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By W. T. Weller

In Part I, a study of pressure build-up curves calculated for conditions under which both oil and gas flow led to the conclusion that the presence of a dispersed free gas phase in an oil reservoir must be taken into consideration to estimate accurately average reservoir pressure and permeability from build-up curves. Familiar methods based on the assumption of no free gas can be extended to the two-phase case by using total compressibility and mobility in place of single-fluid compressibility and mobility. These methods give correct values for average pressure and permeability when gas saturation is small. Errors become larger as the gas saturation increases. However, for the use to which the results will be put, the methods are satisfactory for reservoir engineering purposes. An improved method of calculating the performance of depletion-type reservoirs is presented in Part 2. Because the mathematical relationships describing simultaneous flow of oil and gas are quite involved. simplifying assumptions are made to provide means of obtaining approximate solutions of reasonable accuracy. One such approximate method now in use is the constant-GOR solution. It involves the assumption that at any instant, the ratio of total gas flow rate (both free and disolved) to oil flow rate is the same at all points in the reservoir. The approach is not applicable unless the free gar saturation in the reservoir is everywhere greater than the critical gas saturation. This paper presents a modification which, by avoiding the constant-GOR assumption, makes the method applicable to all reservoir conditions, and so far appears to be more accurate than the constant-GOR solution and to he comparable in required compuctation time. PART I— BUILD-UP CURVE ANALYSIS INTRODUCTION Pressure build-up characteristics of shut-in wells have been used for many years by engineers to evaluate average reservoir pressure, effective permeability thickness of the pay section, effectiveness of well completion (skin effect) and reservoir size. A number of methods of analysis have appeared from time to time."" Without exception, these methods are based on the assumption that the reservoir contains but one fluid of constant small compressibility and constant mobility. It has been suggesteda" hat these single-fluid methods may be applied to data from reservoirs containing both oil and gas by substitution of some effective total properties of the multiphase system in place of the corresponding single-phase properties. The present investigation was undertaken primarily to evaluate this approach. METHOD A number of theoretical build-up curves were calculated for conditions of two-phase flow, under the assumption of certain reservoir and fluid properties, and were analyzed by single-fluid methods with appropriate total compressibility and total mobility values for the corresponding single-fluid properties. Results of the analyses were compared with the assumed conditions. The theoretical build-up curves were completed by procedures similar to those of West, Garvin and Sheldon." Since these calculations require a considerable amount of computer time, an attempt was made to derive an approximate calculation method. The attempt was unsuccessful for calculating build-up curves, but the effort did result in a new approximate method of calculating the performance of solution gas drive reservoirs, which appears to be an improvement over the constant-GOR method" used previously (see Part 2). The West, Garvin and Sheldon calculations involved the following assumptions: (1) the reservoir is circular and completely bounded, with a completely penetrating well at its center; (2) the porous medium is uniform and iso-tropic, with a constant water saturation at all points; (3) gravity effects can be neglected; (4) compressibility of rock and water can be neglected; (5) the composition and equilibrium are constant for oil and gas; (6) the same pressure exists in both the oil phase and the gas phase; and (7) no afterproduction occurs, i.e., the well is shut in at the sand face for build-up. These assumptions make it possible to describe two-phase flow of oil and gas by the partial differential equations:

Jan 1, 1967

By S. R. Balajee, I. Iwasaki

The interaction between British gum 9084 and dode-cylammonium chloride (DAC) at quartz and hematite surfaces was established from coadsorption studies and streaming potential measurements. The cationic DAC interacts with the somewhat anionic British gum 9084, leading to the formation and adsorption of a binary complex of DAC-British Gum 9084 at the interface. The parallel ability to depress quartz along with hematite as a result of the interaction between DAC and British gum appears to be the main reason for the ineffective depressant action of starches and starch derivatives in the cationic flotation of iron ores. Amines are not particularly selective collectors for the flotation' of siliceous gangue from iron ores and, therefore, a suitable iron oxide depressant is needed for a satisfactory separation. Various starches and their derivatives have been extensively tested with oxidized iron ores,'-3 and it has been empirically established that British gums and dextrins are preferable. However, for the flotation upgrading of magnetite-taconite concentrates from 8 or 8.5% Si O2 to about 5% Si 02, British gums, which have been used so successfully on oxidized iron ores, have been found to have no effect and oftentimes are actually deleterious.4 In previous articles,5-7, starches were shown by adsorption measurements, flotation tests, and floccula-tion tests to interact with calcium ions in solution, and it was thought that a study on the interaction between starches and dodecylammonium ions would be able to shed some light on the anomalous flotation behavior described above. In fact, starches are known to interact markedly with paraffin-chain-type surface active agents and, thereby, to precipitate the starch or inhibit the iodine-starch reaction.8 From X-ray diffraction studies and viscosity measurements, the formation of a helical complex between mylose and a surface active agent has been postulated.9 The interaction with other types of hydrophilic colloids, such as synthetic polymers and proteins, has also been investigated and is usually explained in terms of van der Waals' force interaction and/or ion-ion interaction. In the present investigation, the interaction of British gum and dode cylammonium chloride on quartz and hematite was studied by adsorption and streaming potential measurements in an attempt to establish the mutual adsorption behavior of British gum and dode-cylammonium chloride on mineral surfaces and to clarify the anomalous depressant activity of British gum in the cationic flotation of iron ores. All the measurements were carried out at a natural pH of near 7 because dodecylammonium chloride gives maximum selectivity of flotation separation at this pH2 and to avoid any third parameter in the system. EXPERIMENTAL MATERIALS AND METHODS Minerals: The quartz and hematite samples used for the adsorption tests were prepared as described in a previous paper,"J except that the specific surfaces of the samples were increased to 5,860 and 16,000 Sq cm per gm, respectively. For the streaming potential measurements, the 48165-mesh fractions screened out of the original samples were etched with hydrochloric acid, washed repeatedly with water, and stored under water in Pyrex bottles. Reagents:DodecyIammonium chloride (DAC) was prepared1 1 by bubbling dry hydrogen chloride gas through a benzene solution of high-purity dodecylamine supplied by Armour and Co. British gum 9084, received from Corn Products Co., was solubilized by first dispersing it in water to produce a 0.05% solution and then homogenizing it in a blender for 5 min. Distilled water was used in the preparation of the samples and the solutions and for all test work. Adsorption Measurements: The procedure for the adsorption density determinations was also the same as that described in the previous paper.1° The residual concentrations of the British gum and the DAC in the supernatant solution were analyzed colorimetrically by the phenol-sulf uric-acid and amine-picrate methods, respectively. The validity of the mine-picrate method for the colorimetric analysis of DAC in the presence of British gum and the analysis of British gum in presence of DAC were checked by establishing calibration curves between optical density and concentration. Streaming Potential Measurements: The cell assembly for the streaming potential measurements was similar to that described by Fuerstenau.' The streaming potential

