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By C. Y. Ang, C. Wert

Quench aging of supersaturated solid solutions of nitrogen in columbium takes place in reasonable times in the temperature range 300&apos; to 500°C. Changes in internal friction, hardness, and electrical resistivity are found to accompany this change. THERE is practically no detailed information in the literature concerning interstitial solid solutions in either columbium or tantalum. The fact that both of these metals are used extensively commercially in both pure and alloyed states makes studies of their properties of value. While the plan is to study both these metals and their alloys extensively, so far only a small number of measurements have been made. This paper presents data obtained in the initial investigations of columbium. The principal interstitial impurities of columbium are likely to be hydrogen, carbon, oxygen, and nitrogen. The first of these, hydrogen, is outside the scope of internal friction measurements at present and nothing quantitative is known about the initial hydrogen content of the specimens. However, it is believed that it is completely absent after the preliminary heat treatments are carried out. The carbon content of the original samples is low and can be reduced still further during sample preparation. Oxygen is normally present to some extent in columbium and can also be added or removed easily. Nitrogen is also normally present in small amounts and can also be controlled within limits. Since it is not possible yet to remove all the nitrogen from columbium and since it is possible to remove essentially all the oxygen and carbon, initial measurements were made on the alloy system nitrogen in columbium. In this sense then, the alloys are true binary alloys. Little is known about the effects of nitrogen on the physical and metallurgical properties of columbium, so it was necessary to perform some rather elementary measurements on the specimens. These measurements are described briefly in the next section and are discussed in detail in later sections. Scope of the Work That internal friction is associated with diffusion of nitrogen in columbium has been known for some time. It is similar in nature to that for carbon and nitrogen in a-iron. In these latter cases, the information obtained from internal friction has been useful metallurgically.&apos; and it is not too much to expect useful information from similar studies on columbium containing nitrogen. The technique of internal friction measurements is adequately described by Ke2 At a frequency of 1 cps the internal friction peak for nitrogen in columbium occurs at 300°C and that for oxygen at 160°C." So that all the measurements will be meaningful metallurgically, the internal friction has been calibrated by making a measurement of the damping at the two peaks and a measurement of oxygen and nitrogen content by chemical analysis. A comparison of the two gives the following calibration factor: To go from damping capacity expressed in terms of 1/Q to weight percent of oxygen and nitrogen in solid solution in columbium, multiply the peak values of internal friction by about 4 and 3 respectively." Data from which these factors were calculated are presented in Table I. The increase of electrical resistance of columbium caused by the addition of oxygen and nitrogen as interstitial impurities has been quantitatively determined. At room temperature the percentage increase is small for small additions of impurities (<0.1 wt pct); as the temperature is lowered it becomes an increasingly larger factor of the total resistance. An empirical relation has been established to express the resistivity at — 195°C in terms of weight percent of oxygen and nitrogen in solid solution. It is easy to make supersaturated solid solutions of nitrogen in columbium and to observe aging phenomena. The optimum aging temperature, as in the case for carbon and nitrogen in a-iron, occurs at the temperature for which the time necessary for a single place-change in diffusion is about 1 to 10 millisec. This means for nitrogen in columbium that significant property changes should take place for this alloy at about 400" to 500°C in reasonable time intervals. Results of such aging experiments are

Jan 1, 1954

By Bror Nordberg

SAND and gravel are unconsolidated granular materials resulting from the natural disintegration of rocks. The two materials nearly al- ways occur together, variably proportioned in widely available de- posits. A commercial sand comprises the fine granular material, usually less than f in. in diameter (ASTM Designation C58-28), and gravel consists of the coarse, granular material larger than sand (ASTM Designation C125-46T). Gravel falls within the range of 1/4 in. and a top size usually of 3 ½ in. Chemical definition is impossible. Sand and gravel are always of secondary origin. They were formed from various massive rocks through the action of chemical and mechanical forces; then transported, abraded, washed, sorted, and classified by streams, glaciers, waves, or winds, to be redeposited in beds as they are found. Chief disintegrating forces in the reduction of rocks into granular particles were frost, rain, the dissolving action of acid and alkaline ground waters, the mechanical action of streams and waves, and the action of glaciers. Method of formation and deposition have imparted physical properties to sands and gravels that largely determine the commercial value of the materials for particular use and influence the manner of exploitation. In the early days of the commercial industry, purchasing specifications were relatively lenient but in. the past decade much more rigid quality requirements have had to be met for acceptance by all classes of purchasers. The trend to further severity in requirements is a challenge to the industry that commands full knowledge of the nature of raw materials at hand and skillful application of processing into commercial products. Mechanical strength, the ability to resist disintegration, chemica

Jan 1, 1949

By J. A. Knox, R. M. Lasater, J. M. Tinsley

Chemical squeeze treatments have been used to provide temporary relief from certain production problems. The chemical fracture-squeeze technique, combining the effects of a fracturing treatment and a squeeze operation, has been more successful than conventional squeeze operations. Knowledge derived from well stimulation and reservoir engineering research provides a means for predicting the theoretical effective life of such a treatment. Analysis of theoretical equations and concepts developed allows selection of improved treatment techniques based on specific formation conditioins. Theory used in this analysis was developed as an extension of previous electrical model studies made to establish the expected flow and pressure profiles adjacent to a fracture system. The chemical fracture squeeze technique can be utilized in the economic application of corrosion inhibitors, emulsion breakers and paraffin and scale inhibitors. Application of this technique is shown to be effective. The slow return rate of injected chemicals, controlled by the resultant flow profiles and treatment variables, permits extended periods of chemical effectiveness. Results of field treatments are given, showing that the concepts outlined above for chemical fracture-squeeze treatments are valid and that applying this technique can help alleviate many current production problems. INTRODUCTION Much progress has been made in the last 10 to 15 years in developing chemicals for use in stimulating wells, maintaining production and protecting well equipment from damage due to corrosion. Not too many years ago, some wells seemed to dry up or wear out. In many cases the wells were produced as long as possible without any attempt at maintaining productivity. Even with the advent of new and better stimulation techniques, a rapid decline in production was observed. Methods of removing and, in some instances, preventing damage have been developed. Among thosc factors responsible for uneconomical production are scale, paraffin, corrosion, bacteria, water blocks and emulsions. Soluble scale-prevention chemicals have been developed1,2 that can be placed in a formation along with frac- turing sand. As the water produces back across this bed, the solid material dissolves slowly and can provide long-term protection from scale. However, bottom-hole temperature and salinity of produced water vary widely and both these factors influence the rate of solubility. Scale inhibitor composition is also a controlling factor. Some of the solid material may be crushed, increasing the surface area exposed to water and increasing the rate at which it dissolves. Some of the material may never be contacted by water and can be lost. However, this type of treatment has been very successful in many instances and has helped maintain economical production for extended periods of time. Liquid scale inhibitors, which are more widely applicable and more stable, have been developed in recent years; however, because they are liquids, their use has been restricted to treatment down the annulus, using metering pumps to provide proper concentrations in the produced fluid. This has prevented use in wells containing packers, in dually completed wells and in gas-lift and flowing wells. Wells that operate with an open annulus may also experience severe corrosion problems due to introduction of oxygen. Paraffin inhibitors3 have been developed that can be fractured into a well as particulate solids to be slowly dissolved in the produced fluid. These materials are not usually effective in wells with a bottom-hole temperature in excess of 120F since solubility rate may be too fast if that temperature is exceeded or if aromatic content of the oils is unusually high. Corrosion inhibitors have been developed that can be fractured&apos; into a well for long-term feedback, but development of a material with proper solubility or feed rate has been difficult. Corrosion inhibitors are available in many different forms. Liquids have been lubricated down the annulus or sticks or pellets dropped down tubing. Inhibitor squeeze treatments5 devcloped a few years ago led to development of inhibitors with particularly strong film-forming properties.6,7 This technique basically involves displacing a highly concentrated solution of the inhibitor into the formation through the tubing. Kerver and Hanson8 studied the adsorption properties of inhibitors on various types of formations. They showed that, even though the inhibitor was displaced radially into the true permeability, it could be produced back for a long period of time because of slow desorption from the rock. Methods developed for monitoring the return of these inhibitors generally have established 1 to 6 months as the effective limit before retreatment is necessary.9 Inhibitors displaced into the interstices of the formation sometimes cause emulsions that either hamper production or cause treating problems on the surface.

