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By M. H. Sommer

MANY attempts have been made to develop a relation between the tensile properties and the deep-stamping qualities of metals com-monly used in deep drawing. These operations are generally performed cold and the metal is always stressed beyond the elastic limit. However, the problem cannot be readily solved without a proper investigation of (1) the relation between actual stress and actual strain in the plastic range and (2) the stresses that are set up in the metal during the process of deep stamping. Much work has been done in recent years to add to our knowledge on plastic deformation of metals and the shortcomings of the ordinary tensile test, particularly in the plastic range, have been sufficiently recognized. It has been widely acknowledged that the local contraction, which appears in a tensile test after the maximum load is reached, is not a general characteristic of the material but is peculiar to this form of testing. The plastic deformation of materials is explained by the slip of their crystals along certain planes and this rearrangement should be similar whether observed in a tensile, compression or torsion test, and if the results of any of these forms of testing show deviations, it must be due to other influences, as for example the local contraction in a tensile test. For this reason the tensile-test curve as obtained from the measurements taken on a tensile-test machine or registered by an autographic device has been supplemented by the so-called "actual stress-strain curve," which is constructed from the observed tensile-test data by eliminating the effect of local contraction and is in complete alignment with the stress-strain values obtained in a compression or torsion test. The actual stress-strain curve shows the increase of actual unit stress in relation to unit elongation beyond the yield point and

Jan 1, 1934

By Paul M. Tyler, Herbert R. Mosley

Strategically situated in almost the heart of the leading fertilizer-consuming area of the United States, Tennessee long has ranked second only to Florida as a phosphate-producing state. Since 1932 its share of the national output of phosphate rock has increased steadily, and in 1937 its production mounted to an all-time record. More significant even than the increase in tonnage are the forward strides in technology. The Tennessee Valley Authority's research program has led to quasicommer-cia1 operations using hydroelectric power to manufacture concentrated phosphatic fertilizer that is used to further the farmer education program designed to streamline the fertilizer business and halt the appalling waste of farm land by soil erosion. Even more stimulating to chemically minded imaginations is the production of elemental phosphorus by a private company that not only has succeeded in extracting it from the phosphate rock in electric furnaces but actually has contrived to capture it and to transport it safely in tank cars. New values have been created for low-grade phosphate deposits, and the economic life of reserves has been lengthened while the waste of former years goes back into the mills for recovery of its values by modernized methods. Tennessee's phosphate-mining industry dates from the discovery of blue rock in Lewis County in December 1893. Its known reserves are of the order of 101,500,000 tons, which compares with the production of 825,099 tons in 1937; that is, 21 per cent of the phosphate-rock output of the whole nation. The total output reported from 1894 until July 1. 1938, was approximately 19,000,000 tons. Offcial estimates of reserves are overly conservative and evidence submitted before a joint Congressional committee in November 1938 places "probable" reserves at more than 6,000,000,000 tons.

Jan 1, 1942

By Herbert R. Mosley, Paul M. Tyler

Strategically situated in almost the heart of the leading fertilizer-consuming area of the United States, Tennessee long has ranked second only to Florida as a phosphate-producing state. Since 1932 its share of the national output of phosphate rock has increased steadily, and in 1937 its production mounted to an all-time record. More significant even than the increase in tonnage are the forward strides in technology. The Tennessee Valley Authority's research program has led to quasicommer-cia1 operations using hydroelectric power to manufacture concentrated phosphatic fertilizer that is used to further the farmer education program designed to streamline the fertilizer business and halt the appalling waste of farm land by soil erosion. Even more stimulating to chemically minded imaginations is the production of elemental phosphorus by a private company that not only has succeeded in extracting it from the phosphate rock in electric furnaces but actually has contrived to capture it and to transport it safely in tank cars. New values have been created for low-grade phosphate deposits, and the economic life of reserves has been lengthened while the waste of former years goes back into the mills for recovery of its values by modernized methods. Tennessee's phosphate-mining industry dates from the discovery of blue rock in Lewis County in December 1893. Its known reserves are of the order of 101,500,000 tons, which compares with the production of 825,099 tons in 1937; that is, 21 per cent of the phosphate-rock output of the whole nation. The total output reported from 1894 until July 1. 1938, was approximately 19,000,000 tons. Offcial estimates of reserves are overly conservative and evidence submitted before a joint Congressional committee in November 1938 places "probable" reserves at more than 6,000,000,000 tons.

Jan 1, 1942

By William L. Fink, L. A. Willey

Since so many different curves have been published for the solid solubility of zinc in aluminum, it seems desirable to definitely establish the correct curve by two or more independent methods. The curve published in part I1t was based entirely upon X-ray measurements because the other methods employed at that time were not satisfactory. The present paper (the seventeenth of this series on high-purity aluminum alloys) describes the determination of the solid solubility of zinc in aluminum by the measurement of electrical resistivity at temperature and by microscopic examination. Since the publication of our part I in 1932, an investigation of the solubility relations in the aluminum-zinc system has been reported by Schmid and Wassermann2, who obtained their solubility results from lattice-parameter measurements on heat-treated and quenched specimens. The diagram that they published is shown in Fig. 1. In this investigation they also found by X-ray measurements that the parameter of the gamma phase changed continuously with zinc content and at such a rate that it would be identical with that of the beta phase at 60 atomic per cent zinc. It was concluded therefore that the beta and gamma phases, from the point of view of structural relationship, are one single phase. They also suggested a gap of immiscibility between 270" and 350" C. The complete boundary in this region could not be determined satisfactorily by the method employed and therefore was not shown in their diagram. Aluminum-zinc Alloys Materials Used.—Electrolytically refined aluminum3 was used in preparing the alloys for the work reported in this paper. Chemical analysis showed the following impurities: 0.004 to 0.005 per cent silicon, 0.006 to 0.008 per cent iron and 0.005 to 0.006 per cent copper. Also,

