor) is injected, once again the original oil is enriched by successive

By C. R. Barker, D. A. Summers, H. D. Keith

Introduction Historically, the presence of methane has been a problem, mainly in and around the working areas of active coal mines, and only in these areas has drainage been considered. Drainage, where practical, has been achieved through the drilling of holes forward into the coal and the surrounding strata from the working area. These holes generaly have been short in length, although where methane drainage operations around a longwall face have been undertaken, the holes have had to be longer in order to adequately drain from the center of the face into the access gate roads. In recent years, attempts have been made to degasify the coal seams in advance of mining, without disruption of the mining cycle. This is done by drilling much longer horizontal holes through the coal in advance of the working area. Under the aegis of the federal government, methods have also been developed for draining coal seams of their methane content in advance of mining, but from shafts sunk from the surface, without using the active area of the mine as the location for the drill holes. Development of methane drainage has recently been encouraged by the potential use of the drained methane as a commercial energy source, with a need, therefore, to adequately organize a collection system, separate from mining the seam for coal. This has already been successfully accomplished, for example, in the Federal No. 2 mine of Eastern Associated Coal Corp. starting in 1975 (Johns). However, whether the system gains access to the coal through horizontal drilling from a pre- existing mine or via access through a separate shaft from the surface, long horizontal holes are required to adequately tap the methane reserve. It is to this regard-the actual drilling of the horizontal holes-that this paper is directed. It will examine potential benefits that may accrue, both in conventional horizontal hole drilling from a mine site underground, and also in drilling from the surface if a high pressure water jet drill is used to drill the degasification holes. Long Hole Drilling from an Underground Site Personnel from the Bureau of Mines have recently examined methods for conventional drilling of long horizontal holes to gain access for methane drainage. They have shown that it is possible (Cervik, Fields, and Aul) to drill out some 610 m using a conventional drilling system. Three types of bit were used in the program and by alternating between a drag bit, tricone bit, and plug bit, advance rates of between 0.6-3.6 m/min were achieved. Hole diameters varied from 7.6-9.2 cm in surface tests at bit thrusts of 1360 kg. A hole was then drilled and maintained in relative alignment within the coal seam for a distance of 640 m. Thrust levels had to be lowered to between 363-680 kg across the bit. Because the loads were smaller than those used in the surface trial, advance rates in the hole were of the order of 10-38 cm/min. The thrust level was lowered since it was found that the level of the thrust controlled the inclination of the drill so that, for example, a thrust of 363 kg caused the hole to incline downward, while at greater than 544 kg the hole inclined upward with the 9-cm-diam bit. Thrust levels increased 227 kg when the hole diameter was raised to 9.2 cm, although in such a case penetration rates in excess of 56 cm/min could be achieved. Horizontal Water Jet Drilling of Coal The University of Missouri-Rolla has recently undertaken research for Sandia Laboratories on the use of high pressure water jets as a means of drilling through coal. The initial experiment in this program called for drilling a hole horizontally into a coal seam from the side of a strip pit using water jets as the cutting mechanism. A very simple setup [(Fig. 1)] was used in this program and a 15-m hole was drilled at an approximate drilling speed of 1.2 m/min. The nozzle was designed so that the hole dimension was approximately 15 cm across [(Fig 2)] and the thrust was maintained at levels below 91 kg in moving the drill into the coal face. The system used was very crude and comprised a high pressure water jet drill enclosed within a 5.7-cm outer diameter galvanized water pipe to provide rigidity to the drilling system. This pipe sufficed to maintain hole alignment over the 15-m increment. While it is premature to make long-term predictions on ultimate applicability of this sytem to long hole drilling, certain inherent advantages of water jets can be delineated from research results and suggest considerable advantage to further research in development of this application. High pressure water was supplied at approximately 62 046 kPa from a 112-kW high pressure pump, with a 83 L/m flow through the supply line to the nozzle. The drilling system consisted of a nozzle rigidly attached to the front end of the galvanized piping. High pressure fluid was supplied to this nozzle through a flexible high pressure hose that fed from the nozzle back through the galvanized pipe to a rotary coupling attached

