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By Floyd C. Kelly

A. HUltgren, .Söderfors, Sweden (written discussion*).—From the results obtained in his own experiments as well as those of Austin and of Grube Mr. Kelley derives a general law, expressed tentatively in the following words: "whenever two metals are brought into intimate contact at a temperature at which diffusion takes place, a comparatively rapid, or abnormal, grain growth results." It is suggested that,, in order adequately to represent the facts, this definition should he restricted by the following qualifications: a and b are the two metals, b diffusing into a. A. At the temperature in question a should exist as phase a 1 having a limited solubility for b. B. The supply of b by diffusion should be sufficient, in view of the rate of diffusion into a 1, to increase the concentration of b above the saturation value in a 1 so as to cause a new phase a2 to form. (7. The phase a2 should have a range of solubility for 6, thus rendering continued diffusion possible. D. In order that the columnar grains may be preserved in the structure the phase a2 should, of course, not suffer transformation on cooling. The phenomenon thus defined may be described as progressive transformation by diffusion. Its mechanism would appear to he as follows: Fig. 17 shows a portion of the equilibrium diagram a-b, Fig. 18 the distribution of b in solution after various periods of diffusion, Fig. 19 represents the structure in cross-section of a cylindrical rod of a at the end of heating period 3. 1. The first effect of diffusion of b into a will be to establish a concentration gradient in phase a1 (1, Fig. 18). When the saturation value for the temperature of the experiment (m, Fig. 17) is reached at the surface, nuclei of, a2 of composition n will form here, and later develop into a continuous layer. Assuming that diffusion proceeds without irregularities and that transformation at any point sets in without lag—i. e., in the moment saturation is exceeded—the transformation a1-a2 will advance inwards on a cylindrical surface concentric with the surface of the rod. The discontinuity of composition at the transformation surface in the position it happens to have at the end of the treatment (3, Fig. 18) will be preserved at room temperature, if the cooling is not particularly slow, and be recorded in the structure as a marked, smooth line, in agreement with Grube's and the author's observations. The shape of the distribution curves in Fig. 18 is also corroborated by the analyses given by Grube. 2. During diffusion, since the secondary phase a2 is always in immediate contact with the saturated part of the primary phase a1, there should be very little lag in the transformation. This means that the first a2 grains formed should grow in preference to the formation of independent nuclei; in other words, columnar growth results. It does not seem necessary to assume, with Green,' whose conception of the phenomenon

Jan 1, 1929

By C. A. Siebert, D. J. Girardi

PRACTICALLY every metallurgical process in-volves, at some stage or another, the contact of a metal with a gas. Because of this, gas-metal re-actions are of great practical importance and have been subjected to numerous investigations. It has long been recognized that the presence of cuprous oxide in liquid copper has an important effect on its casting characteristics and .physical properties. This has led to the desirability of determining the quantitative relationships between cuprous oxide in the liquid copper and the usual gases present during processing. Such data are not only of practical importance but also of a theoretical interest in that they provide a means of applying the principles of physical chemistry to problems in applied metallurgy. The object of this investigation was to determine the quantitative relationship at equilibrium between the gases carbon monoxide and carbon dioxide and the cuprous oxide content of liquid copper. The reaction and its equilibrium constant may be expressed as follows: 2 Cu (liq) + CO2 (g) = Cu2O + CO (g) acu2o X aco/a2 cu X aco2 Here the underlined symbol Cu2O designates cuprous oxide dissolved in liquid copper and (a), the activity of the various constituents. The activities of carbon monoxide and carbon dioxide are assumed to be directly proportional to their re- spective partial pressures and the activities of cuprous oxide and copper are taken to be proportional to their respective mol fractions. The equilibrium constant may then be expressed as follows: K2 = Ncu2o X Pco [Ncu]2 X Pco2 where N = mol fraction The solubility of carbon monoxide and carbon dioxide in liquid copper is a rather controversial subject.'-' A review of the literature is given by 0. W. Ellis.' It appears that carbon monoxide and carbon dioxide are both only very slightly, if at all, soluble in liquid copper. Volskii and Slobodskoi5 determined the equilibrium between carbon monoxide, carbon dioxide, and liquid copper at 1100°C. Their results show a higher cuprous oxide content for a given CO/CO2 ratio than found in the present work. The system hydrogen, water vapor, and liquid copper was investigated by Allen and Hewitt8 over the temperature range of 1090" to 1350°C. Equilibrium values for the system carbon monoxide, carbon dioxide, and liquid copper calculated from these data agree reasonably well with the present work. Materials and Procedure The copper used was oxygen free, designated as OF and analyzed as 99.98 pct copper with no appreciable amount of any one impurity based upon spectrographic determinations. The carbon dioxide was cylinder gas averaging about 99.95 pct CO2 with air as the major impurity. The carbon monoxide was produced by passing carbon dioxide over heated charcoal. Alundum combustion boats were used as containers for the liquid copper. No appreciable reaction took place between the copper and the alumina. This was evident from the fact that the copper sample after a run did not ordinarily adhere to the bottom of the boat and that the