Jan 1, 1970

By R. H. McLean

Jet impingement produces two mechanisms to clean the bottom of a borehole during jet-bit drilling operations. One is an impact-pressure wave in the immediate area of jet impingement. The other is crossflow, which spreads across the bottom away from the pressure wave. Measurements of the vertical distribution of the cross-flow at several positions beneath a 4 3/4-in. tricone jet bit in a laboratory model show that the maximum velocity in the crossflow is directly proportional to the square root of the product of the rate of flow and the velocity of the jets through the nozzles (QV). Other measurements in the laboratory model show that gradients in the impact-pressure wave are directly proportional to the jet QV if the diameters of the nozzles are held constant. Consistency of the basic relationships through changes in the Reynolds numbers of the jets from 31,000 to 93,000 suggests that the laboratory results should be representative of typical flow in field operations having higher Reynolds numbers. Estimates of the impact-pressure waves under conditions other than those in the jet-bit model may be made by comparison with a less complex model—impingement of a jet against an unrestricted flat surface normal to the jet. Equations derived from current jet technology describe the wave in this simple system for a wide range of conditions. INTRODUCTION The efficiency of rotary drilling operations is strongly linked to the efficiency with which cuttings are removed. Cuttings remaining on the bottom of the borehole will impede further penetration by the bit until they are removed. Wasteful regrinding is prevented if the fluid circulated past the bit removes cuttings as rapidly as they are made. Most investigations of bottom-hole cleaning under bits have been concerned with the rate-of-penetration effects of bit type, nozzle configuration, fluid properties, pressure gradients and utilization of hydraulic horsepower. These investigations have shown that drilling muds, weighted to keep the pressure in the borehole greater than in adjacent formations and carrying material which forms a filter cake, apparently plaster cuttings against the bottom, making them difficult to remove. In addition to a demonstration of the factors causing poor cleaning, the most significant result of these previous investigations has been the increased use of jet bits accompanied by better hydraulic programs and better selection of drilling fluids. Undoubtedly, these practices have improved bottom-hole cleaning, but rates of penetration when drilling with muds are still often lower than would be expected with perfect cleaning." Although there is general agreement with the concept that increasing hydraulic energy at a jet bit often increases the rate of penetration by improving cleaning, research workers have differed as to the best criterion for evalyating hydraulics. Some lean toward maximizing the product of the rate of flow and the velocity through the nozzles (QV) others prefer to maximize the hydraulic horsepower at the bit;'"-' "till another says that neither criterion is universally suitable."' This controversy shows that conclusive field evidence has not established the superiority of either of these criteria. Analysis of the fluid flow which cleans the bottom should contribute to resolving the controversy. Impinging jets clean the bottom by creating two mechanisms capable of dislodging cuttings. One is the impact from the momentum of the jet and the other is the flaw parallel to the bottom away from the area of impingement. The impact force appears in the form of a pressure wave on the bottom and, in this paper, is called the impact-pressure wave. The flow parallel to the bottom is called crossflow. Fig. 1 illustrates these two mechanisms. This paper describes crossflow and the impact-pressure wave beneath jet bits and relates them to controllable parameters. Through these relations, criteria for use in designing hydraulics to achieve maximum use of the mechanisms of cleaning are derived. PROPERTIES OF CROSSFLOW CONCEPTS DEVELOPED IN PREVIOUS INVESTIGATIONS Concepts of scavenging the bottom by crossflow have been well discussed by Bobo, et al." They examine the means by which crossflow may create forces on cuttings and conclude that the cleaning action of crossflow can be increased by increasing the velocity of the flow stream close to the bottom. Using boundary layer theory, they indicate that a reduction in the viscosity of the drilling

Jan 1, 1965

By F. C. Pittman, D. W. Harriman, J. C. St. John

This paper mentions briefly the history of hydraulic jetting as applied to perforating and fracture initiation. It points out the advantages of hydraulic perforation and undercutting as an aid for creating a fracture at the point desired rather than depending upon the weakest point in the formation for breakdown. It describes early experimental work with jet nozzles in search of better nozzle materials. The effect of splash-back damage and its subsequent influence on jet body and tool design during this work is discussed. A series of cutting-rate curves for jets cutting steel and steel-cement-formation combinations is presented to show the effect of hydrostatic head and the point of diminishing returns with respect to cutting time. There is a series of photographs showing various types of rock formation in which perforation and undercutting tests were made. These stones were drilled and the casing cemented in place as in an actual well. The casing was perforated and circularly cut as if preparing for a fracturing job. The conclusion reached in the paper is that hydraulic jetting with sand-laden fluid can be used for perforating and undercutting casing, cement and formation rock for the intended purpose of inducing the formation to fracture at a desired point. INTRODUCTION Hydraulic jetting as a means of cleaning a formation during acidizing has been used for many years. The acid-jet gun was used to clean formation and for drilling cement from casing with acid. This tool was dropped to a seating ring installed on the tubing and could be retrieved by reverse circulation or wire line. In this process, the fluids were directed against the formation to clean and penetrate beyond the mud-damaged area. After the development of the hydraulic fracturing process, interest in jetting the formation with abrasive-laden fluid was renewed. The cutting action of abrasive fluid on pumping equipment, which is a well known problem, has been utilized to perforate and undercut casing, tubing and formation. In this process, surface areas are provided in the formation on which the frac- turing pressures may work to produce a fracture at the location desired. EQUIPMENT The tools used consist of bodies containing two, three or four jets in a single horizontal plane equally spaced around the circumference. The body is threaded to the end of a string of tubing and run into the well. In addition, an expendable tool is available that may be left in the hole after perforating and produced through until necessary to remove the tubing. The bottom of each tool is equipped with a ball-type back-pressure valve. The ball can be reversed to the surface and recovered. This allows reverse circulation so that loose sand which accumulated below the tool while jetting may be removed before the fracturing job. The present jetting tools are of such length that, when screwed together, the jets fall on 12-in. spacing. ANALYSIS OF THE PROBLEM Early work with nozzles indicated that hardened steel was not a suitable material for jets and that more durable material would be required. Ceramics were tried and found to be superior to steel but still too shortlived for most applications. Tungsten carbide, which was tried and found to be the best material available, is now being used for jet nozzles. Analysis of the problems presented by this process indicated that the following information was needed. 1. The effect of submergence on a jet stream and the effect of submergence on the cutting rate of a jet stream. 2. The cutting rate and depth of a jet stream in steel. 3. The cutting rate in various formations and point of diminishing returns. 4. Size of hole or slot cut in a pipe by a given jet. 5. Fluids and sands used. 6. The flow of various weight fluids through the jet nozzle and the discharge coefficients. 7. The type cut formed in the formation by the jet stream. 8. The stretch and contraction of tubing due to temperature and pressure. The cutting effect of a jet stream on a target in the atmosphere is rapid and spectacular as most of the

By Alex Boozenny

The results of potential measurements between 1) a titaniurn electrode in NaCl-TiCl, melts and a graphite-cizlorine reference electrode and 2) a titanium electrode in NaC1-Nu "melts and a graphite-chlorine reference electrode show that the following relationship expresses the equilibrium relationship between the TiCl, and the dissolved metallic sodium concentrations, expressed in mole fraction units, in dilute NaCl welts at 850°C. The results of potential measurenments between a graphite electrode in NaCl-TiCl, melts that were saturated with TiCl, and a graphite-chlorine reference electrode, when combined with the standard free energy data given in literature, gave the following expression for the equilibrium relationship between the TiCl, and TiCl, concentrations, expressed in mole fraction units, in dilute NaCl melts at 850°C. These relationships are for melts in equilibrium with pure titanium. In impure systems, less sodiurn and more TiCI, can be copresent with a given concentration of TiCl,. AFTER 10 years of existence, the titanium metal industry still relies on the original Kroll and the sodium reduction processes for the only important means of converting titanium-bearing ores to titanium metal via production of titanium tetrachloride as an intermediate. Through years of modification and development these two processes have evolved to a point where any further major economic advances in the field of titanium metal production must be achieved through implementation of processes which are distinct departures from simple magnesium or sodium reduction of titanium tetrachloride. Concurrently with the refinement of the Kroll and sodium reduction processes, industries and government have sponsored research and development in the field of producing titanium by electrolysis of oxides,' carbides,' and halides3'4 in fused salt media. However, the incomplete understanding of the physical chemistry of fused salt systems has in many cases hindered the development of promising new titanium production processes to the point where they will have a clear advantage over the processes presently employed. Fortunately the volume of information on fused salt physical and electrochemistry is increasing at an accelerating pace. The first approaches tbward investigating the electrochemical behavior of fused salt systems have been the measurements of equilibrium potentials of metals immersed in melts containing their halides.' Some work on the kinetics of fused salt electrochemical processes has been reported.'09" Some descriptions of the structural composition of fused salt systems are also available. The work described herein is a continuation of the study of metal electrode potentials in fused salts. Specifically, this contribution to the growing store of fused salt chemistry information presents a description of the equilibrium relationships between the concentrations of titanium dichloride, titanium trichloride, and metallic sodium in fused sodium chloride. The investigation of the titanium dichloride-titanium trichloride equilibrium relationships is not completely new. Kellog and Krye and Melgren and opie15 have presented the results of chemical analysis of salts containing titanium chlorides. Flengas and lngrahaml' have published the results of an investigation of these equilibrium relationships obtained by measurement of electrode potentials in a fused NaCl-KC1 mixture. The investigation described herein differed from that of Flengas and Ingraham principally in the use of straight NaCl as the solvent in place of the more costly and more difficult to purify mixture. This investigation was conducted in three parts. First, the equilibrium potentials of titanium in sodium chloride containing known concentrations of titanium dichloride were measured. A graphite-chlorine electrode was employed as reference. Second, the equilibrium potentials of titanium immersed in sodium chloride containing known concentrations of elemental sodium were measured. Third, the equilibrium potentials of graphite immersed in titanium tetrachloride-saturated sodium chloride containing known concentrations of titanium trichloride were measured. The results of these three related investigations are presented in the above order. The results are combined with the thermodynamic properties of titanium chlorides and sodium chloride, obtained from literature, to give the titanium dichloride-titanium trichloride-elemental sodium equilibrium concentration relationships. In the test, whenever a melt contains titanium chlorides in predominantly divalent form, the melt