Jan 1, 1981

By James H. Courtright, Kenyon Richard

SILVER Bell is situated 35 airline miles northwest of Tucson, Ariz., in a small, rugged range rising above the extensive alluvial plains of this desert region. Its geographical relation to other porphyry copper deposits of the Southwest is shown on the inset map in the lower left corner of Fig. 1. The climate is semi-arid. Altitudes range within 2000 and 4000 ft. Opening of the Boot mine, later known as the Mammoth, in 1865 was the first event of note in the district's history. Oxidized copper ores containing minor silver-lead values were mined from replacement deposits in garnetized limestone and treated in local smelters. Copper production had approached 45 million pounds by 1909 when the disseminated copper possibilities in igneous rocks were recognized. Extensive churn drill exploration carried out during the next three years resulted in partial delineation of two copper sulphide deposits, the Oxide and El Tiro. Although the then submarginal tenor discouraged exploitation of these disseminated deposits, selective mining of orebodies in the sedimentary rocks continued intermittently until 1930, providing a production total of about 100 million pounds of copper. The American Smelting & Refining Co. began exploratory and check drilling in 1948 and subsequently made plans for mining and milling the Oxide and El Tiro orebodies at the rate of 7500 tons per day. Production began in 1954 at a rate of about 18,000 tons of copper annually. Formations ranging in age from Pre-Cambrian to Recent are exposed in the Silver Bell vicinity. The more erosion-resistant of these, Paleozoic limestone and Tertiary volcanics, predominate in the scattered peaks and ridges comprising the Silver Bell mountains. The porphyry copper deposits are located along the southwest flank of these mountains in hydrothermally altered igneous rocks. These are principally intrusives which cut Cretaceous and older sediments and are considered to be components of the Laramide Revolution. For three-fourths of its length the zone of alteration strikes west-northwest, Fig. 1. There now is no single structure that accounts for this alignment. However, indirect evidence suggests that a fault representing a line of profound structural weakness existed in this position prior to the advent of Laramide intrusive activity. This line will be referred to as the major structure. It was obliterated by the Laramide intrusive bodies but exerted a degree of control on their emplacement, as evidenced by their shapes and positions. The influence of fault structures on the shapes of intrusives in other porphyry copper districts has been noted by Butler and Wilson' and by others. As shown on the inset map on Fig. 2, a fault of parallel trend and considerable displacement lies to the north. This fault is now marked by a line of small Laramide intrusive bodies. To the south is a third fault of large displacement. Evidence of its age in relation to the Laramide intrusions and mineralization is not recognized, but its conformance in strike with the other two major faults is significant. These three breaks establish a pronounced trend of regional faulting. They are high-angle, and the southerly one may be reverse, Stratigraphic separations on these faults are of the order of several thousand feet. The local Paleozoic section is about 4000 ft thick. It is composed predominantly of limestone with a basal quartzite member. The Cretaceous section appears to exceed 5000 ft. Conglomerates, red shales, and arkosic sandstones (the youngest) characterize the three principal members. Intrusion of alaskite marked the beginning of Laramide igneous activity. It was emplaced as an elongate stock with one side closely conforming to the major structure line throughout a distance of nearly 4 miles. The alaskite was at one time regarded as a thrust block of pre-Cambrian rock'; however, its intrusive relationship and consequent post-Paleozoic age has been established by inclusions of limestone found in outcrops north of El Tiro. The next event was the intrusion of a large stock of dacite porphyry into Paleozoic sediments and alaskite. The stock was some 3 miles wide and at least 6 miles long in a northwesterly direction. It was sharply confined along its southwest side by the major structure line. A number of large pendants of moderately folded Paleozoic sediments occur within and along its southwest edge. Thus the inferred, original major fault between Paleozoic and Cretaceous sediments became a contact between alaskite and Paleozoic sediments and then a contact between dacite porphyry and alaskite. Andesite porphyry may have been intruded later than the dacite porphyry, but relationships are not clear; it may be simply a facies of the latter. The intrusive activity was at this stage interrupted by an interval of erosion. The erosion surface probably was rugged, as there were local accumulations of coarse, angular conglomerate. Subsequently a series of volcanic flows and pyroclastics several thousand feet thick was deposited. A similar unconformity has been recognized elsewhere in the Southwest, particularly in the Patagonia Mountains near the Flux mine some 75 miles southeasterly. Here, as at Silver Bell, volcanics were deposited on an erosion surface cut in Cretaceous and older sediments which had been intruded by alaskite. Though no evidence is offered that closely defines the age of this unconformity, and proper analysis of the problem is beyond the scope of this paper, it is

Jan 1, 1955

By A. S. Nowick, C. Y. Li

It is deMonstrated that quenching from an elevated temperataupe accelerates the grain boundary relaxation in two solid solutions (aAg-Zn and a Cu-Al). This result is consistent with the proposal that, in solid solutions, grain boundary relaxation occurs by a mechanism of' self diffusion. Nevertheless, an alternative possibilitg, that quenching introduces vacancies into the boundary itself, must also be considered. THE phcnomenon of grain boundary relaxation has been well known for many years,1,2 yet the mechanism of this process is very poorly understood. One of the most interesting suggestions which relates to the mechanism of grain boundary relaxation was that of Ke,3 who claimed that the activation energy for grain boundary relaxation and for lattice self diffusion were essentially the same. The implication is therefore that the elementary step in the two processes is the same. This suggestion is particularly startling in view of the fact that activation energy for self diffusion along a grain boundary is very significantly lower than that for volume self-diffusion. Later evidence5-7 showed that there really are two grain boundary peaks, one which appears in high-purity metals, and the other (which develops at a higher temperature than the first) which appears in solid solutions beginning at solute concentrations in the range of 0.1 pct. Data for silver6 show that Kg's hypothesis is surely incorrect for the grain boundary peak in the high-purity metal, since it has an activation energy of only 22 kcal per mole, but that the hypothesis may still be correct for the grain boundary peak in various silver solid solutions, for which activation energies in the range 40 to 50 kcal per mole are observed. If the elementary step in the grain boundary relaxation process were the same as that for self-diffusion, it would be expected that the relaxation process could be hastened by quenching, 2.c. by introducing a non-equilibrium excess of lattice vacancies. Such a quenching effect has already been demonstrated in the case of another anelastic relaxation process, viz., the Zener relaxation effect. The Zener effect, which occurs in essentially all solid solutions, may be attributed to the reorientation of pairs of solute atoms in the presence of an applied shear stress,' and therefore must take place by means of a volume diffusion mechanism. The hastening of this process through quenching9 has been one way of demonstrating that atom movements in the lattice take place through a defect mechanism, presumably single vacancies. In order to see if the grain boundary relaxation is affected by quenching, it is particularly convenient to compare the grain boundary relaxation with the Zener effect, by choosing a specimen for which both relaxation effects appear. Specifically, a fine-grained sample of a solid solution shows in the curve of internal friction vs temperature, first a peak due to the Zener effect, then a second rise (and eventually a peak at substantially higher temperatures) due to the grain boundary relaxation. The same phenomena are also observable in static anelastic measurements, such as creep at very low stress levels. Thus, for the same fine-grained solid solution, the creepstrain, when plotted against log time, falls on a sigmodial curve with a sharp inflection point, due to the Zener effect, which is followed by a second rise and inflection resulting from the grain boundary relaxation. To look for a quenching effect, static measurements are preferable to the dynamic internal friction measurements, due to the fact that quenching effects tend to anneal out too rapidly at the temperatures at which the internal friction is measured.9 RESULTS AND DISCUSSION Creep experiments in torsion were carried out in an apparatus similar to that described by Ke1, whereby a wire is held under constant torque and its angular displacement is observed as a function of time. The alloy Ag-30 at. pct Znwas selected because of the large Zener relaxation that it displays. The two samples used were a "coarse grained" wire with a mean grain size about twice the diameter of the wire (diam = 0.032 in.), and a "fine-grained" wire which had several grains across the diameter. In Fig. 1 a comparison is made of the creep curves at 160°C of these two samples after they had been cooled slowly from 400°C. Curve A, which represents the coarsegrained sample, shows a unique relaxation process due to the Zener relaxation, with a relaxation time, T , in the vicinity of 100 sec. Curve B, which represents the behavior of the fine-grained sample, on the other hand, shows first the same relaxation process as that in A, followed by a turning up of the curve which corresponds to the onset of a second overlap-