By J. Groyecki, M. Markuszewicz, J. Lassota, A. Zawada

The ratio of stable to unstable inclusions was found to ploy an essential role in the process of sccorldar-y recrystatlizalion in Si-Fe. The analysis of the free energy of inclusions in the range of heat-treatment of individual inclusions to be predicted. The effects MnS. ns inslable inclusions. were investigated. TO secure a high induction, the secondary recryslulliztt-lion associated wilh the texture is necessary. To obtain a low core loss an additional refiuing in the solid state is required. It has been found that sulfur can be more easily removed in racunm than in hydrogen and thai this process was hindered by the prescrzce of INCLUSIONS play an essential role in the development of cube-on-edge texture in Si-Fe. Their function consists in restraining the growth of primary grains up to about 900°C and in passing subsequently into solution at higher temperatures. This process is accompanied by the selective growth of secondary grains with (110)[001] orientation. The general effect of inclusions depends on such factors as the type of impurities, their amount. dispersion and stability, the conditions of diffusion in the space of lattice of metal, and the reactions at the metal/gas interface. In recent years, some of these factors were the subject of a special investigation. A positive influence of Mns, siN,&apos; and vN3 has been established. The quantity of impurities4 and their dispersion5 have been found to be of major importance. Attention was called to the vital importance of diffusion and the conditions under which the impurities are removed from metal., It has also been demonstrated that in Fe-Si alloys by the techniques of powder metallurgy a special opportunity exists to obtain the (110)[001] type texture. 6 The aim of this work was to conduct qualitative investigations on the influence of inclusion stability on the development of cube-on-edge texture in a metal containing approximately 3 pct Si. Experiments were carried out on cast alloys and on those manufactured by powder-metallurgy techniques. The results obtained from these experiments were utilized to explain the phenomena involved and to analyze the relationships between stable and unstable inclusions and the magnetic properties of alloys. EXPERIMENTS AND RESULTS The raw materials used in these experiments were the powder of carbonyl iron with the analysis (in pct) 0.044 C, 0.01 Mn, 0.005 Si, 0.009 P, 0.002 S, traces of Cu, 0.06 Ni, 0.0015 Al, 0.03 Cr, 0.02 Mo, 0.01 Ti, 0.002 Co, traces of Pb, and the powder of silicon containing 94.14 Si, 0.003 S, 0.048 C. The powders were ground and mechanically mixed in 100-g batches. and then pressed at 9 tons per sq cm into 74 by 24 by 8 mm blocks. Sintering was carried out at 1100°C for 12 hr in vacuum (2 x lo-&apos; Tr) or in hydrogen. In this instance the material was heated slowly and subjected to prolonged soaking at 350°, 650°, and 750 2C, respectively, to secure reduction of ferro-oxides. This was checked by making measurements of the dew point, which was found to change from -15" to -35°C after reduction. The compacts after sintering were hot-rolled to 2.4 mm, annealed at 800 C, and finally cold-reduced to 0.35 mm with intermediate annealing at 800°C at a gage of about 0.8 mm. Impurities were added in the powdered form and mixed with iron and silicon powders. Sulfur in the elemental state, electrolytic manganese, and pure aluminum oxide were employed. Besides, to obtain a material with low contents of impurities, especially

Jan 1, 1967

By H. Rush Spedden, A. M. Gaudin

IN the belief that a critical study of its operating problems might be a sound investment, the Cuban American Manganese Corporation initiated an ore-treatment research in cooperation with the Massachusetts Institute of Technology. One of the early objectives of this research naturally became the relationship of the microscopy of the Cuban ores of the Corporation to their flotation treatment. The operations in Cuba have already been described by F. S. Norcross, Jr.7 and the laboratory study of manganese oxide flotation goes back a number of years .4 Broadly speaking, the difficulties encountered in the flotation of manganese ores are that the consumption of reagents is extremely high, the concentrate contains more silica than is desirable and the tailing losses are relatively high. An appreciable betterment on any of these scores would achieve a definite betterment in costs, quantity of minable ores, and quality of product. The microscope study discussed in this paper was made on samples from the Quinto mine, from the Ponupo mine, and from mill products at various stages of passage of the ore through the mill. The writers have had access to Company records and in particular to the petro¬graphic studies made on thin sections of ore by the late Professors R. J. Colony and Philip Krieger, of Columbia University. They acknowledge their debt to both of these men for the help derived from the reports. Manganese oxides are black, friable, smudging. It is, therefore, very difficult to judge operations by inspection. The mineralogy of manganese compounds seems to be confused, and the authors believe that many more minerals have been described than actually exist. Much of this difficulty is due to the prevalence of the structural conditions that will be discussed further in this paper; namely, the porosity and the friability of the ores, and the extremely intimate association of minute manganiferous mineral crystals with impurities of various sorts. By all odds the most important manganese mineral in Cuba is the one that in this paper is called "psilomelane." The name "psilomelane" has been used in so many different ways that the choice of it for this ore may not be approved by all. However, it seems to be the best under the circumstances. This mineral accounts for about 97 per cent of the manganese in the ores of the Quinto and Ponupo mines and in the mill feed. The remaining odd 3 per cent consists mostly of pyrolusite together with minor amounts of other manganese oxide minerals. DESCRIPTION OF PSILOMELANE Aggregate Structure In grains or lumps, psilomelane has a characteristic fibrous appearance and seems

Jan 1, 1942

By J. Rourke, F. S. Minshall, E. G. Zukas, C. M. Fowler, O&apos

The Hugoniot curves were determined for Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si. The pressure of the transition increased as the silicon content of the alloy increased. Single crystals of 2.9 wt pct Si-Fe were also studied. The pressure of the transition was not dependent on crystallo-graphic orientation. All of the Neumann bands (mechanical twins) were attributable to (112) planes but not all of the {112} planes showed twin markings. A thorough study of the iron Hugoniot (the relationship between specific volume and pressure) under plane wave shock loading revealed a pressure transition at about 130 kbar shock pressure. The results of this investigation were reported by Bancroft, Peterson, and inshall1 in 1956. At the time of this discovery, it was felt that this was probably the a, to y transition normally found in iron and many of its alloys. Subsequently a number of iron alloy systems were surveyed in which the alloying element has a considerable effect on the normal a, to y transformation. The influence of carbon and nickel and/or chromium have already been reported.2,3 At the present time, there appears to be some doubt that this pressure transition is the usual a, to y transition In this study, Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si were chosen for several reasons. To the present, the transition has been found only in iron-base alloys which were originally in the a, phase (bcc). Secondly, the y loop at atmospheric pressure extends to only about 2.5 wt pct Si. If the transition were a, to y, then one might expect a rather drastic pressure effect for alloys containing more than 2.5 wt pct Si. Finally, single crystals of Fe-Si alloys large enough for shock loading studies are readily available thereby making it quite easy to determine the effect of crystal orientation on the transition pressure and on the twinning behavior of the alloy. EXPERIMENTAL PROCEDURE Fe-Si alloys containing up to 7 wt pct Si were produced by normal vacuum casting procedures. Single crystals of Fe-2.9 wt pct Si were purchased from Monocrystals Co., Cleveland, Ohio. The orientations of these crystals were determined and samples cut so that the shock wave would be parallel (to within 1.5 deg) to either the (loo), (Ill), or (112) principal orientations. Three distinct experimental testing techniques were used. First, the pin technique, described elsewhere,4 was used to determine the transition pressure for the polycrystalline alloys as well as for the (111) and (112) orientations of the 2.9 wt pct Si single crystals. Secondly, the recovery studies, described in detail in an earlier paper,2 were used for determining the effect of alloy composition and crystal orientation on the plastic II compression-plastic I rarefaction interaction zone for several specific shock pressures. Finally, measurements of pressures above the two-wave threshold were made on the polycrystalline alloys so that more complete Hugoniot curves could be constructed for this alloy system. The optical techniques described by Rice et al.5 were used to measure the shock and free surface velocities of the samples from which the Hugoniot data were obtained. This method is applicable only in the single wave region, since velocities are obtained from the measured total transit times of the disturbances through measured sample thicknesses.

