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By Nicholas J. Grant, Rolf Nordheim, Thomas B. King

Constant-load creep-rupture tests were conducted in an argon atmosphere at temperatures of 1600 to 2200°F on two heats of iron containing about 0.06 and 0.09 pct P in solid solution. The tests were conducted in the as-cast condition. Stresses were selected to give strain rates approaching those encountered in the hot working of steel, and within the limits of the creep-rupture test apparatus, namely. from about 0.001 to 50 pct per sec. FOR generations, rolling and forging practices have been developed largely by empirical methods, based on prior experience. While largely successful, difficulties are frequently encountered when new or different alloy compositions are tried for the first time. There is need to know the relationships which exist among temperature, strain rate, composition, and other variables on the deformation and fracture characteristics of steels. It has been shown for aluminum and several high-temperature alloys that the deformation and fracture characteristics follow rather well-defined laws and patterns which are closely related to the effects of strain rate, temperature, and composition.1"3 As the melting temperature of aluminum or its alloys was approached, it was possible to study the interplay of work-hardening factors and recovery or recrystal-lization, the latter resulting in improved ductility and increased resistance to intercrystalline fracture. In particular, the effects of composition are very poorly known. Within the meaning of "composition" should be included impurity elements, such as sulfur, phosphorous, lead, copper, and many others, as well as those elements which are added for alloying purposes in iron. The role of multiphase structures, in contrast to solid solutions, should also be studied in much greater detail. high strain rate creep-rupture tests would provide information regarding the deformation and fracture characteristics of metals at hot-working temperatures. It was also desired to establish the stresses which are necessary to accomplish the desired deformation, and to relate these to the strain rate and temperature. Secondly, it was the purpose of this particular study to determine the effects of phosphorus, within solid solution limits, on the deformation and fracture characteristics of iron at hot-working temperatures. EXPERIMENTAL PROCEDURE Two phosphorus levels were selected, one corresponding to the upper limit normally found for commercial steels, and one substantially higher than this, but within the region of solid solubility at the test temperatures chosen for this investigation. Twenty-pound heats were prepared by induction melting electrolytic iron in air in a magnesia lined furnace. After deoxidation with about 0.2 pct Al, ferro-phosphorus was added, and the heats were then poured into prefired silica molds. The purpose of using silica molds was to obtain a slow cooling rate during solidification to produce a relatively coarse grain size, producing a structure subject to some segregation and therefore more nearly characteristic of ingot structures. The major part of the casting assembly provided a large shrinkage head in order to produce sound castings and to promote slow cooling of the specimens. The primary austenitic grain size varied from ASTM No. 2 to No. 00. The composition of the heats, including a low phorphorus melt, used for comparison purposes, is shown in Table I. It will be noted that the oxygen content of the phosphorus containing heats is relatively high, in spite of the deoxidation practice, a condition which is difficult to control in small melts. Creep-rupture tests were nevertheless undertaken when it was noted that this quantity of oxygen did not appear to give results any different from those from a heat containing 0.01 pct 0, low phosphorus and comparable carbon Content;4 see Table 11.

Jan 1, 1961

By S. R. B. Cooke, W. Philippoff, Donald E. Cadwell

[THE importance of contact angles in flotation has long been recognized, but little has been done to get quantitative relationships between the surface coverage of the mineral by the reagent, the length of the hydrocarbon chain, and the contact angle. It is well known that for a complete monolayer on the surface of a mineral the contact angle ? is determined only by the reagent&apos; and principally by the chain length of the hydrocarbon radical. Although for flotation the monolayer usually is regarded as being complete, early experiments of Wark and Cox2 showed that at very small concentrations of potassium ethyl xanthate the contact angle on galena changed in a continuous way from 0° to the equilibrium value of 60°. Further, Gaudin and Vincent&apos; showed a similar continuity using heptylic acid and sphalerite. This shows that with probably incomplete monolayers, ? varies with the degree of surface coverage. At the time these experiments were made it was impossible to measure the actual amount of surface coverage, especially since the decrease of the collector concentration in the liquor could be influenced by chemical side reactions. Through the use of the radioactive tracer method for the measurement of the amount of collector adsorbed on the surface of the mineral, Gaudin and Bloecher4 were able to determine accurately the actual surface coverage of dodecylamine acetate on quartz, but they did not measure any contact angles. It is believed that the relationship between the surface coverage and the contact angle is extremely important in flotation, especially as Gaudin and Bloecher showed that a 95 pct recovery is possible with a coverage of only 5 pct. Theoretical Considerations The work of adhesion W is the energy bound (in ergs per sq cm) when an interface is formed. It is determined by, the difference of the free surface energies (surface tensions) of the respective phases ?1 and ? 2 before contact and the interfacial free surface energy ?12 after contact. The definition of the contact angle permits the elimination of the unknown surface energy of the solid and hence the calculation5 of W from the surface tension of the liquid ? and the contact angle ?: [W = y (1 + cos ?)[1]] Consider a surface consisting of two components, identified as 2 and 3, 1 being the liquid. The amount of 2 in the composite surface is x, where 0 < x < 1. The respective contact angles with 1 and air are ? and ?3. The total work of adhesion of such a surface is the sum of the values of the components multiplied by their respective areas. A formal relation can be written: [W,,,=x•W2+ (1-x).WR[2] .] in which Wm is the work of adhesion of the composite surface. Eq 1 can be introduced into W2 and W3 but in the case of Wm some discussion is needed. If the two components are segregated, each component forming an integral part of the composite surface there is no physical meaning for a contact angle ?m, calculated from Wm, by using eq 1. If, on the other hand, the area of each patch of the components is small in comparison with, say, the diameter of the bubble used in measuring, it could be expected that ?m would have aphysical significance, because of the action of the surface tension of the liquid-gas interface tending to smooth out sharp corners. How small these patches would have to be is difficult to predict, but by using composite surfaces with microscopically]