Jan 1, 1962

By L. T. Lloyd, H. H. Chiswik

The operative deformation elements in a-uranium single crystals under compression at room temperature have been determined as a function of the compression directions. The deformation mechanisms noted may be arranged with respect to their frequency of occurrence and ease of operation in the following order: 1 — (010)-[I001 slip, 2—{130} twinning, 3—{~172} twinning, and 4bunder special conditions of stress application, kinking, cross-slip, {.-176) twinning, and (011) slip. The composition planes of the (172) and (176) systems were found to be irrational. Cross-slip was shown to be associated with the major (010) slip system, coupled with localized interaction of slip on the (001) planes. The mechanism of kinking was found to be similar to that observed in other metals in that it occurred chiefly when the compression direction was, nearly parallel to the principal slip direction [loo] and was associated with a lattice rotation about an axis contained in the slip plane and normal to the slip direction: the [001] in the uranium lattice. The resolved critical shear stress for slip on the (010)-[100] system was found to be 0.34 kg per mm2 In a single test it was shown that under compression in suitable directions twinning on the (130) also occurs at 600°C. DEFORMATION mechanisms of large grained polycrystalline orthorhombic a-uranium have been studied by Cahn.1 A major slip system identified as the (010) with a probable [loo] slip direction and a minor slip system on the (110) planes were reported; the slip direction of the minor system was not determined. The twinning systems that were identified experimentally included the (130) and the irrational (172) composition planes; observations of other traces which were not as frequent and which did not lend themselves to positive experimental identification led Cahn to postulate on the basis of indirect evidence that twinning also occurred on (112) and (121) planes. In addition to the foregoing slip and twinning mechanisms, Cahn also observed kinking and cross-slip in conjunction with the major (010) system; the cooperative cross-slip plane was not identified. The availability of single crystals to the present authors has enabled them to check these results, particularly with reference to the doubtful mechanisms and the preference of operation of any one mechanism in relation to the direction of stress application. The tests were confined to compression only, primarily because of experimental limitations imposed by the size and shape of the available crystals. The tests were performed at room temperature except for one crystal compressed at 600°C. The compression directions were chosen to obtain a representative coverage of one quadrant of the stereo-graphic projection. To test the existence of some of the deformation elements that were reported by Cahn, but were not found in the present study, several additional crystals were compressed in specifically chosen directions considered most ideal for their operation. Experimental Techniques The single crystals were obtained by the grain coarsening technique described by Fisher? They grinding and polishing on rotating laps, with final surface preparation performed in a H3PO4-HNO3 electropolishing bath. A typical crystal readied for compression is shown in Fig. 1; their dimensions were rather small and depended upon the testing direction. Crystals isolated for compression in a direction close to the [010] axis, which lay roughly parallel to the longitudinal axis of the polycrystalline rod, were about 3 to 4 mm long and 5 mm2 in cross-section, while those prepared for compression in other directions were smaller. Most of the crystals were free from twin markings and showed no evidence of Laue asterism. Several crystals, however, contained twin traces prior to compression; these were identified prior to compression so as to clearly distinguish them from those initiated during deformation. The origin of the twin markings prior to deformation may be ascribed to two sources: thermal stresses and specimen handling during isolation and preparation. Two other types of imperfections in the crystals should be mentioned: inclusions, which were probably oxides or carbides. and three of the crystals contained a small number of spherical included grains (<0.01 mm diam), which were remnants of unabsorbed grains from the coarsening treatment. The volume represented by these imperfections was small, and their presence presented no difficulties in the interpretation of the macrodeformation processes during subsequent compression. Two compression fixtures were employed: crystals A, B, C, E, and G were compressed in a hand-operated screw-driven jig whose compression platens were designed to minimize axial rotation;