Jan 1, 1951

By P. V. Martin

Shortly after the middle of the nineteenth century, the invention of the regenerative open-hearth furnace and the development of the Bessemer process stimulated a rate of steel production whose magnitude created an unprecedented demand for pig iron. Revolutionary improvements in furnace design, auxiliary equipment, and operating technique enabled the blast furnace to keep abreast of the constantly increasing requirements of the steel mill. The development of improved blowing equipment, more adequate facilities for material handling, and particularly the general use of anthracitc and coke to replace the physically weaker charcoal, led to a rapid expansion in both the height and volume of furnaces. Beyond a doubt, however, the greatest single factor in blast-furnace improvement at this time was the use of the higher blast temperatures made available by the replacement of the recuperative iron pipe stoves by the regenerative Cowper brick stove. The increased blast temperature not only resulted in greater output but also reduced fuel consumption . far more than could be explained by the additional heat content of the blast. The progress of iron manufacturing was thus largely mechanical and thermal. Little attention was given the chemistry of the process until the publication of the investigations of Sir Lowthian Bell.1 Bell's painstaking experiments and investigations gave to the blast-furnace man his first real scientific conception of blast-furnace chemistry. Bell's recognition of the dual function of the carbon, the technical importance of reversible reactions and chemical equilibria, and his conception of the degree of oxidation of the carbon as shown by the analysis of the outgoing gases as a criterion of furnace efficiency, laid the foundation upon which has since been erected the structure of blast-furnace theory. Prominent among those availing themselves of Bell's data as .a basis of further study was M. L. Gruner,2 professor of the French School of Mines. His "Blast Furnace Phenomena," published in 1870, presented

Jan 1, 1940

By P. V. Martin

Shortly after the middle of the nineteenth century, the invention of the regenerative open-hearth furnace and the development of the Bessemer process stimulated a rate of steel production whose magnitude created an unprecedented demand for pig iron. Revolutionary improvements in furnace design, auxiliary equipment, and operating technique enabled the blast furnace to keep abreast of the constantly increasing requirements of the steel mill. The development of improved blowing equipment, more adequate facilities for material handling, and particularly the general use of anthracitc and coke to replace the physically weaker charcoal, led to a rapid expansion in both the height and volume of furnaces. Beyond a doubt, however, the greatest single factor in blast-furnace improvement at this time was the use of the higher blast temperatures made available by the replacement of the recuperative iron pipe stoves by the regenerative Cowper brick stove. The increased blast temperature not only resulted in greater output but also reduced fuel consumption . far more than could be explained by the additional heat content of the blast. The progress of iron manufacturing was thus largely mechanical and thermal. Little attention was given the chemistry of the process until the publication of the investigations of Sir Lowthian Bell.1 Bell's painstaking experiments and investigations gave to the blast-furnace man his first real scientific conception of blast-furnace chemistry. Bell's recognition of the dual function of the carbon, the technical importance of reversible reactions and chemical equilibria, and his conception of the degree of oxidation of the carbon as shown by the analysis of the outgoing gases as a criterion of furnace efficiency, laid the foundation upon which has since been erected the structure of blast-furnace theory. Prominent among those availing themselves of Bell's data as .a basis of further study was M. L. Gruner,2 professor of the French School of Mines. His "Blast Furnace Phenomena," published in 1870, presented

Jan 1, 1940

By H. Pew, J. H. Field

To alleviate pollution more restrictive legislation is being enacted, either limiting emission of pollutants or the type of fuel that can be utilized. The nature and magnitude of air pollution problems affecting the mining, preparation, coking and combustion of coal are described. Methods for combatting particulate emissions by use of mechanical separators and electrostatic pre-cipitors are discussed. Proposed methods to meet the problem of gaseous emissions currently receiving considerable attention are described, with special emphasis on methods to decrease pollution by sulfur oxides. Concern about air pollution goes back several centuries, but until very recently most effort has been aimed at coal smoke and other visible pollutants. The classic example of a 'successful' campaign for smoke abatement and control is the fruitful combined effort of the city of Pittsburgh and its surrounding Allegheny County, which eventually led to the reconstruction of downtown Pittsburgh at an estimated cost of one billion dollars. Historically, the city's downtown Golden Triangle district had been afflicted by pollutants evolving from steel mills, from a variety of other industries, and from railroad locomotives. Efforts to alleviate the situation prior to 1943 were virtually ineffective. In 1945, however, a comprehensive redevelopment plan was prepared and backed by state authority. Within a few years a clean, modern metropolis has evolved where once stood America's famous 'smoky city.' But the victory in Pittsburgh, as in various other American cities, has not solved the national problem. Current estimates indicate that 133 million tons annually of air pollutants from all sources still are emitted annually into the atmosphere above the United States. About 10% of this annual effluent is particulate matter so that most of the remaining pollution problems will be solved only when other effluents are reduced. Essentially, these are sulfur oxides, nitro- gen oxides, hydrocarbons, and carbon monoxide. Over the years, both states and local communities have tended to increase the restrictions on smoke and fly ash — problems mostly of concern in the combustion of coal. Prior to the middle 1950's, ordinances sometimes permitted emissions of smoke equivalent to as much as No. 3 on the Ringlemann scale. Since 1956, no ordinance has been passed which allows smoke of greater than No. 2. Under today's conditions of improved fuels, equipment and practice, a few communities have passed laws prohibiting emission of smoke of any density darker than Ringlemann No. 1. The majority of existing laws on fly ash emission in the U.S. limit emissions equivalent to 0.85 lb of fly ash per 1000 Ib of flue gas. In recent years, however, regulations which have been adopted give cognizance to the higher level of performance now obtainable with improved equipment. A comparison of the restrictions of five codes adopted since 1960 is given in Table I. The most stringent of these is the one for New York City which provides for a maximum emission of 0.6 lb fly ash per million Btu heat release (equivalent to roughly 0.51 lb/1000 lb of flue gas). The first comprehensive effort to restrict the emission of SO2 resulted from the passage of a 1937 law in St. Louis. This regulation stipulated that coal containing in excess of 23% volatile matter and 2% sulfur must be washed, thereby presumably producing some effective reduction in the input sulfur content. This was followed in 1949 by a Los Angeles County law which prohibited the emission of SO2 in concentrations greater than 0.2%. Most SO2-restrictive legislation passed since that date has been based on this limiting 0.2% SO2 by volume, although modifications are occasionally permitted under selected conditions, sometimes based on the fact that certain limiting ground concentrations are not exceeded — such as in the rules adopted by the San Francisco Bay area. To date, no legislation has been passed in the U.S. to limit the generation of nitrogen oxides from the combustion of fossil fuels. However, such oxides are considered to be of potential importance in air pollution control because of their possible detrimental effects on health and their reported role in the formation of photochemical smog. Interest in reducing oxides of nitrogen from powerplant and auto exhausts is increasing and regulations limiting their quantity can be expected in the future.