Jan 1, 1963

By R. H. Walpole, J. M. Kane

IN all probability the mining and metallurgical industry as a whole can demonstrate a larger ecorlomic return from installation of dust-control equipment than any other major industrial group. This fact has partially accounted for the marked increase of dust-control installations made during the past decade. While the primary objectives for installation of dust-collecting systems are improved working and operating conditions for men and equipment, the fact that an economic return can be anticipated on salvageable materials is an added advantage which shows in partial or complete equipment write-off. The conditions apply to most phases of the mining, milling, and smelting industry, both non-metallic and metallic. As with any mechanical devices, selection of suitable dust collector equipment involves evaluation of available products with characteristics most nearly meeting conditions of the application at hand. When there is valuable product to be collected, and/or when there are possibilities of air pollution or public nuisance, collector selection is often guided by the maxim of "highest available collection efficiency at reasonable cost and reasonable maintenance." A brief review of dust collector designs will permit outlining of major characteristics of each group. Final selection will involve detailed data against a background of the problem under consideration. The dry centrifugal collectors, see Fig. 1, represent a group of low cost units with minimum maintenance. They are subject to abrasion under heavy abrasive dust loads and to plugging with moist materials. Efficiency drops off rapidly on particle sizes below the 10 to 20 micron group. Because of the large amounts of —10 micron particles in most mining dust problems, they will normally be used as primary collectors and will be followed by high efficiency units. This combination is cspecially popular where the bulk of material is desired in a dry state with wet collection indicated for the final cleanup portion. In remote plant locations, dry centrifugal~ can be used alone if product in dust form has no value or if dust loading is light enough to eliminate a nuisance in the plant area. Where high efficiency dust colleotion equipment must be selected, choice will normally involve fabric arresters, wet collectors, or high voltage Electro-Static precip-itators. Fabric arresters, see Fig. 2, rely on the passing of dust-laden air at low velocity through filter fabric. Velocity ranges from 1 to 3 fpm for the usual installation and may be as high as 10 to 20 fpm in arrangements where automatic frequent vibration or continuous cleaning of the filter media is employed. Fabric is normally suspended in either stocking type or in an enlvelope shape. Collection efficiency is excellent even on sub-micron particle sizes. Equipment is bulky, must be vibrated to remove the collected dust load, and is restricted in applications from temperature and moisture standpoints. Condensation of moisture on the fabric filter mcdia causes plugging of the passages with great reduction in air flow. Temperatures for the usual medias of cotton or wool are 180" and 200°F maximum, although the introduction of synthetic materials such as nylon, orlon, and glass cloth have increased the possibilities of this type of collector for higher temperature applications. The wet-type collector may employ a number of different principles so that entering dust particles in the gas stream are wetted and removed. Principles usually include impingement on collector surface or water droplets, often in combination with centrifugal forces. Variety of wet collector designs is indicated by typical collectors illustrated in Figs. 3 and 4. Collection efficiency is a function of the particular design, although the better collectors will have high collection efficiency on particles in the 1-micron range. Wet collectors have the advantage of handling hot or moist gases, take up small space, and eliminate secondary dust problems during the disposal of the material. At times collection of the material wet is a disadvantage. Wet collectors may also be subject to corrosion and freezing factors. The high voltage Electro-Static precipitator, see Fig. 5, is probably the most expensive type of high efficiency collector. It finds its applications generally in problems in which collectors previously discussed cannot be employed. Its collection efficiency is based on its design features and can be excellent on the finest of fume particles. Material is normally collected dry. Gas temperatures are of no great concern as long as condensation does not occur within the dry type of precipitator and the temperatures do not exceed the limits for materials used in its construction. As with the fabric arrester, provisions

Jan 1, 1954

By M. I. Sherman, J. D. H. Strickland

USE of a hydrometallurgical approach to the oxidation of sulfide ores and extraction of metals therefrom may have advantages over the more common smelting techniques when a low grade deposit is difficult to concentrate or the subsequent separation of metals, coexisting in the ore, is laborious by any known smelting operation. For economic reasons, the most promising oxidants are either atmospheric oxygen or electric power. The use of oxygen, or air under pressure, has recently been revised. Pyrrhotite has been converted to iron oxide and elementary sulfur&apos; and a variety of sulfides have been treated by Forward and co-workers.2-4 Generally sulfate is the end form of the sulfur but with galena in an acid medium, elementary sulfur can be formed." For economic reasons chlorine and ferric iron salts are about the only possible alternatives to the atmosphere as oxidizing agents for base metal sulfides. If aqueous solutions of chlorine or ferric iron are employed, the reduction products can be oxidized electrolytically in situ and used again, thus acting as catalysts for electric power as oxidant. The use of ferric salts for this purpose is established hydrometallurgical practicea but, although chlorine gas has been employed in the dry state at an elevated temperature, its use in aqueous solution at or near room temperature has not found favor. The reaction of chlorine water with the soluble sulfide ion has been studied by several workers,7-9 and both sulfate and elemental sulfur are found as end products, the latter being favored by the presence of a low concentration of oxidant relative to that of sulfide in solutions of about pH 9 to 10. Of direct bearing on the work in hand are an early American patent" and a recent Austrian patent." The former advocates stirring powdered ore with an aqueous solution of ferric chloride chlorine oxides and chlorine. In the latter it is claimed that both metal and sulfur can be obtained by electrolysis, in a diaphragm cell, of a metal ore slurry in brine. Details in these patents are scant and no data or explanation is given for the mechanism of the reaction which, in the Austrian work, is attributed to the (unlikely) action of nascent chlorine at the anode surface. No mention is made of possible differences in behaviour between various ores. Apparatus A complication encountered when working with chlorine water is that a serious loss of chlorine occurs by gas partitioning unless an enclosed system is used and any air space in the apparatus is kept very small and constant. Arrangements were made, therefore, to take out samples for analysis without letting air into the system to replace the liquid removed. For convenience in studying a heterogeneous reaction the apparatus was so designed that a reproducible controlled stirring rate could be maintained and the ratio of surface area of ore to volume of solution was approximately constant throughout any experiment. The apparatus used is shown in Fig. 1. The ground ore was placed in the horizontal cylindrical vessel, A, of about 1 liter capacity, heated by a constant temperature circulating bath pumping water through the concentric jacket, B. By adding chro-mate to this water, an ultraviolet radiation filter effectively surrounded the reaction vessel, greatly reducing any possible photochemical decomposition of chlorine solutions. Stirring was effected by glass paddles, C, attached by an axle to a magnet which was rotated by another powerful Alnico magnet, D, outside the glass end, this magnet being itself rotated by an electric motor electronically controlled to constant speed. Speed could be varied from about 150 to 900 rpm and was measured and held to within 1 pct of a given value. The end of the reaction vessel remote from the stirring magnet was closed by another one-ended glass cylinder, E, connected by thin polyethylene bellows, F, clamped by screw clamps and watertight rubber gaskets to the main vessel. Through E, a glass electrode and calomel electrode projected into the solution and a hypodermic syringe pierced a small bung and allowed acid or alkaline to be added to maintain a constant pH. By pushing the fully extended bellows until the two cylinders touched, from 50 to 100 ml of solution could be forced out through a sintered disk into the three-way tap system, G, either to waste (for flushing purposes) or up into a 10 ml burette where the solution could subsequently be measured out for analysis. The ore samples were introduced at H, the tube being stoppered by a thermometer of —1 to +52ºC range, graduated to 0.1°C intervals. To prevent ore from being ground in the end bearings of the stirrer these bearings were pro-