Jan 1, 1956

By D. V. Edmonds, C. J. Beevers

Tensile tests were carried out on a! titanium containing 850, 1250, and 2700 ppm 0, and up to -500 ppm H. The tests were performed at -196", -78", 20°, 150°, and 300°C at a strain rate of -1.0 x 10??3 sec-1. Increasing oxygen content, increasing grain size, and decreasing test temperature resulted in enhanced embrittlement of the a titanium by the hydrogen additions. Metallographic observations showed that this can be correlated with the influence of these parameters on the introduction of cracks into the a! titanium by fracture of titanium hydride precipitates. CRAIGHEAD et al.1 reported that the hydrogen content normally found in commercial-purity a! titanium (60 to 100 ppm) was sufficient to cause a substantial lowering of the impact strength, and they attributed this embrittling effect of hydrogen to the precipitation of titanium hydride. Lenning et al.&apos; found that in commercial-purity a titanium there is an almost complete loss of impact strength at about 200 pprn H, which is approximately half the value needed to eliminate the impact strength of high-purity a titanium. They also showed that the presence of 3000 ppm hydrogen reduces the room-temperature tensile ductility of commercial-purity material to a value of the order of 10 pct; the corresponding hydrogen concentration for high-purity titanium is over 9000 ppm. It thus appears that the detrimental effect of hydrogen on the mechanical properties of commercial-purity titanium becomes evident at much lower hydrogen contents than for high-purity titanium. The main difference between the two types of a titanium might be expected to be the higher level of interstitial impurity in the commercial-purity grade. Jaffee et a1.3 studied the influence of temperature and strain rate on the hydrogen embrittlement of high-purity and commercial-purity ! titanium. In general, the behavior was the same for both materials; embrittlement was enhanced by decreasing temperature and increasing strain rate. Recent results from tests on commercial-purity a titanium containing 850 ppm O and varying amounts of hydrogen up to -500 ppm showed that the degree of embrittlement by hydrogen is intimately related to the fracture characteristics of titanium hydride precipitates.4 The present paper considers the interrelationship between the mechanical properties and micro-structural features of commercial-purity a! titanium containing 850, 1250, and 2700 ppm 0 and varying amounts of hydrogen up to -500 ppm. 1. EXPERIMENTAL PROCEDURE Three types of commercial-purity titanium supplied by IMI* were used in the investigation, and for the *Address: Witton, Birmingham 6, United Kingdom. purpose of this paper are designated Ti 115, Ti 130, and Ti 160. The principal impurity elements are given in Table I. The material was received in the form of 12.7 mm diam bars having a fully recrystallized structure. Tensile specimens with a round cross-section of 4.5 mm diam and a gage length of 15.2 mm were machined from the bars. In order to develop the same grain size (mean linear intercept of grain boundaries) in each of the three types the specimens were annealed under a dynamic vacuum of <10?5 mm Hg, Table 11. Specimen hydriding was carried out in a modified Sieverts apparatus;&apos; hydrogen was taken into solution at 450°C and after holding the specimens at this temperature for 24 hr they were furnace-cooled to room temperature at an average rate of -100 C deg per hr. By this method nominal hydrogen contents of 0, 50, 100, 250, and 500 ppm were introduced into specimens of Ti 115, Ti 130, and Ti 160 (100 ppm (wt) -0.5 at. pct). The actual hydrogen contents were calculated from the weight differences obtained by weighing the specimens before and after the hydriding treatment. Tensile tests were carried out at temperatures of -196", -78", 20°, 150°, and 300°C on a 10,000 kg In-stron machine at a nominal strain rate of -1.0 x 10-3 sec-1. Fractured specimens were sectioned in planes parallel to the tensile axis, mechanically polished to 0.25 µm grade of diamond paste, and then attack polished using a solution containing by volume 99 parts H2O, 1 part HF, and 1 part HNO3. Although the latter treatment unavoidably opened out cracks and voids visible after mechanical polishing, it did reveal the grain structure, titanium hydride morphology, and deformation twinning structure.