Jan 1, 1962

By P. Somasundaran, D. W. Fuerstenau

The length of the collector is found to influence the flotation of the mineral even at incipient conditions, which are below the concentration at which interaction at the solid-liquid interface begins to take place to form hemi-micelles. To study this dependence, concentration for incipient flotation of quartz was determined as a function of pH with collectors of various chain lengths. The observed effect of chain length on flotation is ascribed to that of collector adsorbed on the bubble surface. In previous studies, it was shown that at low concentrations the alkyl collector ions adsorb at the solid-liquid interface as individuals.''2 At higher concentrations, the collector ions adsorbed at the solid-liquid interface associate with each other to form two-dimensional aggregates called hemi-micelles. Above the hemi-micelle concentration, the length of the hydrocarbon chain is extremely important since the hydrocarbons are in effect removed from water during the association, making the energetic conditions more favorable for adsorption at the interface. Because of this enhanced adsorption, one observes a very rapid increase in flotation associated with the hemi-micelle formation at the solid-liquid interface. However, a dependence of flotation on the chain length at concentrations below that required for hemi-micelle association was also observed,' and this cannot be explained by the above mechanism which postulated hydrocarbon chain interactions only at the solid-liquid interface. This prompted an investigation into other possible reactions of the hydrocarbon chains and an examination of the conditions at the bubble surface involved in the flotation system and how these observations might explain the reactions at the solid-gas interface which cause the particle-bubble attachment required for flotation. To obtain more information on chain length effects, flotation, under incipient conditions, was tested by vacuum flotation techniques. The collector-concen-tration-pH relationships for flotation of quartz with alkyl ammonium acetate collectors was delineated by observing the pH at which quartz particles begin to float to the liquid surface. By investigating flotation as a function of pH, it was also possible to study the effect of neutral molecules on incipient flotation conditions, since the aminium ions hydrolyze to amine molecules at higher pH values. EXPERIMENTAL WORK Brazilian quartz specimens were crushed and sized, and the 270 x 400 mesh fraction was used for flotation studies. The samples were leached with concentrated hydrochloric acid until no coloration of the acid occurred. The leached material was washed free of chloride ions and stored in distilled water. The vacuum flotation technique developed by Schuhmann and prakash3 was used to determine the critical pH-concentration curves. This method, which can be used to delineate conditions for incipient flotation, is fairly simple and rapid. About 0.5 gm of 270 x 400 mesh quartz was placed in a 100 ml graduated cylinder which was then filled to the 100 ml mark with the collector solution made from high-purity alkyl ammonium acetate salts. The water used for the test was conductivity water saturated with air that had been passed through a cleansing train consisting of Drierite, Ascarite, a water wash bottle, and a trap. After the pH was adjusted, the cylinder was then conditioned for thirty minutes. In the tests where an acid pH was desired, sufficient acid was added before the collector solution to avoid any effect due to slow desorption of collector from the quartz surface. After conditioning, vacuum was applied to the system and the flotation or nonflotation of the quartz was noted. The pH at which the quartz particles began to float to the liquid-gas interface was taken as the critical PH. Critical pH curves were thus determined for different concentrations of the various collectors. Hallimond tube flotation data were taken from the authors' previous publication1 for correlation with that from the vacuum flotation. RESULTS AND DISCUSSION The results of vacuum flotation studies for determining critical pH-concentration curves, i.e., curves which delineate conditions for incipient flotation, are shown in Fig. I. In generaI, all the curves exhibit an upper and lower pH limit between which flotation will

Jan 1, 1969

By D. H. Baldwin, R. E. Reed-Hill

Six compositions of polycrystalline ZY-0 alloys, containing up to 4.2 at. pct 0, were tested in tension between 77° and 600° K. The data obtained from each of the compositions corresponded closely to a rela-ion between yield stress and absolute temperature of the form In s/so = BT, where oo is the yield stress extrapolated to zero degrees and B is a constant. In agreement with others who have observed this relationship, it is shown that the activation energy may be expressed as Ho In so/s. In the present specimens Ho is approximately 18,000 cal per mole and is apparently independent of temperature and composition inside the limits of the investigation. It is also demonstrated that this form of activation energy cowesponds to a strain rate sensitivity parameter RT/Ho. Oxygen was also noted to have an effect upon the operative deformation mechanisms. With increasing oxygen concentration there was an increased tendency to observe both nonbasal slip and cross-slip phenomena. Oxygen does not seriously inhibit twinning more than it does slip. Twins were observed in all specimens tested. It is becoming increasingly evident that interstitial atoms in solid solution are able to interact strongly with mobile dislocations. Stein, Low, and seybolt,&apos; have shown that, if the carbon concentration in bcc iron is lowered below the solubility limit, its flow stress temperature dependence is markedly reduced. This suggests that carbon atoms in interstitial solid solution may be responsible for the pronounced temperature dependence of the flow stress normally observed in iron. This view has recently been challenged by Leslie and sober2 who observed a strong flow stress temperature dependence in iron to which a trace of titanium had been added in order to remove carbon atoms from solution. Since the interstitial concentration must be reduced below approximately 1 ppm in order to produce a pronounced effect on the flow stress temperature dependence,&apos; studies of the effect of interstitials on the flow stress in iron necessarily involve serious experimental difficulties in alloy preparation. There are other metals, however, in which strong effects of interstitial solutes upon both the flow stress and its temperature dependence are observed. Of particular significance is zirconium which, according to Domagala and Mcpherson, 3 is capable of dissolving 28.6 at. pct O. The O-Zr alloy system is an almost ideal system for studying the interaction of interstitial atoms with deformation modes since it is possible to form alloys capable of study over an extensive range of compositions. Mills has made such a study using single crystals oriented primarily for single prismatic slip4 and has found an effect of oxygen concentration on the flow stress temperature dependence analogous to that observed in iron due to carbon by Stein, Low, and Seybolt. The present paper is specifically concerned with the effect of oxygen on deformation in polycrystalline zirconium. Although plastic flow in this type of specimen is much more complex than that reported for the single-crystal work, and involves both slip (on several different types of planes) and mechanical twinning, the results of this investigation are in general agreement with the single-crystal observations concerning the effect of oxygen on the temperature dependence of the flow stress. In addition, they also demonstrate that oxygen affects the acting deformation systems. This is in contrast to single-crystal results4 that showed only single slip on a prism plane. EXPERIMENTAL PROCEDURE Material. High-purity hot-rolled zirconium strip, 0.2 in. thick by 4 in. wide, of 0.10-mm average grain diameter, was used for forming alloys. It was obtained from the Carborundum Metals Co., Akron, N.Y., whose analysis indicated the major impurities were, in wt ppm: Hf, 540, C, 145; Fe, 100; and 0, <80. The plate texture was similar to a wire texture, with basal planes generally parallel to the rolling direction and basal poles randomly distributed about the rolling direction. The heat treatments described below did not appreciably alter the basic texture. specimen Preparation. Small threaded-end tensile specimens were machined from the plate with axes perpendicular to the rolling direction. These transverse specimens had gage sections 1 in. long by 0.060 in. in diam. The small gage section diameter was dictated by the fact that the alloys were formed by dif-