Jan 1, 1958

By P. R. Gage, R. W. Bartlett

At high temperatues and reduced oxygen pressuves, molybdenum silicicles oxidize to form SiO(g) vathev than a passivating SiO2 film. This is a sevious problem for low-pressure applications of sili-cide-coated rejvactory tnetals. As oxiclalion pvoceeds, the higher oxidntion potential of silicon initially suppresses oxidation of molybdenum and silicon is depleted near the surface. Eventually, silicon depletion causes secondary passivation (SiO2) mid an active to passiue transition in oxidntion behavior at moderately low pressures. At very low pressures, silicon depletion continues until steady-state oxidation of both silicon and rnolyhdenum can proceed at rates propovtional to their initial stoicliiorrzetvies. Ohsel-vations of &apos;oxidatiou-rate belzcriliov at temperatures from 1101° to 1700°C and oxygen pressures from 10-7 to 1 at in were made using thermogravimetn&apos;c, X-ray diffraction, and elect?*on-rtric?ro/,vobe techniqrres. The experimental results are in good agreement with calculated lirnits for the various types of behavior that were based on tlievtnochernicnl atzd dffusion rate data for the Mo-Si system. A protective oxide film normally forms during the oxidation of elemental silicon. However, at elevated temperatures and reduced pressures this film is not present and oxidation is rapid. wagnerl has shown that this behavior occurs because SiO(g) is more stable than SiO2. The behavior of the silicides at high temperatures is similar but more complicated. Molybdenum and several silicide compounds are involved and the chemical activity of silicon, or the equivalent silicon vapor pressure, can vary considerably in these phases. Also, diffusion in the silicides resulting from reactions in which a higher silicide is reduced to a lower silicide, or molybdenum containing dissolved silicon, must be considered. EXPERIMENTAL AND ANALYTICAL METHODS Isothermal oxidation experiments were conducted using hot-pressed MoSi2 and Mo5Si3 wafers. Each experiment was conducted at a fixed oxygen pressure by controlling the flow of oxygen in and out of the furnace chamber. Most of the experiments were conducted in a molybdenum-wound tube furnace. Special construction features, including use of a high-purity dense A12O3 refractory tube, permitted operation in high vacuum to 1500°C. Higher temperatures could be obtained at higher working pressures and with a sacrifice of tube lifetime. Temperature was measured with three Pt 6 pct Rh/Pt 30 pct Rh thermocouples and controlled with a proportional controller. Weight changes were monitored with a quartz spring balance. The few experiments, at higher temperatures and low pressures, were conducted in a cold wall vacuum chamber using induction heating with direct susceptance of the sample. Because of the variable levitation effect of the induction coil on the sample, weight changes could not be monitored continuously in these experiments. All samples representing both experimental methods were weighed before and after oxidiation and examined with a microscope and analyzed by X-ray diffraction. The analytical treatment assumes equilibrium at interfaces and uses existing thermodynamic data. For convenience, equilibria are expressed as chemical potentials or as vapor pressures of the gases involved. The resulting differences in equilibrium vapor pressure between adjacent interfaces and between the surface and external atmosphere drive diffusion processes in the solid and gas boundary film, respectively. These diffusion processes govern the rate of oxidation. A bibliography of the sources of thermochemical data for the reactions pertinent to the Mo-Si-O system is given in Table I. Reactions are listed with the sources of free-energy data referenced. Since all of these reactions involve one or more gas species, usually oxygen, a plot of the product-gas chemical potential, -RT In Pg, vs absolute temperature for each reaction is given in Fig. 1. These curves can be used to determine equilibrium vapor pressures or to compare the stability of different compounds in the various gases: O2, Si, SiO, and Moo3,. The data of Table I and Fig. 1 were used to determine the analytical results presented in this paper. EXPERIMENTAL RESULTS The weight changes for three MoSi, samples oxidized at 1500°C are plotted against time in Fig. 2. The treatments were identical except for the indicated variance of oxygen pressure and each curve represents one of three characteristic types of behavior that were observed. The upper curve is an example of passive oxidation, which is defined as

Jan 1, 1965

By B. Ramaswami, U. F. Kocks, B. Chalmers

The latent hardening of silver and an Ag-Au alloy was investigated by lateral compression, overshoot in tension and cormpression, and the stability of multiple-slib orientations. The latent hardening of a secondary slip systenz depends on its relation to the primary slip system. For most secondary slip systems the latent hardening is larger for Ag-10 at. pct Au than for pure silver. The maximum increase in. flow stress on a secondary slip system over that of the primary slip system was 40 pct. The work hardening during the lateral-compression test on the latent system after prestress on the primary system is iuterbreted in terms of the preferential distribution of barriers to dislocation movement with respect to the active slip system in work-lzardened fcc crystals. The work-hardening in fcc crystals is mainly due to the dislocation interactions and the barriers to dislocation movement formed as a result of reactions between dislocations of different slip systems. The operation of sources on the latent system depends on the flow stress of those systems; hence, the increase in flow stress of a latent system due to glide on an active system, which is called latent hardening, is an important element in understanding the phenomenon of work hardening. The problem of latent hardening has attracted the attention of many investigators in the past. For example, a theoretical study of the elastic latent hardening of the latent systems due to glide on an operative system has been made by Haasen&apos; and ~troh. These calculations, however, neglect the stress required for the intersection of forest dislocations by the glide dislocations, a factor which would be important for producing macroscopic strains on the secondary slip systems. The importance of this factor will become evident from the results presented here. Attempts have also been made to determine the latent hardening of different slip systems by experimental means by the methods summarized in Table I.3-9 The experimental methods used have been subject to certain limitations. For instance, in the method used by Hauser,9 frictional constraints between the specimen and the compression platen were not eliminated by proper lubrication (see Hos- ford10). Secondly, with the exception of Kocks,6 Hauser,9 and Rohm and Kochendorfer,11 latent-hardening studies have been made on only one of the slip systems, i.e., on either the conjugate or the coplanar slip system; hence, extensive results are not available on the latent hardening of different slip systems in the same materials, with the exception of aluminum.6 It was therefore decided to study the latent hardening of the conjugate, critical and half-related slip systems in silver. Similar experiments were done in Ag-10 at. pct Au to study the effect of solute (gold) on the latent hardening of silver. Lastly, indirect evidence can be obtained by a study of the orientation stability of crystals of multiple-slip orientations in tension and compression. This method has been used by Kocks6 to supplement his studies of latent hardening in aluminum. Similar studies were made at room temperature in single crystals of silver. EXPERIMENTAL PROCEDURE The single crystals of the desired orientations were grown and the tensile test specimens were prepared as described in Ref. 12. The compression tests were made on 1/4-in.-cube specimens. The specimens were cut from single crystals, in the Servomet spark-erosion machine.13 The two cut surfaces were planed using the lowest available planing rate in the machine to minimize the deformation layer. A brass strip was used as the planing tool. This method of preparation ensured plane parallel faces for the compression tests. The deformed material was removed by prolonged etching in a weak etching solution. A weak etching solution was used to prevent pitting of the surfaces and to ensure uniform etching. About 25 to 50 µ of material were removed from all faces by the etching treatment. The specimens were then annealed for 24 hr at 940°C in oxygen-free helium and cooled in the furnace to room temperature over a period of 7 hr. After annealing, the orientation of the specimens was determined by Laue back-reflection technique to make sure that no recrystallization had occurred on annealing. The compression-test technique and setup are described in Ref. 14. The Laue back-reflection technique was used to study the overshoot in tension, the overshoot in compression, and the stability of the axial orientation in tension and compression. The tests were interrupted after every few percent strain to determine the axial orientation. In investigating the overshoot in compression, the operative system was determined by studying the asterism of the Laue spots.