Jan 1, 1936

By C. M. Wayman, J. F. Breedis

The crystallography of the martensitic transformation in the Fe-30 Ni alloy was reinvestigated. The scatter in the habit Plane as determined from measurements on the mid-rib plane was smaller than reported previously, and the orientation relationship was determined from a martensite plate having known direction cosines. From agreement with crystallographic theory and from observations of the morphnlogy of the martensite plates, it is suggested that the mid-rib plane represents the starting region of the transformation. THE crystallography of the martensitic transformation in the iron-nickel system has been the subject of many investigations.&apos;-7 However, for iron alloys containing approximately 30 wt pct Ni, a wide scatter in the reported habit planes exists. In only one instance has a Laue determination of the orientation relationship been made, but the habit plane of the martensite plate studied was not determined experimentally. Because the most successful thermodynamic and kinetic analyses8 of the martensite transformation have been based on Fe-30 Ni alloys, it was considered desirable to reinvestigate the crystallographic features of the transformation in this alloy. Lieberman9 suggested that the most significant information for use in a theoretical treatment involves the determination of all the crystallographic observables from a single plate of the product phase. This was first done in essence by Greninger and Troiano10 for Fe-22 wt pct Ni-0.8 wt pct C, and is the method followed in this investigation. Some theoretical approaches11-13 in describing the martensitic transformation consider the overall transformation distortion to be comprised of a Bain distortion, or lattice deformation (PI, which produces the structure change, and a lattice invariant deformation (G), such as twinning, which together leave the interface or habit plane un-distorted. The incorporation of a rigid body rotation (R) results in a transformation distortion (E) such that the interface plane is left both undistorted and unrotated. In matrix notation, E = RPG where the lattice invariant deformation has "taken place" in the austenite. Bowles and Mackenzie14-16 in formulating a theoretical approach proposed an adjustable scaler quantity, denoted as 6, which represents a uniform dilation in the interface plane. This dilation acts to adjust the lattice spacings of the parent and product structures at the plane of contact. Using the dilation parameter as a variable, these authors were able to account for a continuous variation of habit planes in steels along a curve in the stereogram between {225}A and {259}A. she invariant line strain14 of the transformation is 6 RP, and the corresponding transformation distortion is E/6.) With the dilation parameter known, the invariant line is computed as the triple coincidence of the habit plane, the shear plane of the lattice invariant deformation, and the initial Bain cone.14 The contraction axis for the Bain distortion can be taken9&apos;17 as [010]A, and the correct permutation of the habit plane indices used. Kelly and Nutting 18 have established the shear plane (of twinning) in the tetragonal martensite of Fe-22 Ni-0.8C to be {112)M by means of transmission electron microscopy. The reasonable shear system is then {112}M which is equivalent to {011}A <01l>A. The as-

Jan 1, 1962

By M. E. Learmont, R. J. Lipp, I. Iwasaki

In the selective flocculation of iron ores, the concentration of alkaline earth ions in pulp solutions plays a critical role. Sodium silicate, alone or with sodium tripolyphosphate, has been used as a dispersant. When Ca+ + concentration exceeds 15 to 20 ppm, however, only a strong complexing agent, such as ethylenediaminetetraacetate (EDTA) was found to be effective (Heerema, Lipp, and Iwasaki, 1979). Some iron ores release Ca+ + in excess of 20 ppm. With ores that contain gypsum, the Ca+ + concentration may reach several hundred ppm. The purpose of this investigation was to compare the effectiveness of EDTA with nitrilotriacetate (NTA) in countering the adverse effects of Ca+ +, particularly at high Ca+ + concentrations. Emphasis was placed on the use of NTA since it is more cost-effective than EDTA. It is also used in detergents in some countries (Malaiyandi, Williams, and O&apos;Grady, 1979). NTA, like EDTA, forms a soluble complex with Ca+ + with a 1:1 molar ratio. Its structure and the value of log Kca are given below together with EDTA (Shibata, 1963). [ ] For experimental materials, an equal weight mixture of Lac Jeannine hematite and a high-purity quartzite from Thompson, MN, both ground to - 30 µm (- 560 mesh) was used. Selective flocculation test conditions and procedures were identical to those used in previous investigations (Heerema, Lipp, and Iwasaki, 1979). The optimum level of starch addition for the above mixture was determined to be at 300 g/t (0.6 lb per st). Initially, a series of selective flocculation tests were performed on the mixture pulped with 10-3M CaC12 (40 ppm Ca + +) at pH 11. With no NTA present, flocculation of the entire suspension resulted. The selectivities achieved in tests with 90, 100, and 150% of the stoichiometric amount of NTA were virtually identical to each other and also to the selectivity of separation obtained in the absence of Ca+ + Such an observation could have been expected since Ca+ + concentrations up to a few ppm may be tolerated in selective flocculation (Krishnan and Iwasaki, 1982). A similar series of tests were performed at 10-2M CaC12 (400 ppm Ca+ +). The results are shown in Fig. 1 as grade¬recovery curves. For comparison, the results obtained in the absence of Ca++ are included. At 90% of the stoichiometric amount of NTA, a large enough concentration of uncomplexed Ca+ + was left in solution to cause indiscriminate flocculation. Note in this figure that NTA is capable of countering the adverse effect of Ca+ + even at this high concentration when it is used in excess of stoichiometric amounts. The free Ca+ + concentrations at 100 and 150% are calculated to be 2.5 and 0 ppm, respectively. [ ] The relative effectiveness of NTA and EDTA was then compared at 100% of the stoichiometric amount using 10-2M and 10-3M CaCI2 (Fig. 2). EDTA appears to be slightly more effective than NTA. The free Ca++ of 0.02 ppm in 10-2M CaC12 with EDTA compared to 2.5 ppm free Ca+ + with NTA might account for the difference. As evident, prohibitively high additions of EDTA and NTA were required to complex high concentrations of calcium ion. The use of both of these agents would result in the accumulation of complexed Ca+ + in recycle water.