Jan 1, 1969

By D. A. Munro, G. P. Contractor

Fourteen 50-lb laboratory melts were investigated to determine the effect of uranium on the tenpering characteristics of loo-carbon (0.06 to 0.1 pct C) steels. It was found that uranium additions, particularly in the range 0.30 to 0.45 pct, enhanced the hardness and both ultimate and yield strength of the experivzental steels in the quenched and tempered condition. The structural and morphological chazges indicated that uranium retarded tempering of the tnartensite, thereby hindering the normal formation of polygonal ferrite formed in the late stages of tempering. The effect of this was to make possible the re-tension of the acicilar ferritic structure in the uranium-bearing&apos; steels. The iraniuin-bearing steels also showed IVidnzanstatten-type growth of ferrite plates and had large prior austenite grains containing assenzblies of fine ferrite grains, mainly acicular in geometry. The fine-grained ferrite structure and the presence of more numerous and apparently smaller precipitates in the uranium-bearing steels are thought to he principally responsible for the itnproved tensile strength and hardness of the experinzental uranium-bearing steels. At ternperirzg temperatures above 455% (850&apos;F) the ferrite in the higher-uraniun steels nzaintained acicularity and, hence, its strength and resistance to tempering. Uranium did not produce a secondary hardening peak. However, it retarded softening during the third stage of tempering because of its effect of inhibiting the grouth of cementite particles and of retaining the acicularity of ferrite plates. The resistance to coalescence accounted for the slow grocth of the ferrite grains in the uranium-modified steels and, hence, fov the persistence of the acicular ferrite structure. IT had been found previously1 that uranium additions up to about 0.45 pct had no significant effect on the tensile properties of low-carbon steel (0.06 to 0.10 pct C) in the as-rolled and normalized conditions, Fig. 1. On the other hand, it was observed that uranium in excess of about 0.30 pct had an embrittling effect as revealed by Charpy V-notch impact results. It was also noted that, as the uranium content increased, the morphology of pearlite changed from lamellar to feathery and the ferrite grains showed an etching effect resembling striated or dashed markings, suggestive of precipitation. The sharp drop in the impact properties shown in Fig. 2 warranted an assumption that the uranium content of about 0.30 to 0.45 pct may produce some secondary hardening reaction on tempering, analogous to that associated with a Cr-Mo-V steel, which shows very poor CVN toughness at the secondary hardness peak in the tempering curve.1&apos; With this background and the reported findings of Hasegawa and noda that low-carbon uranium-treated steel showed signs of secondary hardening, the present investigation was undertaken to determine the effect of uranium additions on the mechanical properties of 0.10 pct C steels. No attempts were made to investigate in detail the mechanisms of hardening, although some suggestions based on the experiments are made. MATERIALS AND PROCEDURES A series of 50-lb induction-furnace melts was made using AISI 1008 rimming steel billets as the melting stock. The melting, forging, and rolling techniques proven satisfactory in previous projects&apos;-3 were employed as a guide for this investigation. The steel was deoxidized with aluminum (2 lb per ton) prior to the addition of high-purity uranium. The analysis of each melt is given in Table I. Properties were evaluated as a function of heat treatment and are presented in terms of hardness and tensile strength vs tempering temperatures. The variation of hardness with the tempering temperature was studied on the quenched and tempered specimens, some of which measured 0.50 by 0.25 in. diam and the others 0.40-in. cubes. Before quenching, the specimens were vacuum-sealed in glass tubes and normalized at 900°C (1650°F) for 20 min. Following this treatment, the sealed specimens were hardened by austenitizing at 955°C (1750°F) for 20 min and water quenching, and then tempered for 1 hr in the range 150 to 730°C

Jan 1, 1967

By R. L. Bleifuss

The object of this study was to evaluate the oxidized taconites of the western Mesabi iron range and to establish a correlation between the various basic taconite types and their concentratability. The initial work included a study of the original mineralogical and stratigraphic facies of the fresh taconite and traced the oxidation and leaching patterns developed during the conversion of this material to oxidized taconite. Subsequent studies have extended this work to include the semitaconites and also the wash and heavy media ore types widely developed in the area. Each basic original mineralogical facies or taconite type produces during alteration an equivalent secondary oxidized facies which has a unique mineralogical composition and texture. These control the concentratability of the oxidized taconites. Actually the influence of the original mineralogical composition of the iron formation extends even further and determines whether the most likely product of oxidation and leaching will be a wash ore or a heavy media ore and even to the direct shipping ores where the ratio of hematite to goethite is largely determined by the original taconite type. The relationship between original taconite, oxidized taconite, semitaconites, and wash and heavy media ores is briefly summarized in Table I. The terms are not precise and in some instances tend to overlap. The table is intended to point out only the essential differences between the various materials. The original taconite was dominantly composed of mixtures of magnetite, iron carbonate, iron silicate, and quartz (chert). In a few thin stratigraphic units, hematite was present as an original constituent. The alteration of the original taconite to oxidized taconite has resulted from the circulation of ground waters through an initial fracture system related to minor structures in the iron formation. The chemical reactions have involved the oxidation and decomposition of original minerals such as magnetite, iron carbonate, and iron silicates to hematite or goethite. The alteration at this early stage is characterized by pseudomorphic replacement of the original minerals by oxidation products although retaining the major textural features of the original taconite. There was very little secondary migration of iron at this stage and the total iron content of the rock has been only slightly increased. Further alteration of this material to form a semi-taconite, a wash or a heavy media ore, involves extensive removal of silica in solution and significant redistribution of iron units. Wash and heavy media ores are developed by the growth of coarse secondary iron layers, dominantly goethite, coupled with the removal of silica in solution and decomposition of the cherty layers. This paper is concerned primarily with the materials classified as oxidized taconites which are characterized by oxidation of the original mineral constituents with little secondary enrichment. The area studied, shown on the index map, Fig. 1, extends some 30 miles along the strike of the Biwabik formation roughly from Hibbing to Coleraine. This study was greatly facilitated by the basic stratigraphic and mineralogical studies of Gruner1 and white2. The bulk of the material in this presentation represents a portion of the author&apos;s contribution to a study sponsored by the Great Northern Railway on the oxidized taconites of the western Mesabi.3 METHOD OF APPROACH A total of 106 drill holes, representing some 30,000 ft of drilling, were examined and sampled. The drill holes were logged and some 1500 composite samples were prepared for chemical analysis and bench scale metallurgical tests. These samples were analyzed for total iron and ferrous iron; and magnetite iron was determined by a standard Davis tube test at minus 200 mesh. Standard reduction roast tests using 150-gram samples of minus 10 mesh material were made on these 1500 composite samples with a mixture of H2, CO2, N2, and H2O at a temperature of 650°C. This roasted material was pulverized through 150 mesh and concentrated in the Davis tube. The iron recoveries and concentrate grades obtained on the roasted products were used to assess the concentratability of the oxidized taconites. Detailed mineralogical work was done on thin sec-

Jan 1, 1964

By R. I. Jaffee, F. C. Holden, H. R. Ogden

Alpha solutes increase the strengths of Ti-Mn alloys through solid-solution strengthening. The substitutional a addition, aluminum, decreases, and the interstitial solutes, carbon and nitrogen, increase the rate of nucleation and growth of a from ß. The best combinations of properties of a-ß alloys are obtained when there is a sufficient quantity of a phase in the structure to dissolve the a solutes. OF the many different titanium-base alloy systems, the predominant alloy type is the a-ß alloy. The properties of the a-ß alloys are dependent on solid-solution strengthening and heat-treatment effects involving the a-ß ratio and transformation reactions. Another variable which influences the mechanical properties of a-ß alloys is the a-stabilizer content of the alloy. An a solute may be present as an intentional addition, such as aluminum, or as an impurity element, such as carbon, oxygen, or nitrogen. It is known that these a stabilizers, when added to titanium, form single-phase alloys which are not heat treatable but which obtain their strength from solid-solution strengthening. Thus, it would be expected that a additions to a-ß alloys would increase the strength of the alloys by solid-solution strengthening of the a phase. In addition, they would affect the transformation kinetics of the ß-to-a reactions and other processes based on the instability of the ß phase. The effects of heat treatment and structure on the mechanical properties of Ti-Mn alloys have been shown in a previous paper.6 This system offers a good base to demonstrate the effects of typical a solutes on the properties of a-ß alloys. The three a solutes described in this work are aluminum, representative of a substitutional a solute, nitrogen, representative of an interstitial a solute, and carbon, representative of an interstitial compound-forming element. The effects of heat treatment and microstructure on the properties of a alloys containing these three elements are described in concurrent publications. Some of these data are used for base-line points in several of the curves used for illustration herein. Experimental Procedures Iodide titanium was used as the base for all of the alloys studied in this work. The alloys were prepared as ½ lb ingots by double arc melting in an argon atmosphere. The ingots were forged to ¾ in. rounds, vacuum annealed for 6 hr at 900°C at a pressure of 10 &apos; to 10-5 mm of Hg to remove hydrogen, and hot swaged to 1/4 in. diam rod. After me- chanical descaling, test specimens were prepared for heat treatment. The alloys used in this study together with the fabrication temperatures are given in Table I. Heat treatments were done in argon. For the most part, the specimens were sealed in Vyeor capsules under a partial pressure of argon. Quenching was accomplished by breaking the capsule under water. Other cooling methods used included oil quench, argon cool (simulated air cool in an argon atmosphere), and furnace cool. The times for the various heat-treating temperatures are given in Table 11. The tests performed on the alloys consisted of tensile tests on ? in. diam specimens, hardness tests, and microimpact tests. Specimen sizes have been adequately described in a previous publication.&apos; The micrographs presented in this paper were taken from specimens cut from the shoulders of broken tensile specimens. Final polishing was done with Linde B on a slow-speed wheel, and the specimens were etched with a 1½ HF — 3½ HNO, solution. Ti-N-Mn Alloys The transformation diagram and microstructures of the Ti-0.1 pct N-Mn alloys used in this investigation are given in Fig. 1. The effect of small nitrogen additions on the binary Ti-Mn diagram is to raise the ß-transus temperature with little effect on the a solubility of manganese. Also, as has been noted previously,&apos; high manganese-content alloys containing nitrogen, when quenched from temperatures high in the ß field, contain a subgrain boundary phase which appears to be nitrogen-rich a. Marten-site is formed when alloys containing less than about