Jan 1, 1952

By D. J. Freeh, W. E. Horst, R. C. Kellner

This paper is concerned with the description of grinding characteristics in a batch grinding system. A mathematical model was developed and used for simulating the system on an analog computer. A general equation describing the change of selected size fractions with respect to time is presented. The empirical verification of the model is discussed. In order to understand the performance of a grinding system, it would be desirable to have a mathematical description of the system&apos;s behavior. The development of a mathematical model to describe the performance of a batch dry-grinding operation was investigated. This is the first step toward reaching the objective of a practical mathematical description of a grinding system that could be employed for process control and optimization of a simple or complex grinding circuit. Although this article is concerned only with batch grinding performance, experimental work is being conducted to extend the model to continuous grinding systems. BASIC PROCESS CONSIDERATIONS In a paper dealing with the probability theory of wet ball milling, Roberts1 correlated the rate of change of oversize material, C, with energy input, E, as follows where the energy input is expressed in power/unit mass and k is a constant for each particle size. Experimental grinding studies were made by Bowdish2 to extend the previous work of Roberts. The work of Bowdish also showed that the rate of breaking of oversize particles in a ball mill is proportional to the concentration of oversize particles present. He further demonstrated that breaking of oversize particles is proportional to the surface area of the balls used for grinding. Rate equations were presented and it was concluded that grinding could be considered as a first order phenomenon according to the rate equation [2] di which is in accordance with Eq. 1. In Eq. 2, the effect of ball area is included in the constant k,. Other rate equations were reported to show the effect of a change in ball area and removal of fines during grinding. Correlation studies made by Arbiter and BhranY indicate a first-order rate equation for quartz; however, their data showed less than first-order rates existed for some of the other materials evaluated. More recently Kelsall4 has shown that the rate of breakage of any narrow size range of quartz could be described by a first-order rate equation. Several other investigators5-7 have described grinding behavior in terms of rate equations or kinetics. In general, the rate equations have been described for each particle size; however, the interactions between sizes and the overall relationships that exist have not been considered, at least not in the form of solving a group of simultaneous differential equations. Extensive work has been conducted by various investigators using a probabilistic approach which has expanded stein&apos;s&apos; earlier work. Selection and breakage matrices are incorporated in the probabilistic model as contrasted with the deterministic method presented here. A batch grinding operation may be considered as an unsteady-state process from the standpoint that the conditions within the mill are a function of time. Therefore, a plot of mass fraction of the i-th size versus time would give a set of curves as shown in Fig. 1. In these curves X , represents the mass fraction of large size material, X2 intermediate size, and X3 small size material. An examination of these curves shows a strong similarity to the curves that would be obtained from a chemical reaction of the type9 A?B?C, [3] where A would be comparable to the largest size material being broken to an intermediate size, 3, and

Jan 1, 1968

By J. J. Hauser, H. C. Theuerer

A cathode sputtering technique is described which elin7inates the need for ultrahigh vacuum in preparing thin films of materials sensitive to gaseous impurities. This technique uses a fraction of the atoms sputtering within an anode container to getter actice gases, such as HzO, Oz, and Nz. The gases alzd gettering metal are deposited on the container walls, thus shielding the coating zone of the system from contamination. The use of the method for preparing superconducting-normal metal couples such as Ph-Cu and Ph-Pt is described, and the properties of the individual and composite films are given and discussed. GETTER sputtering is a method which greatly simplifies the preparation of thin films in cases where composition control is critical. A major difficulty with conventional sputtering and other vacuum-deposition techniques is the contamination of the forming film caused by residual gases, such as H20, CO, Oz, and Nz, in the coating equipment. The difficulty arises from the fact that even when the residual pressure in the system is as low as 1 x 10"6 Torr, with a deposition rate of 10A per sec, there are as many contaminating gas collisions with the substrate as there are with film-forming metallic atoms. It is not surprising, therefore, that with reactive metals, such as tantalum and niobium or with semiconductors, such as silicon and germanium, films with properties far different from the starting materials are obtained. In the case of niobium and tantalum, deposited either by sputtering or vacuum evaporation in systems with reactive gases at pressures of the order of 1 x l0-&apos; Torr, the loss of superconductivity is traceable to interstial oxygen or nitrogen. On the other hand, working in vacuum of the order of 1 x l0-" Torr, Marchand and enema&apos; have shown that superconducting films of tantalum with properties approaching those of bulk material are possible. At this level of gaseous impurities -lo6 metallic atoms arrive at the substrate before a contaminating collision occurs again assuming a deposition rate of 10A per sec. It is evident from the above that any successful vacuum technique requires the elimination of reactive gases from the region of the system where coating is occurring. Getter sputtering accomplishes this using conventional vacuum equipment with residual pressures in the 106 Torr range. In fact? vacuum systems with residual pressures of lo-" Torr are adequate for most purposes. With this method, sputtering is confined within an anode can and, by geometric design, sputtering itself is used to purify the argon at the lower and upper parts of the system by the gettering action of the reactive metal. In consequence, the central region of the system where coating occurs is shielded from gaseous contamination. Getter sputtering is particularly useful for the preparation of alloy and compound films. With this method, if a cathode of homogeneous composition is bombarded with high-energy argon ions, transfer of material to the substrate having the same composition as the cathode will occur. This is true after an initial equilibration time, even though the constituents of the cathode may have different sputtering rates. During equilibration, the surface of the cathode changes composition due to differences in sputtering rate, but mass conservation demands a steady-state condition such that the atoms sputtered from the surface have the same composition as the cathode material from which the surface is generated. GETTER-SPUTTERING APPARATUS The original form2 of the getter-sputtering apparatus is shown in Fig. 1. It consists of a closed nickel or stainless-steel can 4 in. tall and 2-3/8 in. in diameter. Mounted symmetrically from each end

Jan 1, 1965

By J. C. Bokros

At temperatures above 950°F, zirconium which has been strained a critical amount will experience critical recrystalli-zation. The large grain size thus formed can result in a reduction in the fatigue life by a factor of 2 to a factor of 9 at both high and low temperatures. The critical strains for zirconium vary from 15 pct at 900°F to about 2 pct at 1125°F, while those for zircaloy III vary from 15 pct at 1050°F to 5 pct at 1200°F. Zircaloy II ,experiences no critical recrystallization up to 1200°F. ZIRCONIUM has become increasingly important for nuclear applications and is being employed in reactors at temperatures where recrystallization can occur. Recent work&apos; on the fatigue properties of zirconium has shown that coarse-grained structures developed in zirconium during recrystallization have much lower fatigue lives than fine-grained material. The development of these large grain sizes under such conditions is well known to be the result of critical recrystallization.2-4 Briefly, critical recrystallization occurs when a metal is strained a critical amount and annealed in the recrystallization range. The critical strain is defined as that minimum strain necessary to promote nucleation in the time unit and temperature considered. The maximum grain size occurs at the critical strain, since at this strain the fewest stable nuclei per unit volume grow into new grains. Recrystallization is not evident below this; strain since the nucleation rate is vanishingly lolw, and metal strained more than the critical amount has a higher nucleation rate per unit volume which results in a finer grained structure. This paper describes the critical recrystallization observed in reactor-grade zirconium, zircaloy 11, and zircaloy I11 as a function of annealing temperature and temperature of strain. EXPERIMENTAL The zirconium used was hafnium-free, double arc-melted sponge obtained from the Bureau of Mines. The ingots were forged and hot reduced to 0.08 to 0.10-in. sheet and subsequently cold reduced to 0.035-in. sheet with intermediate and final anneals at 1200 OF for 15 min. The zircaloy II and zircaloy III used were 0.035-in. sheets in the annealed condition. Compositions of these materials as tested are given in Table I. To determine the critical strain at a given temperature, tensile specimens having a0.065-in. taper in a 2-in. gage length were machined from the sheets parallel to the rolling direction. The specimens were polished, etched, and examined metallographically to ensure that all of them were strain-free, initially. Tukon indentations were made every half millimeter along the gage length of each specimen. These served as fiducial marks enabling the plastic strain to be measured with a microscope and micrometer stage. The specimens were pulled to failure at a rate of 0.002 in. per min in an Instron tensile-testing machine. Three temperatures were used for straining: room temperature, 500 ºF, and 900 ºF. The 500º and 900 ºF tests were run in an argon atmosphere. Since the rate of work hardening changes with temperature, a different critical strain was obtained for each temperature of strain. Specimens, prepared in the manner described, were annealed in vacuunl at various temperatures ranging from 900" to 1200 F for up to 1000 hr, after which they were examined metallographically. The critical strain and the recrystallized grain size as a function of strain were determined for each specimen. Results for the same temperature and time indicated that the critical strain measured was reproducible to within 5 pct of each other. RESULTS AND DISCUSSION Since increasing the time of anneal increases the probability of the nucleation of a new grain, the critical strain decreases with time at a decreasing