Jan 1, 1985

It has been established that molybdenum sesquisulphide, not molybdenite, is in equilibrium with molybdenum metal and sulphur vapor in the vicinity of 1100°C. The S2 pressure for this system has been obtained using the Knudsen orifice method and the standard free energy for the dissociation of S2. THIS work was undertaken to help in determining the thermodynamic properties of the molybdenum sulphide which is in equilibrium with metallic molybdenum and sulphur vapor in the temperature range 1025" to 1150°C. From the results of MontoroL and of Parravano and Malquori&apos; molybdenite would be expected to be in equilibrium with molybdenum metal, while the results of Guichard indicate that a lower sulphide must be in equilibrium with the metal. Thus it was concluded that the problem warranted reconsideration, especially in view of the suspiciously low temperature independent term for the standard free-energy function for the reaction MoS² Mo + S,. The reaction was calculated and duly noted as being low by Richardson and Jeffes,&apos; using the data of Parravano and Malquori.&apos; Experimental Method The general method used in this investigation is that of the Knudsen orifice method for the determination of equilibrium pressure. The apparatus and technique are similar to those described for the determination of the vapor pressure of silver.% owever, a closed-end McDanel tube instead of fused silica was used to maintain the vacuum, a molybdenum effusion cell with a replaceable lid was employed instead of a silica cell, and a titanium getter maintained at run temperature was used to assure that no oxidation of the molybdenum or molybdenum sulphide was taking place. All runs were made at a residual pressure less than 10-5 mm Hg. The data are given in Table I. Runs 1 through 13 were obtained using molybdenite, analyzed 98.5 pct, from the Molybdenum Corp. of America. The remaining runs were done with a sample from the Climax Molybdenum Corp. which was their grade No. 3 and analyzed 59.87 pct Mo. The weight loss of the cell during heating up and cooling down was subtracted from the total weight loss of the cell during the run. Also, when the tem- perature was changed, the Knudsen cell was placed in the vacuum chamber and heated at temperature for several hours in order to allow the sulphide and the metal to adjust their compositions to the equilibrium values, to desorb or adsorb gases into or from the molybdenum cell itself, and to desorb any water from the molybdenum sulphide or molybdenum powder inside the cell. Water may have been adsorbed inside the cell because, after each run, the top of the cell was removed and the material in the cell was stirred to insure that a layer of molybdenum metal would not build up and obstruct the passage of sulphur vapor into the gas phase. It was established that the molybdenum cell alone decreased in weight an inappreciable amount when heated at the highest run temperature for long periods of time. There are two questions to be answered before the data in Table I can be used to calculate thermodynamic functions: 1—Which molybdenum sulphide is in equilibrium with molybdenum metal and sulphur vapor? 2—What sulphur species are present in the vapor phase? It can be assumed safely that no molybdenum is vaporized, since its vapor pressure is almost negligible at these temperatures. It will be shown subsequently that no sulphide of molybdenum is volatile. Question 1 was answered in the following way: The especially purified molybdenite, obtained from the suppliers mentioned previously, was charged