Jan 1, 1956

By V. C. Williams

Some of the physical, chemical, and electrical processes for conversion of saline water to potable or industrial water are economically surveyed from an engineering viewpoint. Since all these processes require energy for drive and equipment for containment, the correlative economic factors are developed which indicate directive influences in the choice of particular regional processes. The supply of natural waters and its distance also affect decision. Any one process will probably not prove dominant in the field because auxiliary considerations such as the saline water source; types and continuing availability of fuel; electric power use or recovery; area economic status and advancement; and the political pressures of population, group demands, and land use tend equivocally to obscure capital and operation cost decisions. Basic engineering considerations, data, and economic factors are presented to assist in the direction of these decisions. An exploding world population, increasing industrialization, advancing standards of living, and the desire of less-privileged nations for betterment focus attention sharply on a major problem: water. *19 Up to now, in retrospect, people have had it relatively easy in the handling of this problem. All the better dams in the most advantageous sites, the better aquifers, the shortest aqueducts have been built. In another phase of the problem, concern is evident that wastes cannot indefinitely be disposed of merely by keeping them dilute and discharging them promiscuously. 7-9 And, perhaps, as past civilizations have done,l5 water, watersheds, streams, and irrigation may have been mismanaged or, at the least, not adequately studied.3,5,36,37 In this last is perhaps the core of the problem. As Gross states, "Ignorance and too often, indifference are contributing factors. Archaeology and theology both furnish ample testimony to the existence of rich lands where deserts now stand; it was man who ravaged his land. Unless education is a companion to water development, development might as well be forgotten. But without water, there is no beginning."13 The U.S. is showing increasing concern about its water for predictions are that by 1980 the daily withdrawals will be 494 billion gal, a figure nearly equal to the dependable supply.Is This is based on a conservative projected population of 230 million. The major categories of withdrawals are: To make available this per capita average of 2150 gal per day will require an expenditure of $219 billion over the next 20 years. The U.S. is not alone in this concern. The United Nations shows as arid zones of the world: all of Africa north of the equator and south of the 20&apos;s parallel; all of the Arabian peninsula; all of the middle east and Iran, Iraq, Pakistan, Afghanistan, northern and central India; a great band about 1000 miles wide along the 40&apos;~ parallel from the Caspian Sea east across Russia through China to the Pacific Ocean; all of Australia except the coastal plain; the Caribbean Islands; the western nations of South America; and the western third of the United States and of Mexico. With one quarter of the earth&apos;s 57,500,000 sq miles of land thus suffering from lack of good water, increasing attention goes to the treatment of brackish and sea waters. The U.S. has been a leader in this field4,12, 16123,24 through its Office of Saline Water in the Dept. of Interior because even now some of its cities and regions are short of potable water. 11j&apos;7,M Industrial water is also of vital concern as a result of ever higher industrialization1,14122 Other nations, among them JaPan, Israel,13188 Germany, Union of South Africa, Australia, Netherlands, France, Yugoslavia, Russia, and groups such as the Organization for European Economic Cooperation (OEEC)&apos; are also diligent. The objective is low cost water, which means that both technology and economics have prominent roles in saline water conversion processes. TECHNOLOGY: SALINE WATER CONVERSION A number of reviews of methods have been made, principally by staff members of the Office of Saline Water (U.S. Dept. of Interior). Jenkins,31&apos;32 Gillam,34p

Jan 1, 1962

By H. W. Schadler

The superplastic behavior of low carbon and manganese bearing steels has been evaluated. The results of elevated-temperature stress-strain rate and elongation tests are reported which indicate that high strain rate sensitivity (>0.5) and adequate elongations are achievable in ultrafine-grained steels 1 to 2 p, but at strain rates which are not commercially attractive. It has been demonstrated that the fine grain size is retained after long times and high strains if the temperature is kept within the range of the two-phase (a + ?) field. INTEREST in superplasticity has been stimulated by the desire to: 1) understand the origin of, and mechanisms responsible for, the large uniform elongations observed, and 2) exploit this property for commercial advantage in metal forming operations. Although the Zn-22 wt pct Al alloy presently being studied as a model material1-5 may find application in sheet forming and extrusion, the potential of super-plasticity should best be realized in large tonnage materials, such as steel and aluminum alloys. The degree of superplasticity in low-carbon and manganese-bearing steels has been evaluated. The results of elevated-temperature stress-strain rate and elongation tests on ultrafine grain size material are reported. Avery and Backofen6 and Hart7 have shown that geometrically stable flow leading to extensive uniform elongation in the tension test is associated with high values of the strain rate sensitivity, m, defined: Lozinsky had reported that titanium and zirconium experience permanent deformation if subjected to a constant load and cyclic heating through the temperature range of the phase transformation. Although strain rate sensitivities in excess of about 0.2 had not been reported previously for steel, permanent deformation had been observed11-13 in a wide variety of steels subjected to a constant load and cyclic heating through the temperature range of the a-? phase transformation. Thus by analogy, steel could be expected to exhibit high strain rate sensitivity but only in the a + ? condition. High strain rate sensitivity has been observed at 650°C (a + Fe3C), but not reported as such, by Bailey, Dickenson, and pearson14 in 1931 at a strain rate of about 10-9 per min. It then remained to determine whether high tensile elongations would be observed in a rate-controlled test at constant temperature and at what strain rate strain rate sensitivity values greater than 0.5 would be observed. Since previous experience8 had indicated the importance of fine grain size to realizing high m at reasonable strain rates, it was first necessary to produce an ultrafine grain size and then keep the grains from growing during the test. The results of this investigation show that fine grain size can be readily produced16 and maintained by restricting the temperature of testing to below the ? transus. Further, superplasticity (high m and large uniform elongation) is observed. However, the strain rate range is only marginally useful for commercial forming operations with the finest grain size produced. MATERIAL The material investigated initially was a 1.9 wt pct Mn, 0.42 wt pct C, hot-rolled bar previously used by Low and Turka1015 and available in the laboratory. The 0.500-in. round was cold-rolled to a 0.090-in. flat, annealed for 4 hr at 850°C in argon, air-cooled, and cold-finished to 0.050 in. Subsequently, four additional steels of the compositions given in Table I were investigated to explore the effects of manganese, carbon, and test temperature on the observed stress-strain rate behavior. These steels were melted under argon, cast to 0.75 by 2 by 5 in. slabs, hot-rolled at 850°C, surface-finished to 0.13 in., and cold-finished to 0.050 in. Sheet tensile specimens 0.200 in. x thickness with 1- or 2-in. gage length were cut parallel to the rolling direction. Table I also includes the nominal transformation temperatures for the AISI 1340 and the four experimental steels. EXPERIMENTAL PROCEDURE Production of Fine Grain Size. Ultrafine grain size (1 to 5 p) was considered essential for this studv. Grange16 has described two techniques for producing