Jan 1, 1965

By B. B. L. Seth, H. U. Ross

A generalized rate equation for the reduction of iron oxide was derived from which two particular equations were obtained: one for rate controlled by the transportation of gas, the other for rate controlled by the phase-boundary reaction. Pellets of pure ferric oxide having diameters of 8.5 to 17.5 mm and a density of 4.8 g per cm3 were prepared and reduced by hydrogen at 750° to 900°C. From the analysis of data obtairzed, it was observed that neither the phase-houndarv reaction nor the transportation of gas controlled entirely the rate of redziction. Rather, the mechanism of reduction can he divided into three stages. In the beginning, the process seems to depend predominantly on the surJrce reaction, hut after a layer of iron is formed the diffusion of gas becomes the controlling factor. Towards the end, however, the rate falls sharply due to a decrease in porosity. The times predicted by the generalized equation for a certain degree of reduction showed an excellent agreement with those obtained experinmentally for pellets of varying sizes. WIDE interest in iron oxide reduction has resulted in many valuable studies pertaining to thermody-namical properties, equilibrium diagrams, and chemical kinetics. Although the thermodynamical properties and equilibrium diagrams are now known with a fair degree of accuracy, the mechanism and rate-controlling step in the reduction of iron oxides presents a problem to research workers which is still unsolved. This is because the field of chemical kinetics is so highly complex. Besides the chemical reaction between oxide and reducing gas, several other processes are occurring simultaneously such as solid-state diffusion of iron through intermediate oxides (FeO and Fe3O4), the diffusion of reducing gas inwards and of product gas outwards, and the sintering of iron if reduction is carried out above the sintering temperature of iron. Furthermore, there is a large number of variables, including the nature and flow rate of the reducing gas, the chemical composition and physical properties of the ore, the temperature of reaction, particle size, and so forth, all of which can affect both the mechanism and the kinetics of reduction. Despite the controversy and diversity of opinion about the mechanism of iron oxide reduction, three main schools of thought have emerged. According to the first, the rate is controlled by the diffusion of gas through the boundary layer of stagnant gas; the second claims that the rate is proportional to the area of the metal-oxide interface, while the third believes the transportation of reducing gas from the main stream to the metal-oxide interface and of product gas from the metal-oxide interface to the main stream to be the rate-controlling step. 1) The boundary-layer theory is true mainly for packed beds where the flow of gas through the bed is important. For a single particle, the boundary layer may be prevented from being the rate-controlling step if a gas flow rate of reducing gas above the critical flow rate is used. 2) Several workers have reported a linear advance of the Fe/FeO interface which provides excellent support for the belief that reduction is controlled by the surface area. McKewanl has given formal shape to this concept with mathematical derivation and has shown it to be valid for reduction of several iron ores, hematite, and magnetite, both by H2 and H2, H2O, N2 mixtures. Some other investigators, however, do not find this theory to be entirely valid. Deviations have been observed2 and further confirmedS3 Hansen4 also agrees that deviations do occur, at least in the latter stages of reduction, while from the data of several investigators summarized by Themelis and Gauvin,5 it is clear that the theory is not always applicable and further that, when it is applicable, it does not hold in the final stages of reduction. 3) Among those who claim the transportation of gas to be the rate-controlling step are Udy and Lorig,6 Bogdandy and Janke,7 and Kawasaki el a1.8 The validity of the theory has also been acknowledged indirectly by other research workers who show that the sintering and recrystallization of iron cause a decrease in reduction rate, for it is only if the transportation of gas is important that this sintering has any bearing. However, the theory has been rejected by some because they have failed to obtain

Jan 1, 1965

By C. H. Lee, R. Maddin

The diffusion rates of Ag110 in cylindrical single crystals of 99.99 pct pure silver, which were twisted to a total surface strain of 0.91 during the diffusion anneal at temperatures of 700°, 750°, and 800°C, were measured by sectioning and counting as a function of the strain rates. The ratio of the diffusivities while strain ing occurred (Ds) to those of the unstrained specimens varies linearly with the rate of twisting and attains values of near 100 for some of the rates used. The enhancement of diffusion by straining is inversely proportional to the temperature at which diffusion occurs. The activation energy for diffusion determined from the data plotted as a function of the rate of twisting decreases from 44,090 cal per mole for zero strain, to an asymptotic value of 21,000 cal per mole for the strain rates of 22 x it)"5 see-l. Qualitative explanation for the observations based on the generation of nonequilibrium number of defects by plastic deformation will be discussed. The initial research of Buffington and cohen1 on self-diffusion in a iron under compressive stresses contributed the first quantitative information concerning the effect of applied stresses on diffusion. These results were obtained from radioactive Fe55 plated on one of the horizontal surfaces and compressing the large-grained specimens while the diffusion-anneal was occurring. Enhancement of diffusion of a maximum of seventeen times was observed provided the strain was in the tertiary stage of creep and the rates of straining were at least as fast as rates used in the normal creep test. On the other hand, Darby, Tomizuka, and Balluffi,2 extending silver single crystals up to 30 pct elongation at rates of straining about equal to those used by Buffington and Cohen observed no effect. For the past two and a half years at the University of Pennsylvania, we have been investigating the effect or torsional strains on self-diffusion in silver single crystals. If enhancement is observed as has been reported1 a possible explanation may be based upon the generation of fairly large numbers of point defects and their role in the diffusion process. Hence, since torsion should produce an abundance3 of point defects, an increase in the diffusivity while the crystal is being twisted should easily be measured. EXPERIMENTAL PROCEDURE Our research uses single crystals of silver prepared from 99.99 Ag by the Bridgman method in a dynamic vacuum of less than 25 µ. As grown, they are about 25 cm long by 1.3 cm in diam. The crystals are cut into 7.5 cm lengths with a jeweler&apos;s saw and machined to the shape shown in Fig. 1. The test length of the crystal is machined to a 0.6 cm diam after which the ends are masked and the test section etched heavily in HNO3, and KCN:(NH4),S2Os , solution to remove the effects of machining. The specimen is then annealed in vacuum for 8 to 12 hr at 800°C to remove any residual stresses and also to recrystallize the end sections. The recrystallized ends are necessary since experiments showed that single-crystalline end sections are too soft to transmit the desired torque. Occasionally, recrystalliza-

Jan 1, 1960

By Y. C. Liu, W. R. Hibbard

Based on pole figure data and microstructural observations, the re-crystallization orientation found in a copper strip previously cold-rolled 99.5 pct from a single crystal with an initial (110) [112] orientation may be described as: a 30° rotation, clockwise and counterclockwise, about octahedral poles of the cold-rolled texture such that all four poles function at a low annealing temperature (400°C) and only three of them function at high temperatures (500&apos; to 1050°C). The relative intensity of deformation stresses on various slip planes can be correlated with the choice of poles affecting the rotations found in the recrystallized orientations. ROTATIONAL reorientation about the poles of densely packed crystallographic planes is an important characteristic of secondary recrystallization" in face-centered cubic metals. Some evidence has also been interpreted to show that such a rotational relationship also exists in the primary recrys-tallization process." In an investigation of the crystallographic relationships in the recrystallization process, several aspects of the experimental procedure should be considered. With cold-rolled poly-crystalline metal as the initial material, pole figure analysis leaves many ambiguities as to whether or not simple indices can be assigned to adequately represent its orientation. The rolling texture does not consist of a single texture. Minor deformation textures are usually present. In all cases, twin textures are present. The presence of both minor and twin deformation textures influences the recrystallization texture. In order to study the recrystallization mechanism, a more precise knowledge of the history of the material before recrystallization is necessary. Tensile deformation of a single crystal usually produces residual stresses which are concentrated at slip bands. Since the exact nature and orientation of these potential nuclei sites cannot be experimentally evaluated, the tensile deformation of a single crystal was not considered adequate. From the work done by Barrett and Steadman6 n copper, it appeared that cold rolling of a single-crystal specimen with an initial (110) [112] orientation would yield a specimen which fulfills the conditions required for the present investigation, namely a highly preferred single rolling texture with relatively homogeneous stress distribution. By investigating the recrystallization texture of this material, additional details of reorientation during recrystallization might be obtained. The purpose of this paper is to describe such an investigation. Experimental Procedure Copper used in the present investigation was cathode sheet with a purity of 99.94 to 99.97 pct. A copper single-crystal specimen, 1.15x0.8720x0.5322 in. (thickness) was cut from a cylindrical crystal which was grown in a Bridgman furnace.&apos; The cutting was accomplished on a horizontal milling machine operated at a very slow speed to obtain a (110) plane in the rolling plane and a [112] direction in the rolling direction. The disturbed surface was removed by electrolytic polishing in dilute orthophos-phoric acid (H3PO4) with a specific gravity of 1.14, and a current density of about 1 to 2 amp per sq cm. A 3-min polishing was needed to eliminate the disturbed surface causing Debye-Scherrer rings and a 45-min polish produced a surface which yielded sharp rounded Laue spots. It was estimated that about 1/16 in. of metal was removed from the original cut surface. The final orientation of this specimen before rolling was about 2" from the (110) plane in the rolling plane with a [112] direction aligned in the rolling direction. It is possible that a small amount of strain was still present in the cube despite the fact that the Laue spots seemed very sharp. It is doubtful, however, that this would be an important factor after a subsequent rolling reduction of 99.5 pct. This copper specimen was rolled on a laboratory rolling mill with two highly polished rolls 37/8 in. in diam in the following manner: 0.010 in. per pass to 50 pct reduction, 0.005 in. to 70 pct, 0.002 in. to 85 pct and, finally, 0.001 in. per pass to a 99.5 pct reduction. Specimens, about 1 in. sq with the rolling edges intact, were cut from the rolled strip by the electrolytic method previously described, after the strip