Jan 1, 1956

By D. C. Hilty

It has long been known that in melting high-chromium steels, some of the carbon might be oxidized out of the melt without excessive simultaneous oxidation of chromium, and that higher temperatures favor retention of chromium. The advent of oxygen injection as a tool for rapid decarburization of a steel bath permits significantly higher bath temperatures, and it was quickly recognized that the use of oxygen injection facilitated the oxidation of carbon to low levels in the presence of relatively high residual chromium contents. Up to the present time, however, specific data pertaining to the chro-mium-carbon-temperature relations in chromium steel refining have not been available. Individual steelmakers have evolved practices more or less empirically, but there has been very little real basis for predicting how effective any given practice can be in permitting maximum oxidation of carbon with minimum loss of chromium. The current investigation, therefore, was undertaken in an effort to establish the fundamental carbon-chromium relationship in molten iron under oxidizing conditions. As reported below, the equilibrium constant and the influence of temperature on that constant have been derived for the iron-chromium-carbon-oxygen reaction in the range of chromium steel compositions with what appears to be a fair degree of precision. The practical application of the result will be obvious. Experimental Procedure The laboratory investigation was carried out on chromium steel heats melted in a magnesia crucible in a 100-lb capacity induction furnace at the Union Carbide and Carbon Re- search Laboratories. The charges for the heats consisted of Armco iron, low-carbon chromium metal, and high-carbon chromium metal, the relative proportions of which were calculated so that the various heats would contain from approximately 0.06 pct carbon and 8 pct chromium to 0.40 pct carbon and 30 pct chromium at melt-down. When the charges were melted, the bath temperatures were raised to the desired level, and the heats were then decarburized by successive injections of oxygen at the slag-metal interface through a ½-in. diam silica tube at a pressure of 30 psi. The duration of the oxygen injections was from 30 sec to 2 min. at intervals of approximately 5 to 30 min. It did not appear that length or frequency of the injection periods had any significant effect on the results; cansequently, no effort was made to hold them constant and they were controlled only as was expedient to the general working of the heats. Between successive injections, the heats were sampled by means of a copper suction-tube sampler that yields a sound, rapidly-solidified sample representative of the composition of the molten metal at the temperature of sampling. This sampling device is a modification of the one described by Taylor and Chipman.1 An attempt was made to vary bath temperatures between samples, but it quickly became evident that, unless the variations were small or unless the new temperature was maintained for a minimum of 15 min. during which an injection of oxygen was made in order to accelerate the reactions, a very wide departure from equilibrium resulted. For most of the runs, therefore, temperature was maintained relatively constant at approximately 1750 or 1820°C. A few reliable observations at other temperatures, however, were obtained. Temperature Measurement The high temperatures involved in this investigation were measured by the radiation method, utilizing a Ray-O-Tube focused on the closed end of a refractory tube immersed in the metal bath. The immersion tubes employed were high-purity alumina tubes specially prepared by the Tona-wanda Laboratory of The Linde Air Products Co. These tubes were quite sturdy under reasonable mechanical stress at high temperature. They were unusually resistant to thermal shock, and chemical attack on them by the melts was slow. With care, it was found possible to keep these tubes continuously immersed in a heat for as long as 5 hr at temperatures up to 1850°C, before failure by fluxing occurred. The Ray-O-Tube—alumina tube assemblage was similar to those supplied commercially for lower temperature applications. In operation, the alumina tube was slowly immersed in the molten metal to a depth of approximately 5 in., and the device was then clamped solidly to a supporting jig where it remained for the duration of the run. A photograph of the equipment, in operation with Ray-O-Tube in place and oxygen injection in progress, is shown in Fig 1. When in position in a heat, the instrument was calibrated by means of an immersion thermocouple and an optical pyrometer. For calibration through the range of temperatures from 1500 to 1650°C, a platinum -platinum + 10 pct rhodium thermocouple in a silica tube was immersed alongside the alumina tube. Output of the Ray-O-Tube in millivolts and the

Jan 1, 1950

By Mark J. Klein

An internal-friction profile induced by nitrogen in Cr-35 at. pet Re was studied as a function of nitrogen concentration and heat treatment. From these studies, the solubility of nitrogen in this alloy was deduced. The equilibrium solubility of nitrogen in chromium does not appear to be substantially changed by the addition of 35 at. pet Re to chromium. However the precipitation kinetics of nitrogen from solution are significantly decreased. IT has been found that rhenium has a beneficial effect on the low-temperature ductility of Group VI-A metals. As part of a study to investigate the mechanism of this increased ductility, it was of interest to compare the concentration of interstitials retained in solution in one of these ductile bee alloys with the concentration retained in solution in its base metal. In this regard, a study of the solubility of nitrogen in ductile Cr-35 at. pet Re was selected for this phase of the investigation because the solubility of nitrogen in the base metal, chromium, has been determined over a fairly large temperature span.1-3 In addition, nitrogen is known to have an embrittling effect on chromium,4 but does not appear to have a comparable embrittling effect on Cr-35 at. pet Re.5 The experimental method selected for this study was the measurement of internal friction. This technique allows interstitial-concentration measurements to be made in bee metals that are sensitive to small changes in the concentration of a particular interstitial, even when other interstitials are present. When subjected to a cyclic stress, interstitial atoms in solid solution give rise to an internal-friction peak whose origin is the stress-induced ordering of interstitials into preferred lat- tice sites. These internal-friction peaks signify a dissipation of elastic energy which is greatest when the period of oscillation is comparable with the relaxation time for the attainment of an equilibrium interstitial distribution. For dilute interstitial binary alloys, the height of the internal-friction peak is proportional to the concentration of interstitial atoms in solid solutions. snoek8 has shown that the internal friction, Q-1, may be expressed by the equation where A is the relaxation strength, ? is the angular frequency, and 7 is the relaxation time. The relaxation strength, A, is proportional to the concentration of interstitials taking part in the relaxation if no interaction occurs between solute atoms. Thus values of peak height, which can be determined as a function of temperature, give a measure of the relative concentration of interstitial atoms in solution at various temperatures. If equilibrium has been attained, the peak heights will be proportional to the interstitial solubilities. The constant that relates A to the interstitial concentration can be determined experimentally from peak-height measurements as a function of concentration for specimens of constant crystallographic orientation. When this has been done, Q-1 measurements can be used to determine solubilities according to the equation C - KQ-1 where C is the soluble interstitial concentration and K is a constant that can be experimentally determined. It is possible, however, that lattice imperfections may bind interstitials to certain lattice sites. Internal friction does not measure these interstitial~, but does measure interstitials which are free to move in the normal lattice sites when subjected to an applied oscillating stress. On alloying the pure metal with a substitutional