Jan 1, 1961

By H. C. Chang, N. J. Grant

Creep of very coarse grained high purity aluminum was studied at 400°, 700°, and 1100°F at initial stresses of 50 to 1200 psi. Local strain measurements were made across the grain boundaries and in different regions of various grains during creep, thereby permitting the drawing of component creep curves. The relative amounts of elongation as measured across a grain boundary and in the grains adjacent to the boundary depend on the temperature of testing. The significance of creep curve equations and activation energies is discussed. THIS paper presents some of the results of a research program devoted to the study of the mechanism of creep in high purity aluminum. Previous publications have dealt with the cyclic processes of alternating grain boundary sliding and migration, and the deformation in the grains caused by these processes;&apos; the direction and the driving force of grain boundary sliding and migration;&apos; the deformation in the grains and the restricting effects of the grain boundaries on this deformation." These previous papers were based mainly on either microscopic observations or X-ray data, or both. Sometimes creep curves across two closely spaced reference marks (about 0.6 to 0.7 mm apart) were also presented with a view to correlating the elongation values with the optical observations in general, and with certain deformation processes in particular. These curves shall henceforth be referred to as component creep curves. No attempts were made, however, to compare either the component creep curves which were obtained in different regions of a specimen, or those obtained from different specimens subjected to different creep test conditions. It is the purpose of this paper to present these component creep curves. Among the factors influencing the behaviors of these curves, those studied were stress, temperature, and grain arrangements in the specimens. It is proposed to show how greatly the deformation can vary from grain to grain and within an individual grain in a coarse grained specimen. The experimental technique and procedure have been presented.&apos; It remains necessary to emphasize that the reference marks were produced by pressing a thin sewing needle into the surface of the specimen before the final annealing at 900°F for 24 hr and at 1150°F for 12 hr. The cold work around the needle indentations was therefore removed. The depth of these holes after electropolishing the annealed specimens was about 0.01 mm. This depth and area were negligible in comparison with the thickness of the specimens, 2.3 mm, and hence would not affect the creep behavior. Results Fig. 1 shows a development diagram of specimen P-8. The dots on the surface locate the needle point reference marks used to obtain the component creep curves. A curve obtained between two dots across a grain boundary measures not only the boundary deformation but also the deformation associated with boundary sliding occurring in the grains in the region between these indents. The original distance between two reference marks was about 0.6 to 0.7 mm. The maximum error of measurement was 0.01 mm, or in terms of percentage elongation, of the order of & 1.5 pct. Whereas the component creep curves shown in the figures to follow were drawn as a gross average of the points, in view of the fineness of some of the steps of grain boundary sliding and migration, as shown in the previous publications,¹,2 it appears logical to expect that some of the finer cycles of movement have not been delineated for the strain sensitivity of the measuring system. It seems justifiable to say that the curves are not as smooth as shown. 700°F Tests: Fig. 2 shows component creep curves across four of the grain boundaries in specimen P-8, tested at 700°F and 85 psi. These curves clearly show alternate cycles of increasing and decreasing

Jan 1, 1954

By R. F. Mitchell, G. F. Dillon, A. F. Armington

In this paper the present methods of boron preparation are discussed with emphasis on the iodide intermediate. Several methods of boron triiodide preparation were investigated, the most satisfactory method being the preparation from the elements. A yield of 60 pct based on iodine is found for this method. Zone-refining, sublinzation, distillation, and fractional-recrystallization results are given for the boron triiodide, with distillation producing the best results. Several methods of decomposition are also discussed. The purity of the resulting iodide boron approximates the puritjl of the best available bromide boron, ELEMENTAL boron has been suggested as a possible high-temperature semiconductor by several workers,&apos; but has never been exploited as a device material. The principal difficulty with boron is the unavailability of pure crystalline material from which accurate information on electrical properties could be obtained. Most boron crystals presently produced are very imperfect in structure and of questionable purity, particularly in relation to carbon content. Several methods of boron purification have been reported in the past few years, all of which produce material with a purity better than 99.0 pct. Most of these methods have been the subject of a recent review by Starks&apos; and will not be elaborated upon in this report. However, of all the purification methods reported, only those using halide intermediates produce a purity approaching that usually required for electronic applications. The bromide intermediate has been most used for the preparation of high-purity boron.&apos;y3 This material is easily prepared from the elements and can be effectively purified by distillation and decomposed by hydrogen reduction. The resulting product contains a trace of silicon, and an uncertain amount of carbon, believed to be approximately 100 ppm. It has been recently reported by Russian workers that high-purity boron can be produced using an iodide intermediate.&apos; In the work cited, boron is reported free of spectro-scopically determined impurities, but the reported detection limits are quite high (- 100 ppm). In addition, no data is given on the carbon content of the product. In the present paper, boron triiodide was chosen as the intermediate for several reasons. First, carbon tetraiodide, which could be a major impurity, is reported to be unstable above 200" and hence could be easily separated from the boron triiodide by its decomposition, since temperatures greater than this are attained during the purification process. The low melting point (45°C) and boiling point (20B°C) and the relatively high vapor pressure of boron triiodide should allow the application of any physical purification technique to the material. The possibility of a lower decomposition temperature than that used for the bromide process is another advantage which might cut down extraneous contamination. The iodide, however, does have certain disadvantages when compared with the bromide, the production cost being the most significant. This is the result of a higher halide-to-boron weight ratio, which means more intermediate must be employed. The cost of the starting material is also greater for the iodide. This cost could be considerably reduced however, by recycling the iodine byproduct. Epitaxial growth of boron, which is probably the best method of producing junctions, should be possible with either the bromide or the iodide as the intermediate. However, this has been attempted only on a limited scale up to the present time because of the unavailability of good crystals. The authors have been relatively successful in laying down a heterotaxy of boron on silicon, however. This will be reported at a later date. Several crystalline modifications have been reported for boron, four of which are now believed to be real.&apos; These are the a! and 0 rhombohedral and the a, and 0 tetragonal. In general, the a! rhombohedral is the low-temperature form and the B rhombohedral is the high-temperature form. The tetragonal structures are detected between 1000"