Jan 1, 1954

By E. J. Dulis, R. M. Fisher, K. G. Carroll

IT is well known that ferritic steels containing more than 15 pct Cr when subjected to temperatures in the range of 700" to 1000°F exhibit increasing hardness and decreasing ductility. The phenomenon has been widely termed the "885 °F embrittlement," after the temperature of most marked effect.&apos;.&apos; In view of the excellent review articles available in the literature3-6 only a brief account of experimentally established facts need be given here. The extent of changes in physical characteristics during embrittlement depends on chromium concentration and time at temperature, higher alloy content and longer time both promoting more rapid and extensive changes. In a 27 pct Cr steel, changes in impact strength and in angle of fracture in bending can be detected after only a 1 hr exposure at 885°F; after 50 hr this steel becomes quite brittle. Hardness increases slowly with time during thousands of hours exposure and may attain a maximum hardness number twice as large as that of the unexposed steel. Microstructural changes accompanying embrittlement have been described as an initial widening of grain boundaries followed by eventual darkening of ferrite grains. Embrittled steels etch more readily, e.g., the weight loss of a 27 pct Cr steel in acid solution may occur at a rate one hundred fold greater following exposure at 885 OF. Marked changes which accompany embrittlement have been observed in electrical resistivity, specific gravity, and magnetic coercive force. Changes in physical properties may be readily removed by heating at temperatures above the embrittling range, such as a treatment at 1100°F for 1 hr. It has frequently been noted that the 885 °F embrittlement suggests precipitation on a submicro-scopic scale of a chromium-rich constituent, the nature of which has not been revealed by X-ray diffraction. Progressive broadening of the body-centered cubic diffraction lines during embrittlement has been observed," and recent observations by Lena and Hawkes&apos; upon single crystals have shown early asterism in X-ray photographs, disappearing within an hour at 900 °F. Many workers have ascribed8-13 the phenomenon to a precipitation of a phase (FeCr), which is known to cause embrittling effects at temperatures much higher than 885°F. Two general observations, however. suggest that a precipitation cannot be responsible for the 885°F phenomenon: 1—prior cold work greatly enhances a formation, whereas it scarcely affects the 885 °F embrittlement, and 2—the presence of an alloying element such as nickel or manganese may have an effect on the 885 °F embrittlement which is opposed to its effect upon a formation. The slight enhancement of a formation and 885°F embrittlement observed in the presence of elements with strong carbide and nitride forming tendencies&apos; is probably a consequence of lessened chromium depletion of the matrix. The bar graph in Fig. 1 shows a typical example, taken from two 27 pct Cr steels used in this work, of the hardness after exposure for 10,000 hr at 900°, 1050°, and 1200°F. Steel A (0.03 pct C, 3.13 pct Mn) showed marked hardening at 900" and 1200°F, whereas steel B (0.12 pct C, 0.63 pct Mn) exhibited only the 900°F hardening. The cr phase was found in steel A at the higher temperatures but not in steel B. Presumably a formation is enhanced by the low-carbon and high-manganese concentrations in A," Thus there are two distinctly different hardening phenomena present which cannot both be ascribed to v precipitation without invoking a transition phase possessing remarkable properties. Materials A number of chromium steels exposed for long periods (5000 to 34,000 hr) at 900°F, as well as unexposed samples of one of the steels, were available for this investigation. Table I gives the chemical compositions and aging treatments of these steels. In addition to these steels exposed in the elevated temperature test furnaces of the National Tube Division, a number of high-chromium steels were heated for short periods in small laboratory air furnaces and lead baths. Supplementing these commercial steels, a sample of high-purity (0.018 pct C, 0.002 pct N) 28 pct Cr iron, exposed 1000 hr at 887°F. was furnished by the Union Carbide and Carbon Corp. In addition, an alloy of iron and chromium of high purity containing 46 pct Cr was used. This

Jan 1, 1954

By G. H. Bishop

The kinetics of the inter granular penetration and embrittlement of [100] tilt boundaries in 99.998 pct pure nickel upon exposure to bismuth-rich Ni-Bi liquids have been determined in the temperature range from 700° to 900°C. The kinetics of penetration are parabolic in time at constant temperature over most of the temperature range. In a series of 43-deg bicrystals the rate of penetration is anisotropic with respect to the direction of penetration into the grain boundaries. In lower-angle bicrystals the penetration rate is isotropic. The rate of penetration decreases with tilt angle at 700°C. The activation energy for penetration in the 43-deg bicrystals is 42 kcal per g-atom independent of direction. It is concluded that the intergranular penetration and embrittlement in the presence of the liquid proceeds by a grain boundary diffusion process and not by the intrusion of a liquid film. This was confirmed by a determination that the kinetics of penetration and embrittlement were the same in the 43-deg bicrystals upon exposure to bismuth vapor under conditions such that no bulk liquid phase would be thermodynamically stable. WhEN solid metals are exposed to a corrosive liquid-metal environment, the grain boundaries are sites of preferential attack. Depending on the temperature, the composition of the liquid, and the composition, structure, and state of stress of the solid, a number of modes of attack are possible. This paper reports a study of the kinetics of intergranular penetration and embrittlement of high-purity nickel bicrystals upon exposure to bismuth which, together with an earlier study by Cheney, Hochgraf, and Spencer,&apos; demonstrates that there are at least two modes of intergranular attack possible in the Ni-Bi system. In the study by Cheney et al., columnar-grain specimens of 99.5 pct pure nickel were exposed to liquid bismuth presaturated with nickel in the temperature range 670" to 1050°C. They found that the majority of the boundaries, which were predominantely high-angle boundaries, were penetrated by capillary liquid films, the attack proceeding by a process which will be termed grain boundary wetting. This process occurs in a stress-free solid when twice the liquid-solid surface tension is less than the surface tension of the grain boundary,* i.e., when 2yLs < YGB In this case the penetration of the grain boundary by the liquid occurs at a relatively rapid rate, resulting in the severe embrittlement of a polycrystalline solid. Grain boundary wetting is a common mode of intergranular attack in systems in which the lower melting component is relatively insoluble in the solid, but the solid has an appreciable solubility in the liquid, for example, the Ni-Bi system, Fig. 1. In systems of this type at temperatures above the range of stability of any intermetallic phases, once the liquid is saturated with respect to the solid so that no gross solution occurs, chemical gradients are small, and surface tensions become major driving forces for attack, provided the solid is stress-free. The results of Cheney et al. appear to be typical of those encountered when grain boundary wetting occurs.&apos; Capillary films were observed in the boundaries after quenching from the exposure temperature. The mean depth of penetration increased linearly with time, and the activation energy for the process was found to be 22 kcal per g-atom. In a study of the Cu-Bi system Yukawa and sinott4 found that the depth of penetration of bismuth into high-purity copper bicrystals of orientations from 22 to 63 deg of tilt about (100) at 649°C ranged from 0.05 to 0.25 in. after a 12-hr anneal. This corresponds to a linear rate of 6 to 15 X 10~6 cm per sec. At the same reduced temperature of 0.68 the rate for the Ni-Bi system&apos; was 7 x lo-&apos; cm per sec. In another study of the Cu-Bi system, Scheil and schess15 determined the kinetics of grain boundary wetting in hot-worked commercial rod. While there were several complicating factors present in this study, there is general agreement with the above results. The kinetics of penetration were linear, the activation energy was 20 kcal per g-atom, and at 650°C the rate of wetting was 2 to 5 x 10-6 cm per sec. The rate of wetting in the A1-Ga system6 is somewhat