Jan 1, 1965

By O. N. Carlson, E. D. Gibson, D. W. Bare

SEVERAL investigators have recently contributed to a clarification of the controversy concerning the allotropy of chromium. Ross and Hume-Rothery1 and Vasyutinskii et a1.2 have reported high-temperature X-ray data on unalloyed chromium from which they have concluded that no allotropic transformation occurs in this metal. Bechtoldt and vacher3 in their investigation of the Cr-Ni alloy system found no evidence for a transformation in chromium and Smart and Haynes4 in critically analyzing the data presented to date concerning this system could find no evidence for a eutectoid reaction in this system. Wyder and Hoch5 in research concurrent with our

Jan 1, 1964

By E. S. Tankins

The main purpose of this work was to study the effect of gold on the activity coefficient of oxygen in the liquid Fe-Au alloy and to determine how copper and silver change the activity coefficient of oxygen. A preliminary investigation has been made of equilibrium in the reaction of hydrogen with oxygen in some of the liquid gold alloys. The experimental method, which has been described in detail elsewhere,&apos; consisted of bubbling accurately known H-A-water vapor mixtures through the Fe-Au alloys contained in alumina crucibles within a vertical closed furnace. When equilibrium was reached, the samples were quenched by rapidly lowering the crucible under an atmosphere of argon to a water cooled brass fixture at the bottom of the furnace tube. The melts were found to freeze from the top in less than 4 sec. The heats were carefully prepared for oxygen analysis. The oxygen content was determined by vacuum fusion analysis.&apos; Only high purity electrolytic materials were used in this investigation. The activity and free energy of oxygen in the liquid iron alloys were studied by means of the reaction; The data for the 80 Fe-Au alloys, obtained as a function of temperature, are summarized in Table I and presented in Fig. 1, where log is plotted against . The results can be expressed by: The data were obtained using water vapor-hydrogen ratios between 0.04 and 0.30, and a 25 pct H2-75 pct A mixture. An oxygen content between 0.030 and 0.060

Jan 1, 1970

By B. D. Cullity, O. P. Puri

The magnetostrictia of nickel after increasing amounts of plastic elongation was measured at field strengths up to 1500 oe. In addition, the residual stress was measured by means of X-ray line shifts. The observed decrease in magnetostriction following plastic strain is shown to be associated with residual compressive stress. If a metal bar, whose longitudinal axis is taken as the x direction, is plastically elongated in the x direction and then unloaded, X-ray diffraction measurements will indicate the presence of a residual compressive macrostress 0%. However, stress measurement by means of mechanical relaxation does not reveal any macrostress. In a previous paper1 the fictitious macrostress indicated by X-rays was ascribed to a particular distribution of micro-stress, namely, one in which the bulk of the material was stressed more or less uniformly in compression and a very small portion in tension. It was shown that this distribution would account for Neurath&apos;s measurements2 of magnetic losses in silicon steel, because of the effect of residual stress on magnetostriction. The present paper is concerned directly with magnetostriction, in nickel, and with the effect on magnetostriction of the residual stress created by plastic elongation. The residual stress was determined by measurements of X-ray line shifts. MATERIAL AND METHODS Commercially pure "A" nickel was investigated. Its nominal composition, in weight percent, is 99.4 Ni + Co, 0.2 Mn, 0.15 Fe, 0.1 Cu, 0.1 C, 0.05 Si, and 0.005 S. Magnetostriction was measured by means of SR-4 electrical-resistance strain gages mounted on specimens 1/4 in. sq and 8 in. long. Magnetic fields up to about 1500 ce were provided by a multilayer, non-cooled solenoid. A considerable amount of heat was developed at the higher field strengths, and, to avoid errors due to changes in the specimen temperature, the following procedure was adopted. Each measurement of the magnetostriction X at a particular field strength H was preceded by demagnetization and an adjustment of the strain indicator to zero; the field H was then quickly switched on and the strain read immediately. Curves of ? vs H were flat for field strengths above about 750 oe for all specimens, and this constant value of X was accordingly taken as the saturation magnetostriction ?s The X-ray measurements of residual stress were made with a Norelco diffractometer on specimens cut from flat bars 1 1/4 in. wide, 1/8 in. thick, and 12 in. long. These measurements were confined to lattice planes parallel to the surface of the specimen. Two reflections were studied: the 311 CrKß line at 28 = 157 deg, and the 420 CuKal line at 28 = 155 deg. The line centers were determined by fitting a parabola to the peak of the line, as suggested by Ogilvie3 and as modified by Koistinen and Marburger.4 The CuKa doublet from the plastically elongated specimens was first resolved by the Rachinger method5. All X-ray measurements were made by counting at fixed angular positions. RESULTS The results of the magnetostriction measurements are shown in Fig. 1 and Table 1. The magnitude of

Jan 1, 1963

By C. W. Sherman, J. Chipman, H. I. Elvander

THE pronounced and usually deleterious effects of sulphur on all ferrous metals and the resultant necessity for its control in metallurgical processes have stimulated many investigations of the system iron-sulphur. The data required for thermodynamic study of the behavior of sulphur in molten iron and steel include the activity and free energy of the dissolved sulphur and its heat of solution. Such data are also of theoretical interest since there is all too little information available concerning solutions of nonmetallic solutes in metallic solvents. It was the purpose of this investigation to attack the problem very directly by a study of equilibrium at several temperatures in the reaction H2 (gas) + S = H2S (gas) [1] K1 = PH2S /PH2 as where the sulphur is present in the liquid iron in amounts up to several percent by weight. Such a method of attack is not new since several careful studies have already been reported. It is planned, however, to extend the study to other metallic solvents and particularly to determine the effects of the various alloying elements on the activity of sulphur in liquid iron. This paper presents the results on molten iron-sulphur alloys containing up to 4 pct sulphur in the temperature range 1530°-1730°C. Literature Review The significant researches on dilute molten solutions of sulphur in iron include those of Chipman