Jan 1, 1968

By N. Mungan

Laboratory water floods were performed in oil-wet and waterwet alundum and Torpedo cores, displacing a refined oil with n-hexylamine or Triton X-100 solution. Also, some floods were performed in which a sucrose solution was displaced with n-butyl alcohol. The Purpose ot the tests was to see if the oil recotlery could be increased and to examine what role the inter-facial tension reduction and wettability change play in the recovery mechanism. it was found that the chromatographic transport of amine was influenced by core wettability. In oil-wet cores, the rate of advance of the amine band could be predicted from equilibrium chromato-graphy, while in water-wet cores the amine band moved faster than predicted, indicating a non-equilibrium process. By reducing the interfacial tension to 1.1 dyne/ cm, oil recovery was increased. More oil was recovered from Dri-filmed cores than from water-wet cores. Reversing the wettability of the porous media from oil-wet condition also resulted in some additional oil recovery. Neutral wettability floods did not increase oil recovery. INTRODUCTION Interfacial forces in petroleum reservoirs are responsible for retention of large quantities of residual oil. Increasing exploration costs have created an incentive to attempt recovery of this residual oil by new and novel processes. One novel process involves changing the interfacial forces by introducing a chemical into the reservoir during water flooding. Recently, several investigators have carried out laboratory displacement tests using amines. lt3.4 The amines adsorbed onto initially water-wet core surfaces, changing them to oil wet. Additional oil was recovered when the cores were flooded in a manner reversing the. wettability from oil-wet conditions. In all these studies, the wettability reversal was considered responsible for increased oil recoveries although it was noted that amines also reduced oil-water interfacial tension. In the present study, displacement experiments were performed in water-wet and Dri-filmed cores. The purpose was to separate the effects of lowering the interfacial tension from changing the wettability. LABORATORY STUDY All experimental data given in this paper have been obtained at a temperature of 70F + 1 and prevailing atmospheric pressure. FLUIDS AND MATERIALS The oil used in these experiments* was washed with H2S04 and passed through two 100-200 mesh silica-gel beds to remove unsaturates and surface active impurities. Normal hexylamine** of practical purity was used, and the alundum cores*** were composed of nearly pure A1203. Fused quartz (SiOi) and Lucalox (A12 )t plates were used in the contact angle measurements. DISPLACEMENT TESTS Displacement tests were performed in alundum and Torpedo cores. Before displacement runs, cores were acidized with 0.1 normal HCI, flushed with distilled water and fired at 1,200F to make them water wet. This procedure also reduced water sensitivity of the Torpedo cores. Oil-wet cores were prepared from water-wet cores by flowing several pore volumes of 1 per cent by weight Dri-film SC-87 solution in heptane through the cores, flushing the cores with nitrogen, evacuating, and finally heating the cores at 300F for 4 or 5 hours. Between floods, cores were cleaned by conventional procedures and treated again as above.

Jan 1, 1965

By Oscar Weiss

An aerial magnetometer survey was carried out by the author's geophysical organization over the Vrede-fort dome, where Witwatersrand beds are wrapped around a granite plug 25 to 30 miles in diameter. The well-known magnetic shales of the Lower Witwatersrand system (to be referred to as LWW) give strong negative anomalies over the out-cropping portion of the dome. This is unusual as these same shales cause positive anomalies over large areas near Johannesburg and along a strike of 130 miles between the East Rand and Klerksdorp. It is suggested that the negative polarization is caused by heat and stresses connected with the doming. This negative polarization of sedimentary beds, which usually cause positive anomalies, is a good example of how "magnetic lows" can be caused by "structural highs." Significant magnetic anomalies should be tested by gravity and seismic methods irrespective of the sign of the anomalies. South of the line X — Y (see Fig 2 and 5) the gravity anomalies are smaller over the LWW beds and magnetic anomalies suddenly become weaker and even change signs by becoming positive. This peculiar phe- nomenon is explained by faulting which truncated the nearly vertical LWW shales at depth. In this manner the mass of the LWW beds has been reduced together with the weakening of the negative magnetic anomalies by positive poles which occupy the truncated end. Furthermore, by uplifting the beds between f1 and f2 (Fig 2) positive polarization becomes predominant, thus causing positive magnetic anomalies. General The Vredefort dome is one of the internationally known geological structures, which, among others, has attracted the attention of numerous American geologists. It was for this latter reason that our aerial magnetic results over this structure were selected by us for publication in the United States of America. A full description of the exposed geology has been published by Nell and readers are referred to this paper, which is subject to only slight modifications inasmuch as the subdivision of the Witwatersrand system (to be referred to as WW system) is concerned. The Vredefort dome is about 60 miles southwest of Johannesburg. The WW system, after being exposed in the vicinity of Johannesburg, plunges with southerly dips beneath the Vent-ersdorp and Transvaal systems. Along a section southwest from Johannesburg, as shown diagrammatically in Fig 4, we see no outcrops of the WW system until the Vredefort dome, where the Upper and Lower WW system are wrapped around an almost circular arc of a granite mass. Here the whole WW system is overturned around the perimeter of a huge granite plug 25 to 30 miles in diameter. Less than half of the circumference of this dome is exposed; the rest is covered by Karroo dolerites and sediments. The determination of the exact shape of the concealed part of the dome has been a matter of considerable interest and obviously geophysical methods were eminently suited for obtaining this information. A good start was made with a gravimeter survey carried out by the Geological Survey of the Union of South Africa.2 Our own