Jan 1, 1970

By B. B. Sandiford

It has been known for many years that the efficiency of a water flood can be improved by lowering the water-oil mobility ratio in the system. Such a change leads to better sweep efficiency and also to more efficient oil displacement in the swept zone. Data from our laboratory water-flood tests of both small cores and long sand packs are presented which show that water mobility can be reduced and oil recovery increased by the addition of certain polymer solutions to flood water. The reduction in mobility, in many cases, is greater than would be expected from conventional viscosity measurements. These solutions, however, do not cause significant reductions in oil mobility. The over-all effect of these mobility changes is increased waterflood oil recovery. Encouraged by results of our laboratory work, we expanded our study to include pilot field tests of floods with such solutions. One such test, made in the West Cat Canyon field, Santa Barbara County, Calif., is described in detail in this paper. Three other field tests are also discussed. INTRODUCTION Oil production from most reservoirs following primary depletion and/or water flooding is often less than 50 per cent of the original oil in place. Heavy oil reservoirs seldom yield over 15 per cent of their original oil. With new reservoirs becoming harder to find, the improvement of oil recovery efficiency is one of our very important problems. We describe here some of our attempts to increase the efficiency of oil displacement by adding a water-soluble polymer, partially hydrolyzed polyacrylamide, to flood water. This technique will be termed "polymer solution flooding". The concept of using high-viscosity water to increase the efficiency of water flooding is not new. In 1944 Detling (Shell Development Co.) obtained a patent covering the use of several additives for viscous water flooding.&apos; His objective was to improve water-oil mobility ratios by increasing the viscosity of the flood water. Other patents2-27 have been granted covering specific water-SO~LIble polymers or specific conditions of viscous water flooding. Barnes&apos;" described his laboratory model study of the injection of a viscous water slug into a reservoir which had been partially invaded by bottom water. He concluded that, for this type of reservoir, "the cost of viscous water should not exceed a few cents per barrel for viscous water slug injection to be economically feasible" Our studies have led us to a somewhat different conclusion in a number of cases where hydrolyzed polyacrylamide solutions have been injected into reservoir models or actual reservoirs. Possible reasons for this difference are discussed in this paper. Our studies have shown that polymer solutions may lead to an increase in oil recovery over that from an ordinary water flood by (1) improving sweep efficiency, (2) improving microscopic displacement efficiency, or (3) a combination of these mechanisms. In the work of Barnes, only the benefit of improved sweep efficiency was considered. Also, our work has shown that there are marked differences in the effectiveness of different water-soluble polymers as flood water additives. Partially hydrolyzed polyacrylamide is better than many other water-soluble polymers we have tested because, even in very low concentrations, it can lead to increased oil recovery. This is an important advantage when either a dilute polymer solution is injected continuously or a relatively concentrated slug is injected followed by water. In the latter case! portions of the slug become diluted and function in the formation as very dilute solutions. As dilution takes place the effective slug size will increase which, in turn, will reduce the cost per barrel of the effective flooding medium. The reason that partially hydrolyzed polyacrylamide solutions are more efficient at low concentrations than certain other polymer solutions of equivalent viscosity (when measured in conventional viscometers) is not fully understood. We do know that the shapes and sizes of macro-molecules dissolved or suspended in liquids influence the flow properties of their solutions or suspensions. Solutions of partially hydrolyzed polyacrylamide cause greater reductions in water mobility than would be expected from conventional viscosity measurements. LABORATORY STUDIES Laboratory water floods were run in linear and radial systems with different water-soluble polymers and under varying conditions of flow. including reservoir conditions of temperature, pressure and fluid composition. Some of these runs are considered in this section. OIL DISPLACEMENT IN LINEAR MODELS In this group of runs the sweep efficiency approached 100 per cent because the linear sand packs used were as nearly uniform as possible. Results reflect primarily the micro-scopic displacement efficiencies. The laboratory models were unconsolidat-ed sand packs the lengths of which varied from about 4 in, to 40 ft. Further information on the flow models used is listed in Table 1. Using conventional procedures, water floods were run on sand packs containing either refined or crude oil at restored state. Frequently, a repeat run, similar to the first, was made as a check. Then a third run was made on the restored-state model using either polymer solution or a combination of polymer solution (slug) and water. Details of these runs are also reported in Table 1. In Figs. 1 and 2 results of two different groups of runs are shown in which the oil used was a 62-cp refined oil and the flooding medium

Jan 1, 1965

By R. W. Fountain, W. D. Forgeng, G. M. Faulring

Precipitation of the phase Co3Ti (Cu3Au type) from a Co-5 pct Ti a11oy has been investigated using single-crystal X-ray diffraction techniques. Oscillation and transmission Laue patterns of specimens aged for short-time periods at 600" C indicate the formation of titanium-rich and titanium-poor zones coherent with the {100} matrix planes. Longer aging times at 600° C establish that the equilibrium phase also forms on the {100} matrix planes as platelets. These observations are corroborated by electron metallography; electron diffraction studies show the phase Co3Ti to be ordered. A probable sequence of the precipitation reaction is discussed. A previous publication by two of the present authors reported on the phase relations and precipitation in Co-Ti alloys containing up to 30 pct Ti.1 The results of this investigation established the existence of a new face-centered cubic inter metallic phase, ranging in composition from about 17.0 to 21.7 pct Ti at temperatures below 1000° C The decomposition of the fcc supersaturated solid solution was studied employing hardness and electrical resistivity measurements. The changes in hardness upon precipitation in alloys containing 3, 6, and 9 pct* Ti were found to be associated with an initial increase in hardness followed by a plateau and then a second, more pronounced hardness increase. Investigation of this behavior by electrical resistivity measurements suggested that two different kinetic processes were involved, which, when interpreted in terms of the kinetic relation,2-4 indicated that initial precipitation was in the form of thin plates. On continued aging, the plates impinged during the growth process. The general features of these findings have been confirmed by Bibring and Manenc,5 while, in addition, they report the phase to be ordered. The present investigation was undertaken to provide more definite information on the structural relationships between the precipitate and the matrix. EXPERIMENTAL PROCEDURE Single crystals of a (20-5 pct Ti alloy were prepared from the melt employing the Bridgman technique. Poly crystalline rod, 1/2 in. in diam, prepared from vacuum-melted material, was machined to 3/8- in. diam to remove any surface contamination that may have resulted from hot-working. The crystals were grown under a purified hydrogen atmosphere in high-purity alumina crucibles heated by induction. Considerable difficulty was encountered in attempting to grow monocrystals because of the high melting point of the alloy and the high solute concentration. However, one crystal about 6 in. long was obtained which was essentially a single crystal except for one or two very small grains around the periphery. The as-grown crystal was solution heat-treated for 24 hr at 1200°Cin a purified argon atmosphere and water-quenched. One-quarter-in. slices were taken from each end of the solution heat-treated crystal for chemical analyses, and the remainder of the crystal was mounted and oriented by the back reflection Laue Method. The chemical analysis of the crystal was as follows: Pct Ti Pct 0 Pct C Pct N Pct H Pet CO 5.29 0.08 0.004 0.002 0.0003 Balance By proper tilting of the crystal, it was possible to obtain slices 1/32 in. thick of [loo] and [110] orientation. The solution heat-treated crystal slices were sealed in silica capsules for the aging treatments, with titanium sponge placed at one end of the capsule to act as a getter. All slices were water-quenched from the aging temperatures, the capsules being broken under the water to ensure a rapid quench. Thinning of the slices for transmission X-ray studies was accomplished by a combination of mechanical and electrolytic techniques, the final thickness being about 0.1 mm. Laue patterns of the solution heat-treated crystal indicated that no strain was introduced by the thinning technique. ELECTRON METALLOGRAPHY After X-ray examination, the structural changes attending the precipitation were followed by examination of direct carbon replicas of polished and etched surfaces of the single-crystal slices and extracted phases. The earliest indication of significant structural change was observed after aging at 600°C The structure of a heavily etched, solution-treated crystal is shown in Fig. l(a). Aside from the etch pit pattern, no regularity of background structure is observed. On the other hand, in the background of the specimen heated for 500 hr at 600°C, the etching pattern shows a directionality indicating the influence of minute precipitate particles, Fig. l(b). On electrolytic dissolution of this specimen in 10 pct HC1 in alcohol, a large volume of very small, flattened cubes