Jan 1, 1951

By N. Mungan

Formation damage, i.e.. reduclion in permeability, has been generally attribuled to clay minerals which expand or disperse upon contact with water that is less saline than the connate water. Luboratory, studies show that penneahility reduction can also occur in formalions containing only nonexpandable clays such as illite or kaolinite, and can be caused also by changes in pH. Furthermore, pH changes can damage even formations that are essentially free of clays. It is suggested that permeability reduction is due to the small passages being blocked by particles, which may be dispersed clays, cemenlion material or other fine parricles. These particles are dislodged by dispersion of clays due to changes in salinity or by dissolution of calcareous cement by acids, or of silicaceous cement by alkaline solutions. In working with reservoir cores, it was found that extracted cores damaged more easily and extensively than nonextracted cores. The extent of damage depended also on tenlperatltre. INTRODUCTION Permeability is an important property of porous media and has been the subject of many studies by engineers and geologists. Many of these studies are conccrned with formation damage, i.e., reduction in permeability, resulting from exposure of oil-producing formations to water substantially less saline than the connate water. This effect causes understandable concern since during drilling, completion and production phases formations are often exposed to fresh water. The damage resulting from contact with relatively fresh water has been attributed to expansion and dispersion oF clay minerals. During laboratory investigation of the use of NaOH as a wettability reversal agent to increase oil recovery from oil-wet reservoirs, several cores used in the displacement studies suffered loss in permeability. Despite the traditional usage of NaOH for conditioning aqueous mud systems, the role of the caustic filtrate in wellbore damage seems to have been overlooked. Browning2 as recently reported on the effects of NaOH in dispersing clay minerals but he was concerned only with complications that may arise in drilling massive shale beds. The following study was made to examine the role of pH and salinity changes in core damage. Where cores from reservoirs were used, tests were performed with extracted and nonextracted cores both at room and reser- voir temperatures, since it was felt that the test environment and core condition may affect the results. Because of its limited coverage and exploratory nature, this study is not intended to provide answers to field formation damage problems. It is hoped that it will encourage research into new aspects of the permeability reduction problems, particularly those allied to new recovery and production processes. PROCEDURE In all permeability tests, fluids were pumped through the cores at a constant volumetric rate. Only deaerated fluids and reagent grade chemicals were used. The fluids were passed through two ultrafine filters before injection to remove any entrained particles. The cores, with the exception of the unconsolidated cores, were mounted in Hassler holders. Water was used to transmit pressure to the sleeve. The inlet endpiece had two entry ports which permitted scavenging one fluid with another to avoid any mixing in the small holdup volume. The cores were flushed with CO2 gas, evacuated for 5 to 6 hours and saturated with the first liquid at a pressure of 1,000 psi for 24 hours to eliminate any free gas from the cores. Pressure differences up to 20 psi were measured by transducers, calibrated in inches of water and continuously recorded. For greater pressure drops, gauges were used. All reservoir cores were cleaned with a light refined mineral oil, then with heptane, and finally dried with CO2. Compatibility tests showed that no precipitates formed when mineral oil and the crudes were mixed. Some cores were extracted in Dean-Stark-type solvent extractors using xylene and trichloroethane and dried in a vacuum oven at 450F. Each test consisted of a sequence of water, test solution, and again water flow. RESULTS AND DISCUSSION STUDIES IN BEREA CORES Salinity Contrast Berea cores 2-in. in diameter and 12-in. long were cut from sandstone quarried in Cleveland, Ohio. The clay minerals were identified by X-ray diffraction to be chlorite, kaolinite, illite and incerlayered illite. Flow of fresh water or 30,000 ppm brinc does not cause any permeability reduction (Fig. 1). However, after injection of brine the core is readily damaged by fresh water. Damage starts almost instantly as the fresh water injection is begun, and at a cumulative injection of 1.2 PV fresh water, the permeability has dropped from 190 to 0.9 md. Upon continued injection, the effluent contains clay minerals dislodged from the core. The final core per-