Jan 1, 1964

By A. W. D. Hills

This paper describes the development of a generalized integral-Wofile method for the analysis of heat transfer dwing solidification. The method is extremely flexible, and can be applied to a wide range of situations. This flexibility has been achieved by characterizing the solid metal layer in terms of two parameters, and by developing two simultaneous nonlinear differential equations for these parameters in terms of the heat fluxes crossing the boundaries of the solid layer. The use of these equations is illustrated in a series of examples which involve the solidification of pure metals at zero superheat cooling under different conditions. The simplicity with which the method can be extended to treat more complicated jwoblems is illustrated in a further example which involves natwal convection effects in the liquid metal. ThE rate at which molten metal solidifies in an industrial casting process, and the structure of the cast product, are both controlled by the rate at which heat can be removed from the casting. A knowledge of heat transfer rates is thus essential to the control of the process and to the control of the structure and soundness of the final casting. Heat transfer rates during real solidification processes cannot be predicted by formal mathematical techniques, however, because nonlinear boundary conditions are involved. Approximate methods are normally used, and these have included electrical and hydraulic analogue techniques, finite difference methods, and the integral-profile method. Considerable effort has been devoted to the development of the first two techniques, but the integral-profile method has been used very little so far. This is unfortunate because the method is capable of providing relatively accurate solutions for the heat transfer equation during solidification without involving large amounts of computer time. A further advantage of the method is its flexibility, although this is not apparent from the integral-profile solutions that have been developed to date. These solutions have been derived for the solidification of molten metal at zero super-heat under cooling conditions involving either a constant heat flux from the cooled surface;&apos; a constant heat transfer coefficient at the surface,&apos;-3 or a specified variation in the surface temperature.4,5 A generalized integral-profile method is presented in this paper which can be used to predict unidirectional solidification rates under a very wide range of more realistic cooling conditions. The use of the method is illustrated in a series of problems involving pure metals, or skin forming alloys, solidifying at zero super-heat. However, the principal advantage that this method has over the previous integral-profile methods is the ease with which it can be extended to treat more complicated solidification problems. This is illustrated by considering a problem in which super-heat is liberated from the liquid metal by natural convection during the solidification process. In the final section of the paper the generalized method is compared with previous methods used to predict solidification rates and its extension to more complicated solidification problems is briefly discussed.

Jan 1, 1970

By D. C. Hilty, W. Crafts

Determination of the solubility of oxygen in iron containing silicon, or manganese, or both, has confirmed the earlier work on silicon, shown that manganese is more effective than expected, and has demonstrated that the combination of silicon and manganese is a much stronger deoxidizer than might have been inferred from their individual effects. SILICON and manganese are of primary impor-tance in the deoxidation of steel, and a study has been made at the Union Carbide and Carbon Research Laboratories, Inc. of the solubility of oxygen in iron in the presence of silicon and manganese, singly and in combination, as a basis for more effective control of inclusion formation. The investigation was carried out with the same equipment and experimental procedure that were used in the determination of the oxygen solubility of iron containing aluminum&apos;. The heats were melted in a rotating crucible furnace under an argon atmosphere. Bath temperatures were controlled by platinum/platinum +10 pct rhodium thermocouples to attain equilibrium at 1550°, 1600°, and 1650°C, so that oxygen solubility isotherms were determined directly without requiring calculation from a temperature coefficient. A detailed description of the furnace and procedure is given in the paper on aluminum deoxidation1. Oxygen solubility in the presence of more than 0.10 pct silicon was found to approximate earlier determinations closely, but some deviation was observed at lower silicon contents. Manganese appeared to be more effective than had been anticipated. The combination of silicon and manganese lowered the solubility for oxygen markedy as compared with either silicon or manganese alone. Although the solubility for oxygen in the presence of both silicon and manganese represents only a part of the information needed to control inclusion formation, it suggests a partial explanation of the benefits of this combination that have been observed in practice. Manganese and Oxygen in Liquid Iron: The study of oxygen in iron in the presence of manganese was carried out in magnesia crucibles of the type furnished commercially for laboratory induction furnaces. Alumina crucibles were unsatisfactory, because the work on the aluminum-oxygen equilibria in iron&apos; had shown that merely melting iron in an alumina crucible limited the solubility of oxygen to a level considerably below that anticipated for moderate concentrations of manganese. Silica crucibles appeared unsuitable because of the dangers of excessive fluxing by the melt. Moreover, as will be shown later, melting iron in a silica crucible also limits the oxygen content below that in equilibrium with

Jan 1, 1951

By H. R. Peiffer, R. Geckle

The silver phase of silver and finely divided alumina composites is shown to grow as single crystabs upon solidification from the melt. These crystals grow without the aid of an externally applied thermal gradient or a mold. The single-crystal growth is more readily disrupted as the alumina content varies from the optimum concentration of 20 wt pct. Pretreatment such as variation of fabrication pressure, and presintering of the specimens appear to play a lesser role in this phenomenon. In actual practice the growth of single crystals of metals from the melt is a tedious, painstaking process.&apos; Care must be taken to insure the proper thermal gradients and rate of growth in a vibration-free environment. Excellent single crystals can be grown when these variables are controlled. When a second insoluble and finely divided phase is present in the melt the growth of single crystals is difficult, if not impossible, even under the most favorable conditions outlined above. During the past few years, a composite of silver and alumina has demonstrated an ability to resist flow even though the major phase, silver, is mo1ten. 2 A more surprising feature of this material is the ease with which single crystals of silver grow upon cooling the composite from temperatures above the melting point of silver to temperatures near room temperature. Observations have been made that demonstrate that single crystals of silver will grow even when conditions most unfavorable for growth of pure silver crystals exist. The crystals grown in this manner are imperfect in that a great deal of subgrain structure exists. It is the purpose of this manuscript to qualitatively describe this process and to attempt to isolate the influencing factors of this behavior. MATERIAL PREPARATION The composite material is prepared by powder-metallurgical techniques. Two items of great importance are the introduction of oxygen into the system and the obvious need for a thorough mixing of the metallic and refractory oxide phases. The oxygen is necessary in order that the silver wets the alumina. Without oxygen the phases separate and the material shows no unusual properties. In order to supply the needed oxygen the silver is added in the form of silver oxide which is readily decomposed to oxygen and silver upon heating. The silver oxide is readily obtained in a finely divided form that allows a uniform mixture of the alumina and silver oxide to be prepared. The correct ratio of alumina to silver oxide is mixed in the presence of alcohol in an ordinary food blender. The mixture has the consistency of a thin slurry and after mixing for approximately 20 min is dried and pressed into billets at various pressures. As is shown in Fig. 1, there is no limit to the shape of the specimens obtainable as single crystals. These billets are heated in air in a predeter-