Jan 1, 1962

By K. R. Carson, J. Weertman

An attempt is made to ascertain the mechanism of tangle and cell formation and its dependence upon dislocation-interstitial carbon interactions. The strain-hardening behavior of single crystals of 3.25 pct Si-Fe was determined at 300° and 425°K and under conditions of both continuous and interrupted tensile strain. Significantly enhanced hardening was observed in crystals deformed at the elevated temperature, and it was further accentuated by interrupted straining. Transmission electron microscopy was used to study the resultant dislocation structures. Strain aging was found to aid tangle and cell formation at 425°K, but at both temperatures embryo tangles formed solely from primary glide dislocations, presumably by a process involving cross slip and "mushrooming". IN the course of plastic deformation all bcc metals and alloys develop a dislocation structure characterized by loose-knit groups of tangled dislocations. With increasing strain the tangles become more tightly knit and grow larger; finally a three-dimensional cellular substructure is formed:1 This process has been observed with the transmission electron microscope.&apos;-l7 However, most investigations were confined to the study of nearly pure polycrystalline metals at relatively low temperatures. At intermediate temperatures, 0.17 to 0.14 Tm where T, is the melting temperature in degrees absolute, the mobility of interstitial impurities such as carbon is high enough to permit migration to nearby glide dislocations but is still low enough so that a significant drag force is exerted.18,19 it is also in this temperature range that a hump occurs in the curve of work-hardening rate vs temperature for iron. Analogous plots for tantalum" and columbiumzo show a definite upward trend in the work-hardening rate. Keh and Weissman1 have pointed out that this behavior may be explained solely on the basis of changes in the dislocation configuration: at low temperatures the dislocations tend to be relatively straight and uniformly distributed, but at intermediate temperatures tightly knit tangles and cellular substructure appear. The interference of these tangles with glide dislocations causes the observed increase in the work-hardening rate. This explanation appears reasonable, yet one might ask what factors cause tangle formation to be so favorable at intermediate temperatures. It seens likely that the strong dislocation-interstitial interactions which are known to occur in this temperature range are at least partly responsible," with the magnitude of the effect being proportional to the interstitial concentration. The purpose of the present work is to study the relationship between tangle formation and strain hardening in a bcc metal in the temperature range 0.17 to 0.4 Tm. Particular emphasis was placed upon a study of the effects of interstitial-dislocation interactions. Single crystals of 3.25 pct Si-Fe containing about 200 ppm of C in solid solution were used in the investigation for the following reasons: 1) The mobility of interstitial carbon in 3.25 pct Si-Fe is negligible at 300°K but increases rapidly at slightly elevated temperature22. Hence, differences between the flow curves and dislocation structures of crystals deformed at 300°K, 0.17 T,, and crystals deformed, say, at 425°K, 0.24 Tm, should be appreciable because of the enhanced dislocation-carbon interactions at the elevated temperature. This effect was accentuated in some samples by interrupted straining, thereby introducing a certain amount of aging. 2) Near room temperature, slip in suitably oriented 3.25 pct Si-Fe single crystals is largely confined to the (110) planes.23&apos;24 Dislocation structures formed under conditions of single glide are the least complicated and their method of formation is the most easily discernable. 3) Dislocations in Si-Fe can be tightly locked with carbon atmospheres by a low-temperature aging treatment. The subsequent thinning of samples to foil thicbess causes little or no rearrangement in the dislocation structure.25 EXPERIMENTAL PROCEDURE Large single-crystal sheets of 3.25 pct Si-Fe were donated by Dr. C. G. Dunn of the General Electric Research Laboratory, Schenectady, N. Y. The orientations of the sheets were determined and slabs 1.0 by 0.25 by 0.05 in. were cut such that the desired tensile axis corresponded to the long dimension. The slabs were mechanically polished and subsequently decar-burized by heating at 1000°C for 3 days in a flowing wet-hydrogen atmosphere. A carbon content of about 200 ppm was introduced by heating at 805°C for 25 min in a flowing atmosphere of dry hydrogen containing heptane vapor. Shaped copper tools were then used to spark-machine at 0.125 by 0.50 in. gage length onto each slab. Vacuum annealing at 1225°C for 2 days followed by a quench into the cold end of the furnace to retain carbon in solid solution concluded the soecimen preparation. Continuous tensile flow curves for crystals of severa1 orientations Were obtained both at 300&apos; and 425°K. A strain rate of 6.67 x 10-4 Per set was used in these and all other tests. Crystals oriented for single glide, B and D in Fig. 1, were subjected to a 3.5 pct plastic elongation to insure uniform slip along the gage length; they were then immediately subjected to interrupted strain cycling as indicated in Fig. 2(a). Each cycle consisted of unloading to 1.5 kg per sq mm, holding