Jan 1, 1950

By B. Post, D. Moskowitz, F. W. Glaser

Lattice parameters of various hafnium compounds, two borides, a carbide and a nitride were determined. Some physical properties were measured and comparisons with the properties of the corre-sponing zirconium compounds were drawn. A LTHOUGH borides of transition metals have A been extensively investigated in recent years, there are few references in the literature to borides of hafnium. This is not surprising, in view of the extreme scarcity and great cost of the purified metal. Becker' reported the existence of a boride, carbide, and nitride of hafnium; he listed the formulas as HfB, HfC, and HfN. However, in his work no mention was made of chemical analyses of the reaction products. In this paper results of a study of various hafnium compounds, including borides, carbides, and nitrides, are reported. It was expected, of course, that these compounds would closely resemble their zirconium analogues, which have previously been extensively investigated. Three borides of zirconium are known: ZrB,² ZrB,² and ZrB212.4 In addition, one carbide, ZrC,5 and one nitride, ZrN,5 have been reported. It should be noted that ZrB and ZrB12 are stable phases only in relatively high-temperature regions, unlike ZrB2, which is stable from room temperature to its melting point." It was felt that hafnium would yield corresponding borides, carbides, and nitrides with similar stability ranges. Experimental Procedures and Results A quantity of hafnium metal that was better than 97 pct pure, with zirconium as its major impurity, was furnished by the Argonne National Laboratories. The boron powder used was approximately 96.5 pct pure. In general, the procedure involved mixing the metal and boron powders in the desired proportions, and subsequently hot pressing them. The resulting specimens were analyzed chemically and phases present were identified by X-ray diffraction methods. A Philips Norelco Geiger counter spectrometer was used for identification of components and for measurement of lattice constants. Filtered copper radiation was used for all X-ray work. Electrical resistivity and density measurements were carried out at room temperature. The stable diboride, HfB2, will be described first. Stoichiometric quantities of boron and metal were heated to approximately 2000°C during hot pressing. The reaction product was shown by X-ray diffraction methods to be isomorphous with ZrB2 (space group Dlgh; P6/mm). Values of lattice constants of HfB2 compared with those of ZrB2 are shown in Table I. The calculated density of HfB2 is 11.2 g per cc, compared with a measured (pycnometric) value of 10.5 g per cc. HfB2 specimens prepared under a wide variety of conditions (including variations in initial Hf-B ratios) showed only insignificant variations in lattice constants, indicating a very narrow range of homogeneity. Like ZrB2,7 HfB2 is an excellent electrical conductor. The resistivity at room temperature of hot-pressed samples, approximately 85 pct dense, is 12 microhm-cm. This compares favorably with the electrical resistivity of 10 mi-

Jan 1, 1954

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'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 Leonard Austin

WHAT Colonel Dwight says regarding the treat-ment of oxidized ores1 holds true also of the silver-lead smelting operations in Utah. The ore sought for was such as would, with appropriate fluxes, yield slag, and "lead bullion," as the lead reduced from the ore and carrying its gold and silver, was called. No matte, and probably little or no speiss, was yielded, and hence there was nothing to roast, either of ore or matte. But, by 1880, when I first took hold in smelting, there was quite a production of matte at the works of the Ger-mania Smelting and Refining Co., Utah, because, by that time, ores containing some pyrite and galena were being smelted. This was due, as at the Grant Works, Denver, to the more attractive price paid for the treatment of such ores. The matte, containing about 5 per cent. copper, was accordingly heap-roasted and returned to the blast furnace for the recovery of its contained metals. By this time there had been built a long-bedded, hand-rabbled reverber-atory roaster with a hearth of about 40 by 10 ft. in size, and in this matte and ore, crushed at the sampling mill, was treated. When, in 1892, I took control of this works, called& now the Germania Lead Works, three other roasters had been added, but the prac-tice of heap-roasting continued. This had the merit of needing no equipment, and of doing good work, because the pieces that were imperfectly roasted went back upon the next roast heap. At this time, when some suitable lump ore was obtainable, I roasted in heaps, in a satisfactory way. By 1892, the Bruckner cylinder roaster had been installed, which, compared with the reverberatory roaster, reduced labor. As such a cylinder revolves, a talus of ore is formed within it and at the same time fresh surfaces are exposed to the air, but the trouble was that the air did not reach to the bottom of the cylinder. This we corrected by placing a steam jet at the fire-box end, to project the air down-ward upon this stagnant ore, thus increasing the speed and completeness of roasting without at the same time increasing dust formation. The firing, if skilfully done, gave a somewhat sintered product, but with certain ores a slight access of heat over the normal would cause accretions to form within the cylinder near the fire end. These could be cut off by running back the fire box and barring off the crusts. It was in 1895 that the Bruckner cylinders at the Arkansas Valley plant, Leadville, were giving unsatis-factory service and I was called in to investigate. The steam jet was put in use as at the Germania Lead Works, but we found that, due to the altitude (10,500 ft.), combustion was feebler than at sea level or even at 4000 to 5000 ft. Later it appears, as Colonel Dwight states, that R. D. Rhodes and Mots sought to increase the air supply by admission through perforated tiles, but the trouble was due to the air itself.