Jan 1, 1969

By J. E. Warren, J. H. Hartsock

Because of the extensive utilization of hydraulic fracturing for the stimulation of low-productivity wells, the two related problems of fracture design and evaluation have become economically significant and, as a consequence, helve motivated this investigation. The producing characteristics of horizontally fractured wells were studied to determine the fracture configuration that should be employed as the basis for the design of the treatment and to develop a method that can be used to establish the degree to which the design objectives have been achieved. The equations which describe the steady-state flow of a single-phase fluid into, and through. a finite-capacity fracture were solved numerically for an idealized reservoir-fracture model. The numerical results were used to obtain an apparent skin effect for each combination of the parameters considered. Based on the computed results, subject to the limitcitions implied by the assumptions that were made, the following general conclusions were drawn. 1. For a radius of drainage at least four times us large as the radius of the fracture, an apparent skin effect that is independent of the radius of drainage can be calculated. 2. The productivity of the hydraulically fractured system, relative to that of the unfructured well, can be determined from the apparent skin effect and can be used to establish design objectives. 3. In the evaluation of a fracture job, it is not Possible to determine both the radius of the fracture and its flow capacity uniquely from the apparent skin effect; an independent determination of one of the quantities is necessary. lNTRODUCTION Although hydraulic fracturing has been employed as a method for stimulating the productivity of literally hundreds of thousands of wells during the past 10 years, it is only in the last few years that improvements in fracture design1-6 and fracturing technique&apos; have combined to increase the probability of obtaining a successful treatment to such an extent that the mechanics of the method may be considered to be standardized. From an economic point of view, however, two related questions must be satisfactorily answered before hydraulic fracturing can be used in the most profitable manner. The two questions are the following. I. For a particular well in a given formation, what are the optimum design specifications for the fracture treatment? 2. Have the design objectives been achieved by the fracture treatment? The significance of these questions has been recoguized, and some attempts to obtain answers have been made. Howard, et al,8 endeavored to determine the optimum treatment, based on maximizing profits, for any given formation; unfortunately, this work was based on a crude method for approximating the productivity of a well. Carter and Tracy9 utilized the same approximation to study the effect of fracturing on the behavior of a well producing by virtue of a solution-gas drive. Electrolytic models were used by van Poollen10 to investigate the variation in productivity due to fracturing; however, only a limited number of results were presented. Later, from the same model results, van Poollen, et al,11 attempted to justify an approximate expression for determining the productivity of a fractured well. It is quite apparent that there is a definite lack of the practical information necessary for specifying the optimum fracture configuration to be considered for design purposes. The only detailed attempt to develop a procedure for evaluating the result of a given fracture treatment appears to be that of van Dam and Horner.12 These authors described a technique for analyzing pressure build-down data, obtained immediately after fracturing, to determine the final fracture volume, the final fracture porosity, the fracture area, the fracture thickness and the in situ fluid loss of the fracturing fluid. While this approach should be useful whenever acceptable pressure measurements are available, it does not yield a value for the flow capacity of the fracture. Since the problems of fracture design and evaluation are inversely related, it should be sufficient to study the effect of the fracture configuration on the performance of a well. The primary objective of this investigation is to evolve a technique for computing the desired solutions. The secondary objective is to analyze these computed results in order to prescribe a method for evaluating fracture treatments. Because this study is exploratory in nature, its scope

By A. Kenneth Schellinger

THE terms surface tension .and surface energy are well known when applied to liquids and are generally described by referring to the excess energy of the air: liquid interface as a result of unsaturated molecular forces surrounding the surface molecules of the liquid due to the presence of the air phase on one side. Such unbalanced forces produce the familiar water droplet of spherical form and are generally summed up as a surface tension measured in dynes per centimeter which can be shown mathematically to be equal numerically to a corresponding surface energy expressed in ergs per square centimeter. A specific surface energy, however, is best thought of as the energy necessary to produce one unit of new surface on a substance. Hence, in producing a bubble in a flotation cell the impeller must supply surface energy corresponding to the air: liquid interfacial area on the interior of the bubble. Inasmuch as it is relatively easy to extend or contract the surface of a liquid, there are a number of successful methods for liquid surface tension, or energy, measurement based upon surface deformation. This happy state of affairs does not, however, extend to solids, which are considered to possess surface energies for the same reasons as do liquids, i.e. because of unsaturated ionic bonds at the solid gas interface. As in the case of the flotation cell producing surface on liquids as new bubbles, it takes energy to produce new surface on solids as new particles. As every mill man knows, this surface is produced on mineral solids in a grinding mill by the action of a tumbling mass of iron balls. But here so much energy usually is wasted by the inefficient action of these balls that a large amount of heat is generated, and the surface energy production may be easily confused with the energy necessary to produce this ineffective heat. The tumbling balls and fracturing minerals ultimately take their energy from a rather large electric motor. It has been variously estimated that from 10 to 20 pct" only of this energy from the motor does not appear as heat and may be presumed to appear as surface energy on the minerals present.. Such a production of new surface on the mineral phases is accompanied, of course, by a size reduction that is inevitable as more and more mineral interior molecules become surface molecules by the fracture exposure. This size reduction of mineral particles, although the most obvious feature and perhaps the sole object of the milling operation, is from this energy viewpoint the outward manifestation of the production of surface energy only. Measurement of the characteristic surface energies of pure minerals and their various mixtures in ores would be a step towards understanding of the energetics of the commercial grinding operation. In addition, the characteristic surface energy of a mineral is probably a physical property specific for that mineral, and therefore, from a scientific standpoint, should be measured. It is interesting to note that, in contrast to the large body of work on the surface tensions of liquid systems and biological systems, the field of solid surface energies has been neglected. Prior to. 1920 it is difficult to find more than one or two references to work on solid surface energies in Chemical Abstracts. Since 1920 such references number somewhat less than 100, while those on liquid systems are numbered in the thousands. Much of this apparent neglect of the field of solid surface energies (the term is intended to be somewhat inclusive at this point and refers both to the solid: gas, and the solid: liquid interface) is because of the lack of a reliable method of measurement rather than any lack of scientific curiosity. It was, and still is, difficult to produce new surface on a solid without the simultaneous production of interior changes in the same solid which may consume part of the energy used. The extension in the surface area can be measured, but the interior crystal-

Jan 1, 1952

By J. N. Chew, C. A. Connally

A correlation is presented for predicting the viscosity of gas-saturated crude oils under reservoir conditions. It is based on the dead oil viscosity and the solution GOR. The correlation was developed from a study which showed that at a fixed solution GOR, the relation between the gas-saturated oil viscosities and the correrponding dead oil viscosities is a straight line on logarithmic coordinates. Data from 457 crude oil samples from the major producing areas of the U. S., Canada and South America were used. The best straight lines through the data were fitted by the method of least squares with a digital computer. The correlation is presented in the form of an equation and also in a convenient gra-phical form. INTRODUCTION The viscosity of gas-saturated crude oils under reservoir conditions is an important physical property used in reservoir engineering calculations. Many difficulties are inherent in the sampling of gas-saturated oils and in the laboratory measurement of their viscosities. Therefore, it is frequently neither possible nor convenient to obtain measured values, so the viscosity must be estimated from other, more readily available data. This paper presents a correlation for predicting the viscosity of gas-saturated crude oils. The correlation is based on the amount of gas in solution and the viscosity of the dead oil at the temperature of interest. A previous correlation of these variables was presented by Beal. In comparison, the correlation presented here extends to a higher GOR and to a lower dead oil viscosity. Over the range of variables covered by both, this correlation is based on approximately 11 times as many oil samples. DEVELOPMENT OF CORRELATION A study was made of the variables or parameters which could be used to relate the viscosity of a gas-saturated oil to its dead oil viscosity. Preference was given to those variables which are easily and commonly measured in the field or in the laboratory. It was found that either the differential liquid formation volume factor or the solution GOR of the gas-saturated oil could be used as a correlating parameter. The solution GOR was se- lected for the correlation because of its simplicity and availability. In an attempt to refine the correlation by introducing a second parameter, the following additional variables were tested: differential liquid formation volume factor at the reservoir bubble point, the formation volume factor at the saturation pressure for the GOR of interest, reservoir temperature, viscosity of C+ fraction at 100°F and atmospheric pressure, weighted average gravity of gas in solution, oil gravity, reservoir bubble point pressure, saturation pressure at the selected GOR and reservoir temperature, and gas mol fraction. None of these improved the correlation to any significant extent. It was found that at any fixed solution GOR, the relation between the gas-saturated oil viscosities and the corresponding dead oil viscosities is a straight line on logarithmic coordinates, for the range of variables investigated. This straight-line relationship was used for the correlation. Viscosity data on a total of 457 crude oil samples were used. The data were obtained with rolling ball-type viscometers. The samples came from all of the important producing areas of the U. S., as well as from Canada and South America. Their geographical distribution is shown in Table 1. The ranges of properties represented by these samples are as follows: For each crude oil sample the viscosity of the liquid phase from each step of a differential liberation was plotted against its solution GOR on semi-logarithmic paper. A smooth curve was drawn through the points and values of viscosity in centipoises were read from