Jan 1, 1969

By A. Yoshikawa, T. Sugeno

To detenmine the origin of the sharp fatigue limit in many ferrous metals, S-N curvces were determined in push-pull fatigue at 18.6 kc per sec at room temperature and - 67°C for various kinds of iron. These differed in carbon and nitrogen content and grain size (25 and 2500 grains per sq mm). Sharp knees appeared in the S-N curves of fine-grained specimens with high interstitial content at both temperatures. In coarse-gruined specimens, knees were not sharp .regardless of the interstitial content and the testing temperature. It is concluded from these results that the controlling factov for the appeavance of the sharp fatigue limit is not strain aging but grain size. It has already been mentioned that iron and some iron alloys show fatigue curves characterized by a more or less sharp knee and a fatigue limit.&apos; Explanations of the origin of this characteristic behavior of fatigue in iron appear to fall into two broad classes. One is concerned with interstitial impurities through the aging or locking effect and the other is based on intrinsic plastic properties of iron. Levy and sinclair2 and Lipsit and Horne3 have suggested that the fatigue limit observed generally in iron and steel is due to interstitial solute aging during the course of fatigue. On the other hand, Thompson and wadsworthl have suggested that the fatigue limit may be analogous to the sharp yield point, in the sense that alternating stresses above the fatigue limit are necessary to break down the dislocation locking. However, there are some experimental results which cast doubt on the general validity of these suppositions.4-8 Ferro and Montalenti&apos; have recently suggested that the typical form of the fatigue curve of iron seems to come from an intrinsic plastic characteristic of the iron structure. This suggestion is based on the experimental result that pure iron containing an insufficient amount of interstitial solute to alldw appreciable strain-aging effects still showed a fatigue limit at room temperature. Although systematic investigations on the effect of grain size are scarce, it is thought that this effect is important in relation to the sharp fatigue limit. In fact, sensible differences were observed by Oates and Wilson4 in fatigue behaviors of a low-carbon steel depending on grain size. Ideally, the fatigue limit will be defined as the upper limit of stress amplitudes at which the life is infinite. This ideal fatigue limit can never be determined because of the limited time available for experiments, and moreover scattered data points often leave the construction of S-N curves somewhat arbitrary. And, it is usually stated that a material has a fatigue limit when its statistical S-N curve becomes apparently parallel to the N axis with a more or less sharp knee. The meaning of the fatigue limit and the sharp knee will be discussed in detail in relation to the construction of S-N curves. The origin of this sharp knee was investigated by determining S-N curves of iron for various interstitial contents, testing temperatures, and grain sizes. EXPERTMENTAL PROCEDURE The material as received was a commercial-grade low-carbon steel in the form of 4-mm-diameter rods with the following composition in weight percent: C, 0.09; Si, 0.017; Mn, 0.43; P, 0.006; S, 0.012; Cu, 0.11. Five different groups of specimens were tested. The grain sizes and interstitial contents in each group are given in Table I. The specimens of group C-02 were decarburized by annealing for 100 hr at 700°C, followed by an additional 100 hr at 850°C in wet hydrogen. Specimens of groups N-2 and N-9 nitrided in a mixed atmosphere of ammonia and hydrogen after an initial treatment identical to group C-02. The specimens of group C-9 were prepared in a manner similar to those of group C-02, except heat treatment was carried out in a vacuum. After polishing their surface with emery paper, the specimens of all groups were given a final anneal for 30 min at 930°C and air-cooled in an evacuated quartz tube. For group C*-9 this

Jan 1, 1965

By J. C. Holm

ALTHOUGH the main constituents of Portland cement are the oxides of calcium, silicon, aluminum, and iron, characteristics of the cement are seriously affected by such contaminants in the raw materials as magnesium, phosphorus, sodium, potassium, sulfur, and others of lesser importance. Sources of cement raw materials comprise a long list of minerals occurring in nature in various degrees of purity. The calcareous raw materials are generally limestone of purity varying from calcite to cement rock (a low-grade limestone of natural, almost correct chemical composition), chalk, marl, seashells, coral, and coral sand. The argillaceous raw materials supplying silicon, aluminum, and iron are mainly various forms of clay and shale, to which may be added silicious sand, iron ore, bauxite, or kaolin for minor adjustment of the chemical composition. The quality of Portland cement in this country, as in most parts of the world, is controlled by rigid specifications limiting both its chemical and physical characteristics, and cement manufacturers must comply with these specifications to market their products. Brandon Raw Materials: An unusual deposit of marl, limestone, and clay occurs 12 miles east of Jackson, Miss., near the village of Brandon. The deposit is of sedimentary origin and of relatively young geological age. Layers of marl vary from putty-like consistency to such hardness that it can be cut with a knife. Interspersed between the layers of marl are bands of limestone varying from very soft to hard. the compressive strength of the hardest layers exceeding 15,000 lb per sq in. The layers of marl range in thickness from a few inches to about 25 ft. The limestone bands seldom exceed 2 to 3 ft but often occur in thinner veins in the quarry face. Above the top layer of the deposit, which may be marl or limestone, a layer of clay ranges in thickness from a few inches to more than 20 ft. Part of this clay is harvested with the raw material to supply part of the argillaceous components, but most of it is stripped as overburden and wasted. A highly silicious clay of extreme fineness, harvested from the bottom of the quarry below the marl and limestone bands, is to correct the silica content. Fig. 1 shows typical examples of the interrelation of the various materials, based on drill logs obtained during exploration of the deposit. The marls vary in moisture content in the bank from 15 to 30 pct and contain up to 70 pct -200 mesh particles and up to 40 pct —10 p particles. A large percentage of the fine fraction is within the colloidal range, making the marl extremely sticky. The limestone beds range in hardness from that of the hardest marl to a medium hard limestone and in moisture content from 2 pct to approximately 14 pct. The line of demarcation is often difficult to draw and the moisture content is possibly the best means of classification. The ratio of soft to hard material is not constant throughout the deposit, but the average is approximately 70 pct soft to 30 pct hard material. Through the years this deposit had been repeatedly explored by cement companies and rejected as unsuitable for cement manufacture, mainly because of physical characteristics. In 1950, after careful exploration of the deposit and comprehensive laboratory and pilot plant tests of the raw materials, officials of Marquette Cement Mfg. Co. of Chicago were convinced that a practical and economical method of processing the raw materials had been devised and authorized construction of a new plant that began production in December 1951. Marl and limestone, common raw materials for Portland cement, usually occur in such a manner that they can be worked separately. Their harvesting and processing normally have presented no difficult problems, as standard equipment and methods are available for handling either sticky or hard materials. No other cement plant utilizes a deposit of the nature of that at Brandon, however, and for this reason no prior art was available for design. When properly blended, the raw materials produced an excellent cement without additives. Basic problems to be solved in designing the cement plant were:

Jan 1, 1957

By J. S. Marsh

OPPORTUNITY to pay tribute to the memory of Professor Henry Marion Howe is a strenuous assignment as well as an honor. Upon recalling Howe lecturers and lectures of the past 25 years, glancing over the list of those earlier, and rereading Howe&apos;s books, I arrive at several conclusions: 1—Many lecturers either worked under or knew Professor Howe. 2—It is virtually impossible to pick a subject on which Professor Howe did not touch. 3—There is precedent for a technical paper based upon pursuit of a single subject. 4—There have been listening lectures and reading lectures. There is solid comfort only in 2: the subject field is wide open. I did not know, nor even ever saw, Professor Howe, so can supply no fitting reminiscence. As a college student I was dimly aware that he counted among the giants. Fuller appreciation of his stature came with reading his books and papers, growing acquaintance with some of his associates, and the intrinsic dignity of the climax of the Annual Meeting, beginning at four o&apos;clock of a Thursday afternoon in the auditorium of the Engineering Societies Building in New York. As for producing the technical paper sort of thing, it is my lot to have reached an age and assignment such that to do so would be to filch information from those who did the work and whose story is theirs to tell; for this I have no enthusiasm. As for the final conclusion, Professor Howe was one of the chosen few so highly expert at expository writing that he could produce a lecture or paper that reads as though it would also have listened well. One of his tricks was the free use of words not ordinarily part of the technical vocabulary, provided that such words were likely to communicate most precisely what he had in mind. How wonderful it would be for all who must read reports by the ton if ability at exposition could be taught with the effectiveness open, say to, differential calculus! Perhaps Professor Howe should be required college reading even if for no other reason than to prove that technical writing need be neither dull nor diffuse. My assignment is clearly still strenuous. Another point to consider is the fact that metallurgy is now so tremendously diversified that hope of finding a topic of universal appeal is negligible, even if one were competent enough to be permitted free choice. That which follows is, therefore, a compromise composed of necessity and of the obligation to attempt to avoid boring to slumber those of you who are not especially interested in the general subject chosen. The Iron and Steel Div. is now essentially a process metallurgy division, heavily concerned with the smelting of iron and the making of steel. The American Iron and Steel Inst. figure for present steel capacity of this country is 125,828,310 net tons; how this is divided among processes is indicated by the production totals for 1953, shown in Table I. The glamor girls and boys make the front page and so it is with steelmaking processes. If there is an Antarctic Daily Bugle, it undoubtedly has carried stories of revolutionary development, such as oxygen processes and vacuum melting, and stories of the incomparably rosy destiny of electric arc melting. All such certainly have their place and their future; meanwhile, it is the sturdy and old reliable open hearth that accounts for the bulk of production reported back on the financial page, and it is the old reliable that is most likely to continue to account for the bulk for some perfectly sound raw material, technologic, and economic reasons. This, plus the fact that next year marks a centennial (for it was in 1856 that Frederick and William Siemens conceived the regenerative open hearth), is reason enough to talk about open hearth furnaces, but is not the real one. The real reason is that in some years of association with open hearths, I have accumulated—in addition to a genuine liking and respect for them—certain odds and ends of fact and fancy that this lecture provides a unique chance