Jan 8, 1922

By W. C. Ellis, E. S. Greiner

METALLIC titanium has been prepared in small quantities since the beginning of the century. Hunter1 reported in 1910 that he obtained a malleable product of 99.9 pct purity by the reduction of the tetrachloride by sodium in a closed container. Later Van Arkel2 and Fast3 prepared small quantities of malleable titanium by thermal decomposition of titanium iodide. Another method for producing malleable titanium from tetrachloride was reported by Kroll4 who used magnesium as the reducing agent. More recently Dean, Long, Wartman, and Anderson5 working at the U.S. Bureau of Mines have reported the preparation of the metal on a pilot plant scale by the reduction of titanium tetrachloride by magnesium in an atmosphere of helium. Their product, which is malleable, was used in the present investigation. Early in 1948 after the work of this paper: was completed Campbell, Jaffee, Blocher, Gurland, and Gonser6 described the strength and working characteristics of pure titanium which was prepared by the iodide method on a scale producing 300 to 600 g per run, in the form of 0.3- to 0.4-in. diam rods. Their product is characterized by low hardness and large capacity for cold work which they attribute to a high degree of purity with respect to oxygen, nitrogen, and carbon. Titanium has a melting point of about 1725°C5 it may be classed as a light metal since the specific gravity is 4.5 g per cc-1. The crystal structure is close-packed hexagonal from room temperature t0 885°C. Above this temperature the structure is reported7 as body-centered cubic. The change in crystal structure has been associated with discontinuities in specific heat8 electric resistance9 and thermoelectric force10 at temperatures near 890°C. It is reported11 that annealed titanium has a tensile strength 0f 78,700 psi which can be increased by cold-work to 123,000 psi. In the present investigation, the lattice constants at room temperature, the thermal expansivity between 30 and 800°C, as well as the electrical resistivity and thermoelectric force against platinum between - 200 and 1000°C have been determined. MATERIALS For the measurements, two series of specimens were prepared from titanium furnished by the U. S. Bureau of Mines. The first was lade from an annealed sintered compact, 0.38 in. thick. Sections of the compact were cold-swaged with intermediate anneals in vacuum to the sizes used. Sizes over 0.25-in. diam were annealed at 1000°C and smaller sizes at 800°C. Specimens originating from the sintered compact are designated in this paper as A. The second series of specimens was lade from a rod of titanium, 0.19 in. in dial, which was cold-swaged with the necessary intermediate anneals to the required sizes. This series of specimens is designated B. The impurities in the specimens of titanium, determined by chemical analysis, are given in Table I. Oxygen and nitrogen which were not determined by analysis, are probably present although in small quantities in view of the ductility of the material.

Jan 1, 1948

By S. A. Herres, A. R. Elsea

Temper brittleness refers to the loss in the notched-bar impact resistance encountered in most medium- or low-alloy steels when they are tempered within the temperature range of 700 to ll00°F or slowly cooled from a higher tempering temperature. Temper brittleness is important because it impairs the service properties of otherwise suitable steels over the range of hardnesses obtained at medium tempering temperatures and because it is impractical to cool pieces of large section rapidly enough from higher tempering temperatures to prevent temper brittleness. The problem of temper brittleness has always been closely associated with ordnance manufacture because armor plate and gun steels require good shock resistance and are often heat treated in heavy section. However, it is now realized that many brittle failures in structural alloy steel parts are attributable to temper brittleness, and there is little question that it contributes to the low impact resistance of alloy steels used in the hot-rolled or normalized condition which are slowly cooled from the hot-rolling or normalizing temperature. Recently Hollomonl has presented a comprehensive summary of the literature on the subject and an excellent description of the manner in which temper brittleness affects the notched-bar impact resistance and other mechanical properties of steel. Carpenter and Robertson2 have given a good analysis of the probable mechanism of temper brittleness, which is similar in many respects to the precipitation-hardening phenomenon. Fig 1 is their diagram illustrating the response to tempering of a susceptible steel. Three changes are recognized as the temperature of tempering a previously quenched steel is raised: (1) pre- cipitation occurs more rapidly and to a greater extent and the notched-bar impact value falls to a minimum; (2) coalescence of the precipitated particles begins to be effective and the impact values for both rapidly cooled and slowly cooled specimens increase; (3) the precipitate goes back into solution at higher tempering temperatures and the impact values of specimens cooled rapidly enough to retain the solution increase, while reprecipitation occurs in slowly cooled specimens and their impact values decrease again. No change must proceed to completion before the following one begins and there is overlapping in temperature ranges. Although there have been a large number of experimental investigations of temper brittleness, insufficient evidence has been accumulated to permit definite identification of the precipitate wnich causes temper brittleness nor have the specific effects on it of various alloy elements and impurities in steel been definitely established. This lack of evidence is largely a result of the lack of a suitable measure for temper brittleness. Temper brittleness is evidenced by an increase in the temperature of brittle failure of notched-bar impact specimens, but most of the data are in the form of an arbitrary susceptibility ratio of the room-temperature impact value for specimens quenched from a high tempering temper to that of similar specimens furnace cooled from the temper. It is obvious that this numerical ratio is dependent upon the type of specimen used and the specific conditions of testing rather than the characteristics of the steel. In general, manganese, chromium, and nickel alloy steels are most susceptible to temper brittleness and molybdenum has heen used to decrease