Jan 1, 1964

By P. E. Schauer

During the initial nine-year deple-tion of the McKamie-Patton pool gas-condensate reservoir, the pressure behavior and fluid analyses indicated pressure maintenance by gas injection would be attractive relative to continued pressure depletion. As a result, a gas cycling program was inaugurated in Aug., 1949, which has since maintained reservoir pressure. In order to evaluate the benefits of this program, the recoveries for natural depletion and for cycling followed by blowdown were determined by calculating the fractional balance of the molar quantities of vapor and liquid remaining in the reservoir and produced at the surface for various stages of depletion. The results of the investigation show theoretical ultimate recovery due to the cycling program will be 42 per cent greater than would be realized under pressure depletion type operation. INTRODUCTION The benefits of gas injection pressure maintenance programs in condensate reservoirs have been recognized and qualitatively described in several papers1-8 during the past 15 years. Some of these papers also describe methods for calculating the increased recovery realized from cycling; however, as a rule, hypothetical reservoirs were used as examples".&apos;.. This paper presents an evaluation of the pressure maintenance program for the McKamie-Patton condensate reservoir and includes a description of the fractional balance method employed to determine the benefits. Reservoir Development and Characteristics The McKamie-Patton pool, Lafayette County, Ark., was opened in June, 1940, with production obtained from the oolitic Smackover lime at a depth of approximately 9,300 ft. The structure is an anticline 8 miles long by 1 to 2 miles wide, and is one of many productive Smackover structures in Southern Arkansas. Of predominant importance is the condensate-bearing gas cap portion of the reservoir, which covers approximately 4,000 acres, attains a maximum thickness of some 200 ft, and has an average thickness of 90 ft. Development of the cap was accomplished with 21 wells drilled on 160 acre spacing. An isopach map of the cap is shown in Fig. 1. In addition, an oil rim is present along most of the periphery of the pool. Production practice includes field separation of black oil, and a high pressure gathering system which carries total well stream from gas cap wells to a plant where condensate is separated and the gas is processed for recovery of natural gasoline, butane, and propane. Since the gas contains appreciable hydrogen sulfide, it is removed by amine contact, after which free sulfur is produced by the Claus process. Core analyses from 1,767 gas cap formation samples averaged 14.2 per cent porosity and 379 md dry air permeability. Connate water was restored on seven samples of gas cap rock by air-brine capillary techniques, from which the interpreted water saturation averaged 28.17 per cent. During the early life of the field, it was believed the recovery mechanism, based on several of the other regional Smackover reservoirs, might be a natural water drive. However, subsequent production and pressure history revealed that the gas cap would not be produced by water drive, but would behave as a closed reservoir. In this respect, during the nine-year period of natural depletion from initial production to Aug., 1949, the cap production of 84.3 billion

Jan 1, 1958

By Fred C. Bond

The Standard method of determining the crushing resistance of rocks consists of crushing prepared shapes under slow compression, and expressing the ultimate crushing resistance at the load causing failure in pounds per square inch of cross-sectional area perpendicular to the crushing force, with the height approximately equal to the diameter. One-inch cubes or cylindrical drill cores are commonly used. Cubes and drill cores are cut by a highspeed steel disk with diamond dust embedded in the edges, and running under a water spray. such a saw will cut one square inch or more of hard stone per minute. An oiled, spherical, swivel compression block of small diameter should be used to equalize the pressure. Each sample is crushed between sheets of cardboard or blotting paper extending about one-half inch beyond the edges of the stone. A cloth is wrapped around it to prevent dangerous explosive shattering. It is probably preferable to place the swivel block below the specimen, with either a rigid head or another swivel block above. Whatever the arrangement, the conditions should be selected that will develop the maximum crushing strength of the specimen, even though its top and bottom planes may not be precisely parallel. The cardboard pads may be dispensed with if the ends of the specimens are polished smooth. The use of lead pads was discontinued because of the observed tendency to split the material. The samples are weighed and measured before breaking, and the density is calculated. Cubes that contain bedding lanes or veinlets are usually placed with these vertical and parallel to the crushing force, in order to develop the maximum resistance possible. A number of compression tests were made on Canadian ores, by Forrest Nagler, of the Allis-Chalmers Manufacturing CO., and are listed alphabetically in Table I. These tests were made on one-inch cubes or on diamond-drill cores approximately one inch in diameter and One inch long. The drill cores represent virgin rock, while the cubes may have been previously weakened by explosives. compression tests have been made in the Allis-Chalmers Milwaukee Laboratory on a number of ores and other materials. These are listed alphabetically in Table 2. In test NO. 1339, on limestone from the Hanna Coal Co., comparison was made between 2 by 2-in. diamond-drill core segments and one-inch cubes cut from the cores in the same strata. Results for the cylinders are tabulated directly below those for the cubes. The bedding planes were normal to the compressive force in breaking the cylinders and parallel in breaking the cubes, which accounts for the lower strength obtained from the cylinders. The percentage of net linear compression at the ultimate pressure was measured in test No. 1055 for Fontana TV A quartzite as 0.30 for cube A, and 0.37 for cube D.

Jan 1, 1947

By J. S. FINLAY

OPERATING a "muck stick" never appealed to me. It always seemed a terrible waste of energy to "put rocks in the box" by hand-particularly when my own personal energy was involved. But during the past forty years, there have been periods-more or less extended when I was compelled, against my finer instincts, to muck or quit eating. For about the same length of time, I have devised schemes to make mucking faster and more painless. There was always something mechanically wrong with these designs-too many;" parts to wear out and need replacement, and excessive cost incidental to a complicated mechanism. The idea of a shovel unit comprised of a single, rigid assembly which would roll from a digging to dumping position solved the problem of simplicity and durability. Ingersoll-Rand&apos;s utility engine provided a splendid power plant, small enough and powerful enough for the job. In the machine finally developed, known as the Eimco-Finlay loader, roller chains are preferred to gears for power trans-