Jan 1, 1956

By Michael P. Robinson

It has been suggested that streaming potentials are not nomlally logged because the streaming potentials known to be generated across mud filter cakes are substantially cancelled by streaming potentials generated in contiguous shale beds. Laboratory measuments of streaming poterztials acrons hand specirnens of shale have been adduced as evidence to support the suggestion. The experiments show that streanzing potential depends on the resistivity of the equilibrating solution and on pressure drop. Meizsurenlents were made perpendicular to the bedding planes of the shales. The mechanism of streaming potential generation in shale which the suggested cancellation theory iniplies has been critically examined. Conclusions reached are tested by comparing self potentials logged before and immediately after changing the resistil~ity (but not the weight) of mud in a borehole. The resultant SP change is found to equal the theoretical electrochetnical potential change, i.e., cancellation of .strearning potential is independent of mud resistivity. Since streaming po/entials generateal across mud filter cakes depend critically upon mud reistivity, shale .strearlling potential in situ must he equally sensitive. Using plausible values for the pemleahility, porosiy arzd compressibility of shale, the van Ererdingerl-Hurst approach shows that the pressure drop between horehole pressure and formation pressure in a radially honzogeneous shale is unlikely to coincide with the zone of filtrate invasion. If, perchance. this coincidence occurs with one mud a chatzge 10 a second must result in non-coincidence, i.e., a .YP logged in the second mud should show a streaming potenlial. The dilernrna may he overcome by postrrlating: (I) perrneabilities of shale7 parallel to their beddine planes greatly exceed their cross-bedding permeabilities; (2) a resistivity-sensitive mud cake of low permeability forms either on the face of, or probnhly in the lanlinations of, many shales. These postulates are examined with reference to the pres.sure and SP histories of the McClosky and Aux Vases zones in the Illinois Basin and some srcpport for them found. It is concluded that a definitive solultion to the streaming potential problem does not exist. INTRODUCTION Recently Gondouin and Scala&apos; published a contribution to the streaming potential problem which is notable particularly for the elegance of its experimental techniques. The conclusions drawn by Gondouin and Scala from their studies amplified those previously suggested by Schehck&apos;. In essence they suggested that the streaming potentials known to develop across mud filter cakes" are not normally observed on SP logs because they are largely cancelled by streaming potentials generated in adjacent shales. This suggestion appears so reasonable that many workers in the logging field will be prone to accept it. We incline strongly to the view that the suggestion is basically correct. Nevertheless, it is important to realize that the cancellation hypothesis in the form put forward by Gondouin and Scala does not appear to meet all the known experimental facts. It is the principal intention of this note to call attention to what appears to be a flaw in the relevancy of the experimental evidence adduced by Gondouin and Scala and to suggest an alternative hypothesis to remove it. The consequences of the new hypothesis are compared with field data which, we believe, are unique. A second but not less important purpose of this note is to emphasize that even the new hypothesis does not fully explain all field observations. Hence we conclude that further study of the streaming potential problem is required before it can be said that a definitive solution to it has been attained. The bare experimental bones of laboratory data on streaming potentials appear to be as follows. 1. A streaming potential is developed across a mud filter cake. This streaming potential is virtually independent of cake thickness but depends on the mud resistivity. The relationship is of the form, 2. A streaming potential is developed across a shale. This potential is independent of shale thickness but depends on the resistivity of the permeating solution if the shale has been first equilibrated in this solution. The relationship is of the form, The relationship in (1) was determined first by Wyllie3, confirmed by Gondouin and Scala and qualita-

By J. A. Coll, R. W. Cahn, A. Lawley

WHILE the creep properties of pure face-centered-cubic and close-packed-hexagonal metals have been thoroughly investigated and are well established, body-centered-cubic metals have been studied less extensively. Moreover, very few fundamental studies on the creep of solid solutions, irrespective of crystal structure, have been reported. The present study is concerned with the creep of a series of body-centered-cubic solid solutions. The present position concerning creep of pure metals is, briefly, as follows.1"3 Creep at first takes place at a steadily decreasing rate; this is the stage termed primary or transient creep. Except at the lowest temperatures this is succeeded by a stage of secondary or steady-state creep. At high temperatures and stresses, this may be succeeded by an accelerating stage, termed tertiary creep, with which we shall not here be concerned. There is no well-defined physical model at present for the transient stage; in general terms, transient creep is best regarded simply as a manifestation of work-harden ing. Steady-stage creep can certainly take place by several different mechanisms: the choice of dominant mechanism depends primarily on temperature. We shall here be concerned only with high-temperature steady-state creep, a term usually reserved for creep at absolute temperatures higher than 0.5 Tm, where T, is the melting point. In this range, the activation energy for creep is, for many metals, equal to the activation energy for self-diffusion, and this is generally interpreted in terms of a "climb mechanism.1-4 The creep rate is determined by the speed at which dislocations, impeded by obstacles the nature of which is disputed but which are probably established during transient creep, can climb by means of a diffusion process, until they are able to by-pass the obstacle. In solid solutions, the intrinsic resistance to the slip motion of dislocations may be much larger than in the solvent, to the extent that the motion of dislocations in the glide plane, rather than their escape by climb out of this plane, may become the rate-controlling factor. weertman5 has considered this possibility from a theoretical point of view, and concluded that some form of "viscous slip" is likely to be rate-controlling at comparatively low stresses. The resistance to slip may arise from "atmospheres" of impurities forming around dislocations; a high Peierls force in materials of high cohesion; or some structural peculiarity such as clustering or ordering of solute atoms.= We shall be concerned here with the case of ordering. The only published investigations concerned explicitly with the effect of order on creep refer to creep in ß-brass by Herman and Brown,7 and in Ni-Fe alloys, by Kornilov and panasyuk8 and by Suzuki and Yamamoto.9 Recently, Herman and Brown&apos;s paper has been supplemented by a determination of the tensile yield point of ß-brass as a function of temperature.10 Both studies showed a sharp drop in resistance to deformation of ß-brass over a range of a few degrees just above the critical temperature Tc at which order finally disappears. These observations are especially noteworthy, because in ß brass the degree of order diminishes steadzly to zero as the temperature approaches Tc. It is, therefore, the disappearance of the last traces of long-range order which has the largest effect on the resistance of the alloy to plastic deformation. In the Ni/Fe alloys of various compositions, resistance to creep at a given temperature and stress is maximum at the stoichiometric composition, both below Tc, (long-range order), and above T,. (short-range order).&apos; Near Tc, the creep resistance of an ordered alloy is much higher than that of the same alloy in the disordered condition.9 The aim of the present investigation was to study the creep behavior in the neighborhood of Tc, of another system of ordering alloys. The iron-aluminum alloys were considered the most suitable. because: i) The order again diminishes steadily to zero as the temperature approaches Tc; there is no sudden drop in order at Tc, and it therefore is

Jan 1, 1961

By R. W. Cahn, C. D. Graham

The rate of growth of a single grain growing into a strained aluminum single crystal, measured by the conventional heat-cool-etch technique, is shown to decrease with time at temperature. The growth rate measured by means of X-rays, with the sample continuously at temperature, is found to be linear. Evidence is presented to show that the decreasing growth rate obtained by the conventional technique is due to abnormal recovery in the strained grain, and that the recovery in turn results from the heating and cooling cycles, rather than from the effects of etching. The experimental apparatus is described in an appendix. FREQUENTLY, the rate of grain boundary motion during recrystallization is determined by heating a sample to a known temperature for a given time, cooling to room temperature, and etching to reveal the boundary position. The cycle of operations is repeated as many times as necessary to establish the rate of boundary motion. Although this heat-cool-etch technique has been used by a number of workers over a period of many years,&apos;-!&apos; other investigators have encountered difficulty with the method."&apos;. " They have attributed the erratic results to the effects of repeated heating and cooling, or of etching, or both, and have adopted an alternative experimental procedure in which a number of identical samples are employed, each sample being cooled and etched only once. This alternative method ove1.comes some difficulties, but introduces others. In particular, the incubation periods of the observed grains are unknown: any effect of crystal orientation on growth rate cannot be determined easily. A preferable method would be to measure the motion of a recrystallizing grain boundary with the sample at temperature without etching," but such measurements have in the past been restricted to nonmetals. This paper describes the construction and operation of a device, the goniometer furnace, with which the position of a moving grain boundary between a recrystallizing grain and the strained single crystal into which it grows can be measured by means of X-rays, with the sample maintained continuously at temperature. Goniometer Furnace The operating principle of the goniometer furnace is shown in Fig. 1. The sample, in the form of a bicrystal strip, is surrounded by a furnace, not shown in the sketch, and can be rotated about the two axes A and B which intersect at the point where the X-ray beam strikes the strip. The strip is oriented so that one of the two grains gives a strong Bragg reflection, which is detected by a suitably placed Geiger-Miiller counter coupled to a counting-rate meter When the strip is moved parallel to its own length in the furnace, arrow C, so that the X-ray beam strikes the second grain, there is in general no strong reflection. By noting the position of the strip at which the drop in Geiger counter reading occurs, it is possible to determine the position of the boundary. Measuring the change in boundary position with time at temperature gives the rate of growth of the recrystallizing grain. Details of the construction and operation of the goniometer furnace are given in the Appendix. Measurements showed that the temperature in the furnace was uniform within ±10°C over its working length of about 28 cm. The temperature at the measuring position, i.e., at the point where the X-ray beam struck the sample, was estimated to be constant within ±2oC. Using the goniometer furnace, the position of a stationary boundary could be measured with a reproducibility of ±0.3 mm. At elevated temperatures, 500" to 625"C, with the boundary in motion and the X-ray reflection less sharp, the estimated accuracy of each measured boundary position dropped to about ±1 mm. Experimental Results The test pieces were single crystals of 99.6 pet A1 —principal impurities 0.19 pet Fe and 0.12 pet Si— 1 mm by 1 cm in cross section and 6 to 10 cm in length, grown by the strain-anneal method. This relatively low purity material was used because of the difficulty encountered in producing strain-anneal single crystals of very high purity—99.996 pet—