Jan 1, 1950

By MCA Woolsey

(Butte. Meeting, August, 1913.). IN metallurgical circles it is known widely, but somewhat vaguely, that the ease of: reduction of metallic oxides depends largely on the way they have been prepared. It is likewise known that different forms of carbon have different and greatly varying reducing powers. It is the purpose of this paper to show somewhat more definitely and scientifically these facts. Some years ago the writer published an account of pyrometric determinations of the reduction- temperature of zinc oxides variously prepared and of several kinds.1 In said paper it was shown that the temperature it which zinc oxide evolves zinc according to the equation Zn0. +' C = Zn + CO depends upon the ;nature of:., the.' two reacting bodies. The determinations bad a range of accuracy of from 2° to. 6° C.,whereas differences were found to. amount to an extreme. of 90° C. :.86 the differences are real ones and must have, definite cause. The equation of boiling water, (H20)4 = 4 (H2O) has a fixed temperature for equilibrium of 100° C. at 760 mm. pressure. , In general, all equations. reacting e in .the liquid or the gaseous phase have-well-defined constant physical conditions which govern the equilibrium point and reaction velocities. In a reaction where we have one or more solid phases, the temperature conditions requisite for the unbalancing of the stable system are found to vary. These variations are due to the fact that in a solid there is a very complex molecule and it is not, a question solely of the tearing away of two interlocked atoms, but also of the destruction of a complex molecule containing hundreds, or possibly thousands, of smaller molecules.

Jan 7, 1913

By K. E. Gray, M. S. Seth

In Part I of this work,1 equations of elasticity were formulated for transversely isotropic, axisymmetric, homogeneous, porous media exhibiting pore fluid pressure. Equations of elasticity and the thermal analogy method were used to determine transient horizontal, tangential, and vertical stresses and radial displacement in a semi-infinite cylindrical region when either a constant rate of pressure or a constant rate of flow is maintained at the wellbore. In this paper, the approach presented earlier is extended to finite reservoirs for the cases of (1) steady-state flow, (2) constant pressures at the well bore and outer boundary and (3) constant pressure at the wellbore and no flow at the outer boundary. Results of this work show that radial and tangential stress gradients are high near the wellbore but diminish rapidt; away from the well; the vertical stress gradient behaves in the same way but is less severe. Radial stresses are compressive or neutral, whereas tangential and vertical stresses may be tensile, neutral or com-pressive, depending upon the boundary conditions, the physical Properties of the system and the radial distance involved (vertical stresses are always compressive in an unbounded system1. For constant boundary pressures, both radial and tangential stresses increase with time whereas they both decrease for a closed outer boundary and constant pressure at the wellbore. The vertical stress decreases with time for both systems. For steady-state systems, radial displacement may be positive or negative, depending upon the dimensions of the system, the pressure differential and the porosity. Radial displacement may be positive or negative for a closed outer boundary but is positive for constant pressures at both boundaries. INTRODUCTION The importance, utility and complexity of a realistic appraisal of the stress state at and local to a wellbore were indicated in Part I. In this paper the analytical approach presented earlier is extended to finite, cylindrical reservoir geometry for the cases of (1) steady-state flow, (2) constant pressures at wellbore and outer boundary and (3) constant pressure at the wellbore and no flow at the outer boundary. Other than the outer boundary of the reservoir being finite, the physical system and assumptions pertinent thereto are the same as before. The reader may wish to review the mathematical development through Eq. 49 of Part I before proceeding here. SOLUTION FOR GENERAL BOUNDARY CONDITIONS THERMAL STRESSES AND DISPLACEMENTS Since normal stresses do not exist at the free boundaries of a system subjected to thermal stresses, the boundary conditions are

Jan 1, 1969

By O. Cuscoleca

The Austrian plants at Donawitz and Linz were the first to blow steel with high purity oxygen. The paper shows how the process was developed and gives a survey of the results achieved to date. Compared with open hearth steel of equal quality, the obvious advantages of oxygen steel are the low investment and conversion costs. The nitrogen content of oxygen steel is not higher than that of good open hearth steel. Rimmed and killed steel products made by the oxygen process are superior to rimmed and killed steel products made by the best open hearth process. TWO new steel plants using the principle of making steel with high purity oxygen went into operation in Austria, one at Linz (Vereinigte oster-reichische Stahlwerke) in November 1952 and the other at Donawitz (dsterreichisch-Alpine Montan-gesellschaft) in May 1953. An estimated 330,000 metric tons were produced by the two plants in 1953, the first year of operation. In 1954 production by Austrian plants- using the high purity oxygen approach will be raised to 450,000 metric tons. This will be in addition to facilities in Huckingen (Man-nesmann A. G., Düsseldorf, Germany), those planned and under construction at Hamilton, Ontario, Canada (Dominion Foundries and Steel, Ltd.), and elsewhere. It is expected that by 1955 a total capacity of one million tons of high purity oxygen steel will be available. At the close of the last century, because of increasing availability of scrap, open hearth steel production forged ahead at an ever increasing pace. This caused world steel production to rise faster than pig iron production and finally to overtake it. In 1911 65 million tons of steel were produced against 64 million tons of pig iron. World steel production was 209 million tons in 1951, while pig iron output was only 147 million tons. The 1951 breakdown for steel shows 118 million tons made from pig iron, while the balance, 91 million tons or 44 pct of the total tonnage of steel produced, was made from scrap. This increase in crude steel production on a basis of high scrap consumption led to the world market scrap shortage and soaring scrap prices. In the United States and other nations, production of converter steel has fallen far behind that of open hearth steel. The surplus of processing scrap, un-absorbable by converting mills and thus a welcome source for open hearth and electric melting shops in the past, together with regular scrap purchases, no longer can meet requirements of both open hearth and electric steel production in Europe. In addition, recent modification of the basic bessemer process, blowing with oxygenated blast, substantially raised the scrap capacity of these plants. Any further expansion of world steel production will necessitate utilization of self-containing processes in regard to scrap because of the shortage.