Jan 1, 1935

By John C. Calhoun, Frank T. Bethel

Glass beads have been surface treated with Dri-film to render them oil wet by n-octane to varying degrees, and capillary desaturation curves have been determined by the restored state method. The desaturation curves show a regularity of increasing displacement pressures as the oil wetness increases. This has been used to compute apparent contact angles between n-octane and water on glass. The family of desaturation curves also shows a regular crossover, such that the residual wetting liquid saturation values are in reverse order to the displacement pressures. A semi-logarithmic variation is shown between the apparent contact angle and the residual saturation. The desaturation data are interpreted to mean that the wetting liquid ceases to be a continuous phase within individual pores before the capillary pressure can be raised sufficiently to force out the wetting phase completely. The saturation of wetting liquid at which this break in liquid continuity occurs is higher as the oil wetness decreases. INTRODUCTION The petroleum industry has for some time been using measurements of capillary pressures on porous media for research correlations and engineering calculations. It has been generally recognized that the capillary desaturation curve reflects the character and arrangement of the pores within the media and the distribution of fluids within the pores. Methods have been proposed for computing pore size distributions, tortuosity factors. and relative permeabilities from capillary desaturation data.&apos; There is little doubt that the interactions between porous rocks and their contained fluids resulting from surface forces play a dominant role in determining the magnitude and direction of capillary pressure measurements. There have been attempts to introduce as variables two quantities — inter-facial tension and contact angle — generally used to char- acterize surface forces, but in spile of the wide interest in these quantities as important variables, few definite conclusions have been drawn concerning their qualitative or quantitative significance. INTERFACIAL TENSION The interfacial tension appears in a capillary pressure function given by Leverett for correlating capillary desaturation type curves. Use of the interfacial tension in this function seems to be justified by other experiments reported. Apparently, interfacial tensions have little bearing on wetting phase residual by desaturation. CONTACT ANGLE The contact angle was utilized as a variable by Bartell and co-workers"." in tests on displacement pressures, later recognized as the initial point of capillary desaturation. Although Leverett did not include contact angle in his original formulation of the capillary pressure function, later workers suggested its addition. Few reports are available to show variation of residual liquid with contact angle as a result of capillary desaturation.&apos; The problems attendant to measuring contact angle within a porous medium are great. As a consequence of the lack of a concrete approach to a measurement. the workers in this area of research have adopted the general expression of "wettability" to indicate the relative position of two liquids saturating a porous body. It has been shown that gross measurements on porous systems, including capillary desatura-tions, are sensitive to wettability. Attempts at giving a scale to wettability in terms of contact angle through capillary desaturation curves have been made and these apparently are steps in the right direction. In these attempts presence of many other variables precludes attainment of exactness. Also, as a result of other variables, it has been impossible to correlate changes in apparent contact angle with changes in other physical measurements of the systems in question. The present work is an attempt to eliminate as many variables as possible in measuring capillary desaturations resulting from changes in contact angle within a porous medium.

Jan 1, 1953

By C. Kremer Bain

UNDER present economic conditions the necessity of mechanizing the mines of our country has become a very important problem. More and more mines are looking toward increased or complete mechanization of their operations, so in the writer&apos;s opinion it is quite pertinent that some of the associated problems that accompany such a program be pointed out. The following generalization on attempting a comparatively slight change in mining methods at the Southeast Missouri properties of the St. Joseph Lead Co. is an attempt to point out to anyone faced with a mechanization program that much time and C. KREMER BAIN, Member AIME, is Assistant to General Manager, St. Joseph Lead Co., Bonne Terre, Mo. AIME Sun Francisco Meeting, February 1949. TP 2743 A. Discussion (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Dec. 27, 1948; revision received Oct. 13, 1949. effort can be saved, and many headaches avoided, if company policy can be established whereby everyone in the organization from the top down is desirous of improvement and is working towards the common objective. Any changes in mining methods, machinery, and so on, must entah coordination of all the other phases of mining as they all have to mesh as accurately as a smooth running chain of gears if satisfactory results are to be obtained. The purpose of this paper is to point out some of the problems which :have to be surmounted when any mechanization program is attempted, rather than to go into the mechanical details and actual operating data of the equipment employed. After all, machines have to be adapted to best suit the local conditions, so no general formula can be given that would apply to other properties. Although St. Josepll Lead Co. has been mechani-cally-minded for a number of years, as shown by the fact that over 110 million tons have been loaded mechanically since 1922, any further mechanization or changes always present a problem. When our ore bodies were of great height and area the breaking and loading were developed to a high degree of efficiency according to known standards. But in recent years, when our ore bodies became smaller and more scattered, the amount of tonnage we were able to break was not sufficient to supply our shovels with enough rock to keep them working to capacity. Our first step in attempting to rectify this situation was to develop a technique of moving the shovels to the broken ore in various stopes, which sometimes entailed a move each shift. A shovel is not producing when being moved, so within the last two years we have been endeavoring to devise some means of getting more rock broken in these smaller stopes and it was then that we became interested in jumbo drilling. To illustrate the fact that mechanization is a process of a chain of developments rather than a stroke of genius can best be shown by a general summary of conditions and obstacles which were encountered in our present attempt to establish template drilling of a standardized round. Our first jumbo was more or less the conventional type with two machines mounted on a crossbar. This arrangement proved to be impractical to duplicate satisfactorily the regular routine of slabbing in a more or less radial pattern as carried out by column drilling. One machine was either too close to or too far from the face and there was another disadvantage in that one drillman was frequently delayed while waiting for his partner to bottom a hole. Our next step was to eliminate the crossbar so the machines could operate independently of each other, but we still encountered the same objections mentioned above except that one drillman was free to drill three holes instead of one in a vertical plane independently of his partner. Time studies while trying to adapt the jumbo to the regular slabbing practice as accomplished by column drilling, revealed that twice as much time was spent in maneuvering the jumbo into position and aligning the holes as was consumed in drilling.