Jan 1, 1966

By E. W. Dewing

The solubility of A14C3 in cryolite melts has been determined by holding the melt with aluminum in a graphite crucible for 4 hr at temperature, quenching the crucible in water, and analyzing the frozen salt by CH4 evolution. The solubility is given by log(wt % Al4C3) = 1.298 -1.l74 (wt ratio NaF/AlF3) independent of temperature in the range 985" to 1080°C. Additions ofA1203, .NaCl, CaF2, or LiF up to 10 wt pct do not affect the solubility, provided that LiF and CaF2 are replaced by equivalent NaFin calculating the ratio. The variation with ratio can be accounted for quantitatively on the hypothesis that the Mechanism of solution is Al4C3 + 2AIF3 = 3Al2CF2 since the solubility varies as (aAIF3) 2/3; Mechanisms involving C", C2- , AlC- , A12C2+, and Al2CF+are re-jected. At ratios above 1.5 truces of c;- are also present. It was noticed some years ago in this laboratory that carbon specimens made cathodic in a cryolite bath decrease in diameter over a period of time.&apos; It was also found that cryolite which had been melted with aluminum in a graphite crucible was sometimes yellow, and that A14C3 could be seen intimately embedded in the cryolite crystals. CH, could be recovered by acid attack. There was thus reason to believe that A14C3 had a genuine solubility in molten cryolite, and the object of this work was to measure it. EXPERIMENTAL AND RESULTS A graphite crucible, 2 in. ID and 2.5 in. deep with a close-fitting lid, contained about 150 g of cryolite (plus additives) and about 20 g of 99.99 pct pure Al. It was placed in a vertical Inconel furnace tube, covered with refractory brick to provide thermal insulation, and the top of the tube was roughly sealed with disks of asbestos paper. An alumina tube led argon down to the level of the top of the crucible to expel air, and an alumina sheath with a Pt-10 pct Rh ther-mocouple inside was positioned between the crucible and the wall of the Inconel tube. The tube was heated in an electrical resistance furnace for the desired length of time; the refractory bricks were then removed, and the crucible was lifted out with tongs and quenched in water. After such a crucible was broken open it could be seen that its inner surface was yellow owing to the presence of A1,C3, and sometimes needle-like crystals could be observed (at X75 magnification) growing out into the nielt. It was concluded that Al,C, had been present as a separate phase when the crucible was at tenlperature and that the melt had been saturated: in

Jan 1, 1970

By J. B. Pullen

THE United Verde mine is in the north central part of Arizona, on the northeasterly slope of the Black Hills, near the town of Jerome. Ore was first discovered in the district about 1875, and the first mining claims were located by M. A. Ruffner and associates in 1877. In 1888 the late Senator William A. Clark secured control of the property and under his ownership it developed into one of the country&apos;s most important copper producers. The property was sold to the Phelps Dodge Corporation in 1935, and since then has been under this Corporation&apos;s management. Except for shutdowns caused by general world-market conditions, production has been continuous from 189o to date. GEOLOGY The mineralized zone ranges in area from approximately 12 acres to less than 5 acres. All mineralization occurs in the pre-Cambrian intrusives. The first intrusion, according to geologic records, was the quartz porphyry, which later was intruded by augite diorite. Following the diorite intrusion through a series of intrusions of lesser magnitude, a pipelike mass of massive sulphide, quartz and rock was formed. The diorite forms the hanging wall of this mass, and the porphyry the footwall. Between the footwall and the sulphide a band of chlorite schist was formed, probably owing to metamorphic conditions. Commercial ore occurs along the contact of the schist and sulphide extending into the sulphide, sometimes entirely through the schist, and fingering out into the porphyry. The ore deposit was formed by replacement similar to deposits formed in limestone areas. Faulting and deformation occurred in pre-Cambrian times and again in the Tertiary period, removing approximately 2000 ft. from the top of the main United Verde ore body, forming the United Verde Extension ore body, the only other major ore body in the district. Major development work has shown that the sulphide mass extends to the 3300-ft. level, and diamond drilling below this level has indicated that the mass might extend below the 3700-ft. level, but in a diminished quantity. While many copper minerals exist in the mine, the chief commercial mineral is chalcopyrite. A plan and vertical section of the mineralized zone showing the principal geological features is shown in Figs. I and 2. GENERAL DESCRIPTION AND PHYSICAL CONDITION OF MINE After over 50 years of active production, ore still exists on almost every level of the mine. This condition is due to many causes -mine fires, which broke out as early as 1894, caused the abandonment of certain areas; subsidence and ground movements retarded the cleaning up of others. Furthermore, in the early days there was such an abundance of ore that when mining became difficult it was a simple matter to replace the production by going to a deeper level. Several attempts were made to recover the ore in the fire zone, both by glory-holing

Jan 1, 1941

By R. F. Decker, J. R. Mihalisin

Phase transformations in a series of relatively pure nickel-titanium-aluminum binary and ternary alloys were studied. The purpose was to clarify age-hardening mechanisms, especially in predominantly titanium-hardened compositions. The micro-structures, as determined on a tirne-temperature-transformation basis by light and electron microscopy and X-ray diffraction, were correlated with room temperature and hot hardnesses. The stability of the ? phase under nonequilibrium conditions was shown to be important in this system. MANY of the alloys designed for service in the temperature range of 1200oF (649°C) to 1800°F (980°C) are austenitic iron-.nickel base alloys hardened by titanium and aluminum. The control of high-temperature properties of these alloys has been advanced by the knowledge of microstructures provided by the equilibrium diagrams of Taylor and Floyd1 and Taylor.2, 3 However, there have been notable instances in the predominantly titanium-hardened alloys where the correlation of properties with microstructure and the equilibrium diagrams has been unsuccessful. Mihalisin and carrol14 have noted in electron microscope studies of commercial alloys of this type that a fee phase precipitates and transforms to 71 (hep Ni3Ti) in stress-rupture tests. Bieber5 found that this fee phase remained in nickel-chromium-titanium alloys even when aluminum was excluded. Age hardening in iron-nickel base alloys has been attributed to 71 by Craver, Aggen, and Dyrkacz,6 ? (fee phase based on Ni3Al) by Beattie and Hagel7 and both phases by Lena,8 Yet, on the basis of the nickel-titanium-aluminum equilibrium diagram of Taylor and Floyd shown in Fig. 1, it has been difficult to understand the presence of ? in low aluminum alloys. Furthermore, the characteristic coarse dispersion of 71 has not been commensurate with the marked aging response. Also there have been anomalous grain boundary transformations in the iron-nickel base alloys which have markedly reduced notched stress rupture properties.9 These have been related to boron content and residual cold work. Recently, Golubtsova and Mashkovich,10 Buckle and Manene11 and Bogaryatskii and Tyapkin12 have noted a transition fee Ni3Ti in titanium-hardened nickel-base alloys. It was apparent from the latter studies that a transition phase was important in the nickel-titanium-aluminum system. The purpose of this study was to identify this phase, measure its transformation characteristics and kinetics, and attempt to correlate these findings with age hardening. It was believed that time-temperature-transformation studies, because of their adaptability to transition phases, would be of most value for this investigation. Accordingly, this method of study was undertaken on relatively pure nickel-titanium-aluminum alloys with controlled variations in boron content and residual cold work. EXPERIMENTAL PROCEDURES Compositions were selected from the nickel-titanium-aluminum isothermal section of Taylor and Floyd.&apos; These compositions are plotted in Fig. 1 and were selected to obtain equal aging potential of approximately 15 pet by volume of the equilibrium precipitate. The materials were vacuum melted from