Jan 1, 1955

By E. A. Holbrook

MINING Metallurgy, and Petroleum Engineering department in our colleges are facing a crisis; indeed, conditions that threaten their very existence. Unless the Army, Navy, and War Manpower Commission change their present policy, within two years mineral industries education as now carried on will die, because no ablebodied students will be left in the course. If this is the decision of our responsible governmental agencies we of the mining schools must perhaps accept it as a war measure. It might be well however, for the executive of our mining metallurgical, and oil companies to look ahead a, to where they are to recruit a supply of young technically trained engineers. You can no more operate a mine, a steel plant or an oil company without trained engineers than you can operate a battleship without mechanical and electrical engineers.

Jan 1, 1943

By W. A. Hockings, M. E. Volin, A. L. Mular

Batch grinding tests at short times were made in a laboratory rod mill with 10 x 14 mesh quartzite in corn syrup-water mixtures of varying viscosity. The weight fraction broken and size modulus were found to be independent of viscosity up to 20 cp, but at higher viscosities breakage of the feed decreased while the size modulus increased. The mechanisms of the effect of viscosity are discussed on the basis of particle dynamics. The effect of viscosity of the suspending medium on grinding has not been accorded much attention, although both wet and dry grinding are used in bene-ficiation processes and the viscosities of water and air differ greatly. schweyerl investigated the rates of grinding of quartzite in a pebble mill with air, water and glycerol as the suspending media and found the rate in terms of new surface developed per thousand revolutions of the mill to be constant and dependent on viscosity up to 20,000 rev, but to decrease and become independent of viscosity for longer grinding times. Based on considerations of the drag forces exerted on suspended particles and on the grinding media under turbulent and laminar flow conditions, viscosity can be expected to inhibit the rate of grinding in a given system as it changes the flow conditions from turbulent to laminar. The objective of this study was to determine the effect of viscosity of the suspending fluid in the batch grinding of a homogeneous feed of uniform size for short residence times, a region of more practical interest than the long times investigated by Schweyer. In actual grinding operations, the viscosity of the fluid does not change, but the consistency (apparent viscosity) of the pulp increases with additions of fines. In this study the consistency of the pulp was not measured because it was thought that the grinding times were too short to alter the apparent viscosity appreciably.* *Minus 200 mesh quartz at 65% solids has an apparent viscosity of about 25 cp as measured by a simple consistometer. Personal communication from D. F. Kelsall to A. L. Mular. For the purposes of this study, the effect of viscosity on grinding can be shown sufficiently well on the basis of the cumulative weight fraction finer than the feed size at any time, and the size modulus, ku, of the finer than feed sizes. The parameter, ku, is obtained from a form of the Gaudin-Schuhmann equation. METHOD AND MATERIAL The grinding tests were accomplished in a laboratory rod mill 10-1/2 in. long and 8 in. bore with a 20-lb rod charge consisting of two 1-in., eight 3/4-in., eight 1/2-in., and eight 1/4-in. diam rods. The mill speed was 43.2 rpm. Charges of 400 g 10 x 14 mesh Wisconsin quartzite** were ground for times of 60, **Courtesy of Minnesota Mining and Mfg. Co. 120, 180 and 240 sec in 500 cc of fluid made up of corn syrup and water in measured proportions. The temperature of the pulp was measured immediately upon completion of grinding, and the size distribution of the quartzite was determined by a wash-wet-dry screening technique. Corn syrup was chosen because of its high viscosity and ideal viscous behavior, and also because its density is not greatly different from that of water. The viscosity of each fluid mixture was measured with an Ostwald viscometer at 25 C. and a correction was made for the temperature of the pulp according to tabulated values for sucrose solutions. The density differences were so small that they probably did not significantly affect breakage. RESULTS AND DISCUSSION The conditions of the grinding tests, computed viscosities, weight fractions finer than the feed size and values of a and ku are listed in Table I. The values of a and ku were taken from the linear portions of the log-log plots of cumulative weight fraction finer vs size for the various grinding times. The plots for tests in fluids of average viscosity 8.6 cp are shown in Fig. 1. In general all of the sets of curves were linear throughout most of the size