By J. S. Browning

The U.S. Bureau of Mines has been experimenting with flotation processes to separate the spodumene-beryl ores mined at Kings Mountain, N.C. The success to date as well as the present status of the process is discussed. Further experimentation is underway and studies will be made on the milling costs involved in the flotation process. The pegmatites of the Kings Mountain-Lincoln ton, N.C., area constitute the largest known domestic reserve of beryl and spodumene. The reserve is estimated to contain 90 million tons of pegmatic material with 1,280,000 tons of recoverable Li,O(lithia) as spodurnene.&apos; The pegmatites also contain 0.4 to 0.5 pct beryl disseminated throughout the orebodies. The pegmatites may contain a potential reserve of 240,-000 tons beryl, equivalent to approximately 34,000 tons of BeO. Different flotation methods for separating beryl from feldspar or quartz, or both, have been developed by various investigators.2-7 On the other hand, published information is limited on concentration of spodumene-beryl ores. As the response of beryl and spodumene to flotation is essentially the same, a successful separation of the two minerals depends upon use of a selective depressant or a selective collector for one of the minerals. Several years ago, the U.S. Bureau of Mines, recognizing the need for developing a large domestic supply of strategic beryl, undertook studies to develop improved methods of recovering this mineral. Because of the low beryl content of the pegmatites, economic production of the beryl entails its recovery as a byproduct of spodumene flotation. Thus, the development of procedures that would provide for maximum recoveries of the spodumene, as well as the beryl, was a primary objective of the studies. Tests were made on run-of-mine ore and spodumene flotation tailing from the Foote Mineral Co.&apos;s spodumene concentrator at Kings Mountain (Fig. 1). Pet-rographic analyses of the ore and flotation tailing are given in Table I. Detailed analyses and examinations of the ore and tailings revealed that the beryllium was present in the form of a low-alkali beryl. The crystals were small, rarely larger than 14-mesh diam, and were clear and colorless. About 10 pct of the Li20 content of the ore was present in the mica and feldspar components of the pegmatite. In some weathered ores the associated clays also contained small amounts of lithia. This is typical of pegmatites in the Kings Mountain area. LABORATORY TESTS In the past, a vigorous chemical treatment of the spodumene surfaces with acid or caustic soda has been considered essential for satisfactory selective flotation of the spodumene from the other minerals in pegmatites. Many tests were made during this investigation to determine if chemical treatment of the spodumene could be eliminated in favor of a reagent combination that would depress the other minerals while selectively floating the spodumene. A simple reagent combination and process was developed that gave better spodumene recovery and grade of concentrate than the more elaborate acid or caustic treatment methods previously used. The finely ground ore pulps were conditioned with either an ammonium, alkali, or alkaline earth lignin sulfonate and sodium fluoride, and the spodumene was floated and cleaned using oleic acid as the collector. The spodumene tailing was deslimed, conditioned with sulfuric acid and coco amine acetate, and floated to reject mica. The mica tailing was thickened and conditioned with hydrofluoric acid, then washed to remove the acid. The washed pulp was conditioned with sodium hydroxide for pH control, and the beryl was floated and cleaned with oleic acid as the collector. Table II summarizes the results of the laboratory test work. About 77 pct of the spodumene and 75 pct of the beryl were recovered from the pegmatitic material. The spodumene concentrate assayed 6.1 pct Li20 and 0.01 pct BeO, and the beryl product assayed 3.0 pct Li20 and 1.57 pct BeO. Similar results were ob-

Jan 1, 1961

By Frank C. Kelton

It is perhaps not widely realized that extraction and saturation processes carried out on oil well core samples alter the properties of these samples to varying degrees. On the other hand it is felt by some that quick-freezing of core samples increases their permeability and porosity significantly. Accordingly, laboratory tests were carried out on 49 pairs of horizontally adjacent samples in order to differentiate between the effect of quick-freezing per se on permeability and porosity of the samples, as distinguished from the effect of the identical saturation treatment on permeability and porosity of the companion samples. Also, additional field data were obtained on comparison of frozen vs unfrozen companion samples. LABORATORY INVESTIGATION OF FREEZING us SATURATION EFFECTS Procedure The samples used in these tests were two-cm cubes cut in horizontally adjacent pairs from cores from eight Gulf Coast and Mid-Continent wells, which cores had not previously been frozen. These samples were extracted with carbon tetrachloride, dried, and air permeabilities run in the conventional manner. They were then evacuated and saturated with brine of 25,000 ppm sodium chloride content, and porosities determined by gain in weight. The samples were partially desaturated by evaporation down to an average brine saturation of 68 per cent. One sample from each pair was quick-frozen by covering with dry ice after wrapping in a single layer of paper, and allowed to remain frozen for about two hours; the companion sample from each pair was not frozen. After thawing the frozen sample, all samples were immersed in tap water overnight in order to leach out most of the brine. Air permeabilities were re-run, and the samples were again saturated with brine to determine a second porosity value. For purposes of averaging of data, the samples were grouped according to four permeability ranges, from 0 to 10, 10 to 100, 100 to 1,000, and 1,000 to 3,840 md. Average permeability and porosity changes for the frozen vs the unfrozen adjacent samples are shown in Table 1. Discussion As may be seen from Table 1, the averages of the per cent permeability increases for the quick-frozen samples ranged from 3.8 to 12.9 per cent among the four permeability groups. The average changes among the four groups of unfrozen companion samples ranged from a decrease of 0.2 per cent to an increase of 9.3 per cent. There was no particular correlation of these changes with magnitude of permeability; however, the increase for each group of frozen samples paralleled the increase for the corresponding unfrozen samples. The differences between the two sets of values are believed to be a valid indication of the effect of the quick-freezing in itself, since the treatment of the two samples in each pair was identical except for freezing. The permeability changes which are strictly the result of the quick-freezing are shown in the sixth column of Table 1. These range from a decrease of 0.9 per cent to an increase of 4.0 per cent; the overall weighted average is 1.2 per cent, as compared to an average increase of 6.8 per cent caused by the saturation treatment of the samples not frozen. The average porosity changes are in general smaller than the changes in permeability, and range from a decrease of 2.3 per cent to an increase of 3.3 per cent. The overall weighted average change ascribed to the quick-freezing is 1.0 per cent of porosity. Many factors can contribute to the changes in permeability and porosity observed when subjecting cores to the simple processes used in these tests. Such are: hydration and swelling of clay, adsorption of ions, changes in surface structure and wettability, expansion and compression effects due to ice formation, shrinking and cracking, leaching of salts and colloids, displacement of particles resulting in either blocking or enlarging of pore openings. Whatever particular mechanisms are involved. however, it is apparent not only from this study but also from other investigations in the literature&apos; not directly concerned with quick-freezing, that the effects produced by commonly used extraction, saturation and drying techniques may be of considerable magnitude The results of this study indicate that for the particular samples and techniques used, such effects are of the order of five to six times the effect of quick-freezing. insofar as changes in permeability are concerned. It may be argued that these samples might not include extremely shaly material where the effect of freezing upon permeability may be much greater. However, had such material been available for these tests, it would undoubtedly have been very susceptible also to alteration by the extraction and saturation treatment used. To investigate this point further, the individual sample data were re-grouped according to the magnitude of the average per cent permeability increases for the pairs of samples, irrespective of permeability. The results

Jan 1, 1953