Jan 1, 1969

By F. D. Rosi

The slip and twinning behavior in extended titanium crystals were studied in some detail. The formation and appearance of coarse kink bands are discussed. Their crystallographic geometry was determined by X-ray analysis. A phenomenological interpretation of the complexities in kink band development is also presented. The critical resolved shear stress, coefficient of shear hardening, and plane of fracture were determined for several crystals extended at room temperature. THE slip and twinning elements observed in the room-temperature deformation of titanium were enumerated in a previous paper1 in which considerations were advanced regarding the nature and selection of these elements and their effect on the known mechanical properties of this metal. The present study concerns the crystallographic, microscopic, and mechanical aspects of flow in relation to the slip and twinning elements, and includes a prediction of slip systems, nature of slip and twin markings, inhomogeneities of plastic flow, and stress-strain characteristics. Unless otherwise noted, arc-melted titanium sponge (99.77 pct) was used in these experiments. The method of production of crystals, their dimensions, and the surface preparation for micrographic examination have been reported.&apos; For obtaining stress-strain characteristics, only those crystals which traversed the entire width of the specimen and were at least 8 mm in length were used. Tensile deformation of the crystals was performed with conventional grips for sheet specimens and a constant-stress loading beam, designed after the method of Andrade and Chalmers.&apos; The specimens were loaded by allowing sand to flow from a reservoir into a bucket suspended from the longer end of a balanced 6:1 lever arm at a rate controlled to load the specimen approximately 2 kg per min. Strain measurements were made using the Baldwin SR-4, bonded, resistance-wire strain gage, Type A-8, which permitted a reading accuracy of 2 microinches per inch. The formulas used in the evaluation of shear stress and shear strain, as in deriving the coefficient of shear hardening, are given by Schmid and Boasv n terms of the original orientation and change in length of the crystal. For calculating the critical resolved shear stress, the standard equation was used. The crystallographic nature of the unpredictable slip observed in a number of specimens was determined by the single-surface X-ray method of analysis as described in ref. 1. Experimental Results Prediction of Slip System: It was reported&apos; that room temperature slip in titanium takes place predominantly on {10i0} and in a <1120> direction, giving three potential slip systems. Hence, it should be possible to predict the operative primary system in the manner used by Taylor and Elam&apos; for alu- minum (i.e., the one with the greatest component of shear stress in the direction of slip). The stereo-graphic construction in Fig. 1 shows that this is true. In all cases, slip was found to occur initially on the (0110) plane and, in a number of cases, in the [21f0] direction. (The direction of slip was not determined for all orientations.) It follows that duplex slip can be expected when two slip systems are geometrically equally favorable for slip, as demonstrated in Fig. 2. In both crystals slip took place simultaneously on the (1700) and (olio) prismatic planes, as indicated by Fig. 2a and b. In the case of crystal B the movement of the specimen axis with increasing extension was toward the (10i0) direction, which represents the stable end orientation resulting from alternate slip on the [2ii0] and [1120] directions. This is analogous to the duplex slip process in face-centered cubic metals." Unpredictable Slip: In a number of crystals whose orientations were well within the operation of a single slip system, secondary slip occurred on planes not predicted by the criterion of maximum shear stress. Examples are shown in Fig. 3. In addition to

Jan 1, 1955

By H. R. Gardner

The heat treatmmt of plutonium was studied using the Jominy end-quenching technique commonly used for determining the hardenability of steel. Plutonium specimens were end-guenched from temperatures in each of the ß, y, d, d&apos;) and E phases. One series of specimens with a low-iron content, 165 pprn Fe, and another gvoup with a high-iron content, 678 pprn Fe, were used in order to study the effect of a Pu-Pu,Fe eutectic network on the hardness and micro-structure. Hardness traverses indicated no significant variations in hardness with either cooling rate or quench temperature. Metallographic studies indicated major effects on microstructure. Grain size was found to vary markedly with quenching temperature and cooling rate. It was determined that the Pu-PueFe eutectic network could be modified extensively by heat treatment, including spheroi -dization in the y phase and 6 phase below 413°C. An unidentified spheroidal inclusion was observed to go into solution in the delta and higher temperature phases. 1 HE element plutonium is unique among metals in that it has six allotropic forms in the solid state.&apos; These have been designated&apos; as the a, ß, y, d, d&apos;, and phases. The respective phase transformations occur at approximate temperatures of 122", 210°, 319°, 450°, and 480°C with a melting point at 640°C. With this number of phase transformations it becomes pertinent to consider the effect of heat treatment and cooling rate in the various phases on the microstructure and hardness of plutonium. To determine; the effect of a wide range of cooling rates, the Jominy end-quenching technique was applied to cylindrical plutonium specimens. In addition, since the presence of iron in amounts greater than 500 pprn is common in plutonium and results in a network of the Pu-Pu6Fe eutectic, it was decided to study heat treatment effects on two bomb reduced plutonium buttons with different iron contents. A low iron button containing 165 ppm Fe and a high iron button containing 678 ppm Fe were selected for this comparison. EXPERIMENTAL PROCEDURE Experimental Material. The cylindrical bars for Jominy quenching were cast from button stock in vacuo in MgO coated graphite molds. Metal pouring temperature was approximately 950°C and the molds were preheated to 300°C. The castings were machined to 0.5 in. diam. by 2.5 in. long cylinders. Chemical analysis and density data for the two groups of Jominy specimens containing different iron contents are presented in Table I. Except for iron, heats 19-12-1 and 20-2-1 are comparable within the limits of analytical accuracy. Representative specimens from the low-iron and high-iron bars were taken for metallographic examination. The low iron specimen was found to have extensive microcracking, Fig. 1. In addition, numerous unidentified spheroidal inclusions were present, Fig. 17. The average grain size of the low-iron plutonium is 0.068 mm, Fig. 4. In the high-iron plutonium, a Pu-Pu6Fe eutectic network is prominent, Fig. 7. The average size of the network is 0.100 mm. Unidentified spheroidal inclusions were also common in the high-iron plutonium. The average grain size of the high-iron plutonium is 0.036 mm. Experimental Technique. A Jominy end-quenching fixture was fabricated for glove box use. A 2.5 in. water height was used with an orifice of 0.250 in. ID. The orifice to specimen distance was maintained at 0.5 in. Annealing temperatures of 160°, 265°, 400°, 465°, and 535°c were chosen for the study of the effect of quenching from ß, y, d, d&apos;, and e phases on microstructure and hardness. During quenching, cooling curves were obtained from the Jominy specimens at distances from the quenched end of 1/16, 1/8, 3/8, 3/4, 1-1/4, and 2 in. Cooling rate calculations were made from the cooling curves for temperature intervals of 100° to 110° 160" to 170°, 330" to 340°, 420° to 430°, and 490° to 500°c. These temperature intervals were chosen