Jan 1, 1951

By P. T. Bail, J. E. Bobek

In reservoirs containing soft shales interbedded with oil-producing sands, it is possible to have water movement from the shales into the sands during reservoir depletion. This paper presents the results of scaled flow-model tests performed to investigate the efficiency of oil displacement by this vertical influx of water into oil-producing sands. In these model tests, the effects of rate of influx and rock wettability were considered. Oil recoveries by shale-wafer influx and by water flooding were cornpared after 0.4 hydrocarbon volume of water entered the producing sand. This comparison was made for water-wet and oil-wet systems. In water-wet sand, shale-water influx produces slightly less oil than conventional water flooding; in oil-wet sand, shale-water influx produces about one-half as much oil as conventional water flooding. In another type of comparison, it was found that shale-water influx followed by water flooding recovers less oil than water flooding alone. This is true for both water-wet and oil-wet sands. A comparison of tests run at different rates of shale-water influx shows that oil recovery is insensitive to rate in water-wet sand; in oil-wet sand, oil recovery decreases with decreasing rate of influx. INTRODUCTION Localized subsidence of the earth&apos;s surface has accompanied the depletion of some oil reservoirs, particularly in California,1, 2 along the Texas Gulf Coast,3 4 and in the Bolivar Coastal fields of Venezuela. Subsidence occurs when fluid withdrawals reduce the pressure in the reservoir. The reasons for subsidence accompanying a reduction in reservoir pressure are not known with certainty.10° However, there is considerable evidence that compaction of soft shale beds adjacent to producing oil sands can be a major cause of this subsi-dence.3, 6, 10-12 When the shales compact, a limited amount of water moves from the shales into the producing sands. A schematic illustration of this oil-producing mechanism is shown in Fig. 1. As the pressure in the sand declines due to oil production, a predominantly vertical pressure gradient develops at the sand-shale boundary. This causes water to move from the shale into the sand as indicated by the solid arrows. This paper reports the results of scaled flow-model tests to investigate the efficiency of oil displacement by the vertical influx of shale water into producing sands. The model tests were not performed with the aim of duplicating the recovery behavior of any specific reservoir. The primary purpose of the tests was to obtain a better understanding of oil displacement by shale-water influx. A knowledge of the oil- and water-production characteristics of even a simplified reservoir system should be of value to engineers estimating the performance of reservoirs where shale-water influx is occurring in conjunction with other production mechanisms. The following limitations and assumptions apply to the model work. 1. The sand of the prototype reservoir is homogeneous and horizontal. 2. The shale-water influx is uniformly distributed along the top and bottom of the sand member being studied. 3. No effects of edge-water drive or dissolved-gas drive that might accompany shale-water influx are considered. PROTOTYPE RESERVOIRS Scaled-model tests were performed to study oil displacement from three prototype reservoir sections. The reservoir sections modeled consist of single sand layers out of a sequence of -sand and -shale layers, as illustrated in Fig. 1. Each prototype represents a homogeneous, high-permeability, unconsolidated sand layer. In the field, the prototype is oriented in such a manner that one end is at the radius of drainage of a producing well and the other end is pointed toward the producing well (Fig. 2). The sand and fluid properties and the dimensions of the three prototypes are given in Table 1. The capillary pressure relationships for the three prototypes are presented in Figs. 3, 4 and 5. The oil-water per-

By J. B. Cheatham

Applications of the mathematical theory of plasticity promises to lead to the solution of many drilling and rock mechanics problems. ,Because of mathematical considerations, the inelastic behavior of rock has frequently been represented by a perfectly plastic model in conjunction with a yield criteria of the Coulomb or Mohr type. The totality of all stress states for which a solid ceases to behave elastically can be represented as a limit surface in stress space. ,Probing of such limit surfaces indicates details of strain hardening which are not provided by the standard triaxial testing procedure. Probing tests of the limit surfaces have been performed on Cardova Cream limestone to provide data for extending plasticity theory to cover situations in which consolidation and strain hardening are present. Test results indicate that this highly porous limestone undergoes a permanent volume decrease when it is subjected to hydrostatic pressures in excess of 3,500 psi. A virgin sample tested under a confining pressure of 1,500 psi has a yield strength of 1,700 psi; however, if the sample is subjected to a consolidation pressure of 5,000 psi, before testing at 1,500 psi, the yield strength is raised to 2,300 psi. Thus, both consolidation and strain hardening are important considerations in describing the mechanical behavior of this limestone. Tests conducted with the axis of the core having different orientations indicate that this rock is also anisotropic. Portions of the initial and subsequent limit surfaces are determined for samples loaded either perpendicular or parallel to the bedding planes. INTRODUCTION Previous experimental work in rock mechanics indicates that no mathematically tractable constitutive theory is inclusive enough to describe the mechanical behavior exhibited by all types of rocks under all conditions of stress and temperature. Indeed, the type of deformation encountered in a single type of rock is known to depend upon the stress and temperature conditions in the rock during deformation.l-5 Certain rocks and minerals, notably those minerals composed of ionic salts, have been shown to exhibit plastic deformation when tested under conditions of high confining pressure.2 Since the mathematical theory of plasticity provides simplifications over the theory of elasticity in certain types of problems, such as those in which limit analysis can be applied, it is of interest to know under what conditions plasticity theory may be applied to rock mechanics problems. The following factors determine the nature of the deformation a particular specimen will undergo: (1) the microscopic structure of the rock, i.e., the structure visible under an optical microscope, including number of phases, porosity, distribution of phases, (2) the mineralogical structure of the solid phases, (3) the conditions of stress and the rate of change of stress and (4) the temperature. Extensive experiments on Yule marble, Carthage marble, Solenhofen limestone and other calcerous rocks indicate that these relatively nonporous rocks deform plastically under certain conditions of loading, and creep under other conditions of loading.l-3 This study is concerned with the behavior of Cordova Cream limestone (Austin chalk) which is also composed almost entirely of calcite and thus has the same mineralogical composition but, because of a rather large porosity, it possesses a different microscopic structure. This investigation was undertaken to learn if Cordova Cream limestone deforms plastically despite the embrittling effect of the pore spaces, and to provide data which can be used to determine whether the mathematical theory of plasticity can describe the mechanical behavior of Cordova Cream limestone. A brief discussion is given of some of the underlying principles of plasticity theory concerning stress space and limit surfaces. Strain hardening is defined and a discussion is given of how the mechanical behavior of a material can depend on the previous history of the loading. This is followed by a description of the experimental procedures

By P. Chaudhari, Michael B. Bever

The heat of solution at infinite dilution of selenium in bismuth, the heat of mixing of selenium and bismuth, and the limit of solubility of selenium in bis~rzuth have been determined at 573, 623; and 663°K by metal solution calorimetry. The heat of forrrzation of the compound Bi2Se at these temperatures has been determined from the heat effects associated with the precipitation of the compound from a saturated solution oj selenium and bismuth. The published information on the thermodynamic properties of the system Bi-Se is limited. The heat of solution at infinite dilution of selenium in bismuth at 623°K has been measured.&apos; The heat of formation at 273 K1 and room temperature2 and the heat capacity at 80 K3 of the compound Bi2Se3 have been reported. An estimate of the heat of formation of the compound BiSe at room temperature has been published.2 Information on the phase relations in the system Bi-Se is available.&apos; In the investigation reported here the following quantities have been determined at 573", 623", and 663°K: 1) the heat of solution at infinite dilution of selenium in bismuth, 2) the heat of mixing of selenium and bismuth in bismuth-rich solutions, 3) the limit of solubility of selenium in bismuth, and 4) the heat of formation of the compound BizSe. These quantities were determined by the addition of selenium to bismuth-rich solutions in a metal solution calorimeter. The determination of the heat of formation at the tem- perature of the calorimeter bath involved the precipitation of the compound from a saturated solution in the calorimeter. 5,6 This method differs from that commonly used which requires the addition of the compound and of a mechanical mixture of its components and yields the heat of formation at the temperature from which the additions are made (273 K EXPERIMENTAL PROCEDURE AND CALCULATIONS The solution calorimeter has been described in detail.&apos; Pure bismuth (99.999+ pct) was used as the bath at the start of a run. The calorimeter was calibrated with small amounts of bismuth added from 273°K; the differences of the heat contents of bismuth at 273°K and the temperatures of the baths are listed in Table I. After the calibration, additions of hexagonal selenium (99.999+ pct) were made. Loss of selenium by evaporation was negligible. No unusual experimental difficulties were encountered.9 The differences in the heat contents10 of selenium at 273°K and the temperature of the bath, listed in Table I, were subtracted from the measured heat effects to give the "adjusted heat effects". The methods by which the heat of solution at infinite dilution, the