Jan 1, 1957

By R. E. Reed-Hill, W. H. Hartt

High-purity magnesium single crystals, oriented with basal plane parallel to stress axis, were deformed in tension at room temperature so as to form second-order (1011)- (1012) twins. Investigation by optical and replica electron microscopy revealed that these twins can support very large internal strains approaching 1000 pct and that fracture follows as a direct consequence of these strains. At low strains the basal plane within (10i1)- (10i2) twins rotates with increasing deformation until it becomes approximately parallel to the twin boundaries. This rotation is not consistent with deformation by basal slip in the double twin, but may be rationalized in terms of nonbasal slip. Observations also indicate that basal slip in the primary (1011) twin, prior to second-order twinning, may contribute to this rotation. Deformation markings that are difficult to interpret in terms of slip on previously observed systems were noted in the twin bands. A possible means of rationalizing these markings is to relate them to grain boundary shear. The fracture associated with these twins is thought to initiate by formation of voids at the twin boundaries. These grow into microcracks, with ultimate fracture occurring by tearing of the interconnecting regions. THE significance of deformation and fracture along second-order (10i1)-(10i2) twins in polycrystalline magnesium1-&apos; and many magnesium alloys4 was discussed in a previous paper.5 It was noted that this double twinning mode effectively controls the room-temperature deformation and fracture of magnesium single crystals, oriented with the basal plane parallel to the tensile axis. Reed-Hill and Robertson6 observed that, although these crystals may fracture at a macroscopic strain of less than 1 pct, shear strains up to 1000 pct could occur within (1011)- (10i2) twin bands. They concluded that the fracture was "ductile" and resulted from concentrating the deformation into a very small volume. The present research was undertaken to obtain a better understanding of the deformation and fracture associated with these twins. EXPERIMENTAL TECHNIQUES The experimental procedure involved straining high-purity magnesium single crystals in tension at room temperature. Specimens were oriented so that the applied stress direction was within 2 deg of the [1010] crystal axis. The specimen cross section was rectangular with faces closely parallel to (1210) and (0002). The specimen preparation and testing procedures have been described in detail elsewhere.5 Second-order (1011)- (1072) twins nucleated during straining were studied using optical and replica electron microscopy techniques. For the latter, cellulose acetate-carbon double replicas were employed. Observations were made on the (1210) crystal surface, which is the plane of shear for twins of this type. In addition to the single crystals, some investigations were carried out on longitudinal polycrystalline specimens. These were obtained from high-purity magnesium plate with a texture in which the basal planes of the grains tended to be nearly parallel to the specimen axis. All. polycrystalline specimens were annealed prior to testing in order to produce a coarse grain structure, permitting Laue back-reflection X-ray photographs to be obtained from grains of interest. EXPERIMENTAL RESULTS a) Deformation Within ( 101 l )-( 1072) Twins. Fig. 1 is an optical micrograph demonstrating the extent of the plastic deformation that can occur in (1011)-(10i2) twin bands. Notice at the lower left corner of the photograph the large displacement of the dark band (a polishing step) where it crosses the twins. The shear strain in the twin band at this position was computed to be 700 pct, using the ratio of step width to twin thickness. It was previously shown5 that (1011)- (1012) twin bands are often composed of small, separate twins aligned close to the macroscopic habit plane. Fig. 2 is an electron micrograph from near the upper end of the twin band in Fig. 1. This illustrates that the twin habit often does not coincide exactly with the macroscopic band habit, but may be inclined at a slightly smaller angle to the matrix basal plane. Figs. 3 through 6 are electron micrographs of the twin band in Fig. 2 illustrating successive steps in the development of deformation inside the band. A twin band such

Jan 1, 1969

By R. E. Delavault, H. V. Warren

In normal soils there are usually 10 to 50 parts of copper in every million parts of .soil. Only 0.2 to .5 pct of this copper can be found by any simple cold chemical attack. Now, with rubeanic mid reagent paper, a prospector or field geologist can detect as little us 4 ppm of readily available copper ill soil. This degree, of sensiticity is enough to determine the presence. of copper anamalous an as and, ecentually, to discouer copper mineralization. Circumstances determine whether it is better to make analyses in the field or in a permanent laboratory. The rubeanic acid test described in this article has been designed primarily for field use: it is simple and virtually foolproof, and it requires a minimum of field kit." It is sensitive, easily de- • Ed. Note: Persons Interested in purchasing kits suitable for rubeanic acid prospecting can obtain information by writing Eldrico Geophysical Sales Ltd., 633 Hornby Street. Vancouver 1, B.C. The University of British Columbia does not produce these kits for sale and has no financial interest in their production tecting 4 ppm of readily extractable copper in a soil. This is by no means a quantitative test, but it is accurate enough to provide a valuable indicator of copper anomalous areas for both prospectors and field geologists. The easiest method for detecting metal deposits that do not produce visible float or stains is to make a simple chemical test for the metal in overlying soil, or in the silt of a stream that may have picked up metal farther upstream. In Brief: Testing for copper may be done easily by shaking a soil sample with strong acetic solution in a small test tube and pouring the mud into a small filter, the tip of which rests upon a strip of reagent paper impregnated with rubeanic acid (di-thio-oxamide). When copper is present—and only when it is—a blue spot develops. The more copper, the darker the spot. If the copper content is merely the small amount present everywhere, there is a pale blue or hardly visible spot; if it is abnormally high, the spot will be dark. There are, of course, intermediate cases where the experienced geochemist cannot tell offhand whether a medium-strength spot represents rich agricultural soil, weak copper mineralization, or distant rich copper mineralization. Reagents and material are inexpensive; the test may be readily done on the spot with a simple kit easy to pack and handle. Anyone interested in general problems of soil sampling as applied to prospecting may refer to an article recently presented to the AIME. In exploration work it is the contrast between the metal content of anomalous and background areas that is important; absolute values become of greater interest when an anomalous area is being investigated in detail. With specific reference to copper, it has been the authors&apos; experience that the amounts of metal extracted from anomalous and normal soils with buffer solutions of decreasing pH show better contrast if an acid reagent is used. This contrast tends to increase with increasing acidity until 3 to 4 pH is reached. Using a short cold attack on unheated soil, it has been found that further increases in acidity do not produce better results, and only increase the hazards involved in carrying strong acids. An acidity of about pH 4 is satisfactory for direct determination of copper by dithizone. But dithizone itself introduces some problems: it must be made up fresh at frequent intervals, and with some soils, notably those with much ferric iron, oxidation mag take place before all the copper has reacted with the dithizone. Rubeanic acid keeps its strength unimpaired for long periods, is unaffected by oxidation, and is practically specific for copper at pH 4. Consequently it seems an ideal reagent to use in prospecting for copper. History and Background: Rubeanic acid (systematic name: dithio-oxamide (SC-NH2) has long been known as a spot test reagent for some heavy metals with which it gives a number of compounds. Only copper and some metals of the platinum family are believed capable of providing any ru-beanate compounds under conditions of moderate

Jan 1, 1959