Jan 1, 1962

By AIME AIME

COMPLETION of the Rainbow Bridge across the Niagara River and Gorge this fall marks a new page of achievement in the annals of bridge- building. Symbolic of the amity between two great nations, the new bridge provides an additional gateway across the most peaceful border in the world. Ground was broken for the project May 16. 1940, at a site close to that formally occupied by the Falls View Bridge which was destroyed by a record ice jam in 1938. At this point, about 2000 ft. deep and 1000 ft. downstream from the American Falls, the gorge is about 200 ft. deep and 1000 ft. wide. The great steel arch of the bridge has a span of 950 ft. and rises from its supporting abutments on the American and Canadian sides of the river to the level of the top of the gorge. This is said to be the longest hingeless arch in the world.

Jan 1, 1941

By Uros Bajzelj

To mine very weak carboniferous schists subjected to high ground pressures the underhand cut-and-fill stoping method was proposed using an artificial plate roof. An experimental stope was mined using three consecutive levels. Rock pressures, deformation of the reinforced concrete plate, and the quality of stowing were evaluated. It was found that roof deformations were minimized if the reinforced concrete plate and uncemented backfill were replaced with cemented backfill containing reinforcement near the bottom. The mining method prevented the occurrence of high rock pressures at the face. The method is suitable for mining subvertical ore bodies with large horizontal areas.

Jan 1, 1984

By J. S. Osoba, J. W. Graham, P. H. Monaghan

Of the many factors which affect the productivity of hydraudically fractured wells, the wettability of the propping sand has received little attention in the pas/. This paper shows that the wettability of the propping sand is an important factor which shorcltl not he overlooked. An analysis of relative permeability data shows that fractures packed with water-wet sand should be more permeable to oil than are fracturer packed with oil-wet sand. Laboratory results verify this conclusion. Cnlculations show that higher permeability to oil in the fracture should provide higher well productivity. A method is presented which ensures that the propping sand in an induced fracture is water-we1 even though oil is used as the fracturing fluid. The rnethod has been used in more than 150 field jobs: the field resrrlts are discussed briefly. The fluidized nature of water-wet sand in oil has giver1 unexpected benefits. This characteristic of water-wet sand and how it has been used advantageously in field operations are discussed. INTRODUCTION Hydraulic fracturing of subsurface strata to increase the productivity of oil and gas wells has been practiced for about 10 years. Today, fracturing is used more often than any other method of well stimulation. Basically, the process consists of breaking down (fracturing) a subsurface formation with pressure applied by means of a carrier fluid, usually oil or water, and propping the induced fractures apart by means of an agent, usually sand. suspended in the carrier fluid. Currently about 68 per cent of all fracturing is done with a simple mixture of refined oil or lease crude oil and sand&apos;. The research of other investigators has suggested that dry sand is rendered oil-wet when it is contracted with certain types of crude or refined oils.&apos; Hence, it may be expected that some fracturing operations employing an oil as the carrier for sand leave fractures packed with oil-wet sand. Conversely, those operations which employ water as the carrier for the sand probably leave the fractures packed with water-wet sand. Since the permeability of a sand-packed fracture to a mixture of oil and water is dependent upon the wettability of the fracturing (frac) sand, research was undertaken to determine to what extent the wettability condition (water-wet or oil-wet) controls fracture permeability which, in turn, affects well productivity. Additional research was directed toward the development of a method for obtaining the desired fracture wettability. In this report both theoretical and experimental evidence is presented to show the desirability of employing water-wet sand in fracturing operations. A method to obtain water-wet sand is discussed, and field results are reviewed briefly. DEPENDENCE OF WELL PRODUCTIVITY ON FRACTURE WETTABILITY To determine the dependence of well productivity on the wettability of the frac sand, it is necessary to know, first, the effect of fracture wettability on fracture permeability and, second, the effect of fracture permeability on well productivity. The relationship of these variables is considered separately in the order indicated. Effect of Wettability on Permeability Fig. 1 shows relative permeability relations for 20-30 mesh Ottawa sand. Inspection of these curves reveals that the relative permeability to oil when a small amount of water accompanies the flow is considerably higher when water rather than oil is the wetting phase. For