Jan 1, 1968

By E. I. Alessandrini, A. U. Seybolt

Selective oxidation (preferential oxidation of a single alloy component) can be an important oxidation mode in the case of alloys such as Si-Fe, Al-Fe, and so on, when heat-treating in atmospheres of low oxygen potential. It was the purpose of this work to identify the oxide films formed on iron containing 31/4 pct Si at low oxygen potentials, and to make some observations on the H2O/H2 ratios required to form them. EXPERIMENTAL METHOD HYDROGEN of varying water content offers a very convenient method of establishing a wide range of oxidizing power, or oxygen potential. The method chosen to provide a desired H2O/H2 ratio was to nearly saturate hydrogen at room temperature by bubbling the gas through water at room temperature, and then to wring out the excess water by passing the wet gas through a long glass spiral immersed in a refrigerated liquid at a desired dew point. After oxidation, the samples were examined by electron diffraction in order to identify any film which might be present. PREPARATION AND TREATMENT OF SAMPLES The samples were prepared from a Si-Fe alloy made in the laboratory using electrolytic iron and 96 pct ferro-silico11, vacuum-induction melted, hot-rolled then cold-rolled to 0.015-in. thickness. After the cold-rolling the samples were annealed at 1000°C. Transmission Laue X-ray patterns showed very little evidence of preferred orientation, but it is likely that a weak texture could have escaped notice. The chemical analysis was as follows: 3.34 Si, 0.01 Al, 0.001 0, 0.006 C, 0.002 N. Before each sample was oxidized, it was polished through 4/0 emery paper, cleaned and dried using benzene, carbon tetrachloride, acetone, absolute alcohol, and ether. The method of oxidizing the samples was as follows: Samples about 1/2 by 1 by 0.015 in. were held in the upper, cool part of a vertical vacuum furnace until the desired temperature was established in the furnace, Fig. 1. The sample was then lowered into the uniform hot zone where it was heated quickly to the desired temperature, and subjected to hydrogen of controlled moisture content (dew point) as mentioned previously. Temperatures from 400" to 1000°C were used, and dew points from room temperature to —78°C were explored. In general, the runs lasted about 6 hr, but a few runs were of different duration, as will be indicated later. After the predetermined period of time had elapsed, the specimens were withdrawn by the hollow stainless steel-quartz holder to a cool zone at the top of the furnace. EXPERIMENTAL RESULTS The results are summarized in Table I. Most of the electron-diffraction patterns were obtained by glancing-angle reflection, but in a few cases it was possible to strip the oxide films from the surface by a total immersion in a 3 pct bromine-methanol solution. Some of the thinner stripped films yielded quite satisfactory transmission patterns. However, both diffraction techniques yielded the same results; the patterns while most frequently showing a (low) tridymite, also showed a (low) cristobalite in some cases. A few patterns showed evidence of both phases. Because of the known nonequilibrium behavior of silica, it is not surprising that both forms of silica could coexist on one sample. It was noted that at fairly low dew points such as —40°C, there was a tendency for diffuse diffraction rings, suggesting a very small crystallite size. Also some subsequent experiments to be reported later show that thin silica films can be amorphous.

Jan 1, 1959

By D. O. Wyble

Five water-driver fields, for which pressure predictions had been made within a few years after discovery, were re-studied when four to five years of additional pressure and production data became available. It was fortnd that forecasts of the pressure in water-dri~fe reservoirs may be subject to considerable unccrtainty. Predictions car be erroneous when there is insufficient presswe history to define the cllaracteristics of the aquifer, and when there are errors in the pressure, production or geologic data. INTRODUCTION The efficient operation of an oil or gas reservoir requires that the important characteristics of the reservoir be determined soon after its discovery. It is especially desirable to evaluate the pressure-production relationship quickly, for this relationship provides a basis for deducing the type of production mechanism that is operative, and for making pressure predictions. The pressure predictions, in turn, provide a basis for calculating efficient rates of production, determining whether water or gas should be injected, etc. The importance of pressure prediction is such that forecasts should be made as accurate as possible, and the limits of error well defined. Historically, pressure forecasts for some fields have proved very accurate, while for others the forecasts were so erroneous that they resulted in the adoption of wrong, or at best, unnecessary production practices. Pressure predictions made for water-drive fields are especially subject to error. Accurate forecasting for these fields requires that much be known not only about the reservoir proper but about the adjacent water-filled rock as well. The water-containing rock, or aquifer, may extend for many miles, and often there is only meager data regarding its thickness, permeability and porosity. Much of the information must be inferred from the previous pressure behavior of the reservoir. A brief pressure history may provide little information about the characteristics of the aquifer. Hence, pressure predictions made early in the life of water-drive fields can be incorrect. The work described in this paper was done to determine the degree of reliability which can be expected of pressure predictions made within a few years after water-drive fields are discovered. Five fields, for which the original pressure predictions had been based on less than seven years&apos; history, were re-examined with the aid of four to five years of additional pressure data. Where the predictions were inaccurate, the reasons for failure were ascertained. The studies were accomplished by use of the electric reservoir analyzer.&apos; The analyzer was first adjusted to repeat the original pressure-production match using the same values for the various parameters as were used in the original study. Then, the actual production rates experienced during the time elapsed since the initial study were set into the analyzer, and the pressure behavior indicated by the machine for this period was compared with that which actually OCcurred. Where the pressure profile traced out by the analyzer deviated from the observed field behavior, the analyzer was readjusted to obtain a better over-all match. The old and the new solutions were compared to determine the reasons for any differences. COMPARISON OF PREDICTED RESERVOIR PRESSURE BEHAVIOR WITH ACTUAL PERFORMANCE Field A The original pressure-production match is entirely adequate as evidenced by the pressure match of the field&apos;s history subsequent to Jan., 1952 (see Fig. 1)&apos;.