Jan 1, 1961

By J. H. Bramwell

The following experience in rebuilding a furnace crucible while in blast may not be wholly uninteresting to some, notwithstanding its purely practical character. Few are aware of the frequent calls made on a furnace manager&apos;s skill and ingenuity, to meet the irregularities which present themselves with kaleidoscopic variations in the operations of furnaces. Unfortunately the methods pursued in overcoming these practical difficulties are too seldom recorded, and much valuable information is lost that could not fail to be of value to many, and to none more so than the educated technical manager, with a limited practical experience, who, without a literature or record of any kind to refer to, finds himself, in times of emergency, dependent and looking for assistance from those whom it is his province to instruct and direct. With positive data, however, that like difficulties have been successfully overcome, he can confidently resort to similar expedients, with such modification; as the circumstances may demand in his particular case, and pull through seeming impossibilities in the face of ignorant prejudice. The Quinnimont Furnace (60 x 15 feet) had been in operation but two months, when it became necessary to draw the tuyeres out a distance of 18 inches, in order to give them a resting-place; the brickwork under them being completely cut away, so that after each

By John M. Hird

Control of artesian ground water has played an important role in the development of Texas Gulf Sulphur&apos;s phosphate mining venture in eastern North Carolina. To facilitate dry mining methods, 60 million gpd of fresh water is pumped through wells from a limestone aquifer underlying the uniform flat-lying ore section. Hydrologic information revealed from pumping tests has been used in successfully developing a depressurizing system. Computer assistance is used to plan well patterns. High volume pumping has lowered water levels in water wells over a large area in the Coastal Plain without detrimental effects on water quality in the aquifer. Cooperative effort between mining firms will be required to control the ground water as new mines are developed in the district. An intricate observation -well system is monitored regularly over the wide area of pumping effect to ensure that gradient reversals have not caused salt water encroachment.

Jan 1, 1972

By J. H. Brophy, J. Wulff, H. W. Hayden

The mickel-activated sintering of tungsten occurs in two stages of densification. A kinetic analysis of the second stage has been based on an appropriate model of the process. As in the first stage, the rate-controlling mechanism for the second stage is also the solution of tungsten in the nickel carrier phase. The transition from the relatively rapid first-stage results from the spherozdization of pores and the initiation of grain growth. Finer grain size due to higher-nickel content leads to more rapid and higher degrees of densification 1 HE sintering of tungsten is accelerated by small additions of nickel, cobalt, and iron.&apos; Experimental evidence in detail has shown that nickel-coated, hydrogen-reduced tungsten powder may be sintered to more than 90 pet of theoretical density at l100o C.2, 3 Simultaneously, a kinetic analysis of the process showed that it took place in two distinct stages. In the first stage, nickel evidently served as a carrier phase through which tungsten atoms could move. This stage was kinetically similar to the "solution-precipitation" step postulated when the carrier phase is a liquid,4 although in the Ni-W case, there is no evidence of the existence of a liquid phase either in equilibrium phase relationships or in microstruc-tures at the temperatures under consideration. It has been shown that this stage corresponds to a process which is rate controlled by a phase boundary reaction.3 More recent evidence has been presented5 showing that after the initial rapid stage of sintering, densification continues in the final stage but at a slower rate, although no mechanism for this stage of densification was defined. An analysis of later stages of densification in solid state sintering has been presented,6 but it is not directly applicable in the present case of activated or carrier phase sintering. It is the purpose of this investigation to study the final stage of nickel activated tungsten sintering in greater detail The effect of varying nickel content has been examined, and a possible kinetic mechanism defined. EXPERIMENTAL PROCEDURE AND RESULTS Commercial hydrogen-reduced tungsten powder from Wah-Chmg Corp., having a nominal particle size of1 µ and a B.E.T. specific surface area of 5500 sq. cm per g was mixed with aqueous solutions of hydrated nickel nitrate in proportions sufficient to produce nominal compositions of 0.25, 1, 3, and 5 wt pet Ni. This solution was then evaporated to dry-ness at approximately 150" C for 15 hr. Following evaporation, the resulting powder cake was broken with a mortar and pestle and reduced in hydrogen at 800oC for 1 hr. Following reduction, the powder

Jan 1, 1962