Jan 1, 1965

By J. J. Gilman

Examination showed that characteristic cleavage step patterns are observed on the cleavage surfaces of undeformed, slipped, bent, twinned, compressed, and indented zinc crystals; and the effect of temperature is discussed. Dimples were seen to produce cleavage steps in a treelike pattern in otherwise undeformed crystals. The steps seem to originate when cracks intersect screw dislocations. IT has been known for a long time that the path of fracture in polycrystals may be discontinuous (see Jaffe, Reed, and Mannl for review). Recently, Kies, Sullivan, and Irwin2 have proposed, and given evidence, that crack propagation is discontinuous within individual crystals as well. Other evidence has been given by Low.' When discontinuous cracks within a crystal join together to make a macrocrack, the lamellae between each set of two cracks are torn somewhere, forming small cliffs. These cliffs appear as lines when the cleavage surface is observed microscopically.4,5 The lines have been called vein, tree, and riverlike markings by various authors, and they have sometimes been mistaken for fissures. The descriptive term cleavage steps is used in this paper. Cleavage steps vary in height over a wide range of values, from molecular dimensionsG to lor. and larger. Kies, Sullivan, and Irwin,2 as well as George,' have shown that the gross cleavage step patterns for plastics, polycrystalline metals, and for mono-crystals are sometimes similar. Thus, they depend mostly on the mechanical variables that prevail during cleavage and are relatively insensitive to the structure of the material. For example, parabolic markings2,7,8 sometimes result when cracks open up ahead of, and not coplanar with, the main crack front. If the advance crack has the same velocity as the main crack, their intersection line is a parabola, otherwise it is a hyperbola or an ellipse. The patterns are strongly affected by differences in crack velocities. This results in chevron patterns which point to the place of origin of the main crack. It is the purpose of this paper to demonstrate the existence of a mechanism of cleavage step formation which is a continuous rather than a discontinuous process. Also, certain characteristic step patterns are described, and the strong effect of temperature is shown. The specimens were zinc monocrystals (grown from 99.999+ pct pure metal). These were cleaved at room temperature and at — 196°C. Results and Discussion Cleavage step patterns are highly variable from point to point on a given specimen, as well as from one specimen to another. Although the patterns shown in the photographs are typical, they have been selected for graphic illustration. Figs. la and lb compare undeformed crystals that were cleaved at —196 °C and room temperature, respectively. Cleavage at room temperature (Fig. lb) resulted in a higher density of high steps (dark black lines) and enhanced the visibility of the fine background markings. Deformation by simple slip caused no marked change in the step patterns until the glide strain reached about 1.0. But, as Fig. lc shows, the density of high cleavage steps was greatly increased by large glide strains. Corrugations lying perpendicular to the slip direction may also be seen in Fig. lc. These are caused by deformation bands. The cleavage resistance of the crystal of Fig. lc was very high compared to undeformed crystals (estimated by the force on a needle required for cleavage). Striking and varied cleavage step patterns were observed on bent crystals. Two characteristic patterns that were observed on crystals bent at 25°C, and cleaved by reverse bending at —196°C, are shown in Figs. 2a and 2b. The first, Fig. 2a, consists of V-shaped lines similar to the parabolas of other materials2,7 Fig. 2b shows a pattern that is the equivalent of Fig. la, consisting of faint background lines with a few higher step markings. Cleavage of bent crystals at room temperature resulted in Figs. 2c and 2d. Now, the cleavage step lines show a strong tendency to follow one of two perpendicular paths. In Fig. 2c (bent once), many of the cleavage step components that lie parallel to the bend axis are assembled into irregular lines. In Fig. 2d (bent twice), the cleavage steps again tend to consist of two perpendicular components, but neither of the components is assembled into lines. Also, the step density is higher.

Jan 1, 1956

By W. C. Ellis, E. S. Greiner

Metallic titanium has been prepared in small quantities since the beginning of the century. Hunter1 reported in 1910 that he obtained a malleable product of 99.9 pct purity by the reduction of the tetrachloride by sodium in a closed container. Later Van Arke12 and Fast prepared small quantities of malleable titanium by thermal decomposition of titanium iodide. Another method for producing malleable titanium from tetrachloride was reported by Kr0ll4 who used magnesium as the reducing agent. More recently Dean, Long, Wartman, and Anderson5 working at the U.S. Bureau of Mines have reported the preparation of the metal on a pilot plant scale by the reduction of titanium tetrachloride by magnesium in an atmosphere of helium. Their product, which is malleable, was used in the present investigation. Early in 1948 after the work of this paper was completed Campbell, Jaffee, Blocher, Gurland, and Gonser6 described the strength and working characteristics of pure titanium which was prepared by the iodide method on a scale producing 300 to 600 g per run, in the form of 0.3- to 0.4-in. diam rods. Their product is characterized by low hardness and large capacity for cold work which they attribute to a high degree of purity with respect to oxygen, nitrogen, and carbon. Titanium has a melting point of about 1725 C," it may be classed as a light metal since the specific gravity is 4.5 g per cc-I. The crystal structure is close-packed hexagonal from room temperature to 885°C. Above this temperature the structure is reported7 as body-centered cubic. The change in crystal structure has been associated with discontinuities in specific heat,8 electric resistanceg and theimoelec-tric force10 at temperatures near 890°C. It is reportedll that annealed titanium has a tensile strength of 78,700 psi which can be increased by cold-work to 123,000 psi. In the present investigation, the lattice constants at room temperature, the thermal expansivity between 30 and 800°C, as well as the electrical resistivity and thermoelectric force against platinum between — zoo and I000 C have been determined. Materials For the measurements, two series of specimens were prepared from titanium furnished by the U. S. Bureau of Mines. The first was made from an annealed sintered compact, 0.38 in. thick. Sections of the compact were cold-swaged with intermediate anneals in vacuum to the sizes used. Sizes over 0.25-in. diam were annealed at I000°C and smaller sizes at 800°C. Specimens originating from the sintered compact are designated in this paper as A. The second series of specimens was made from a rod of titanium, 0.19 in. in diam, which was cold-swaged with the necessary intermediate anneals to the required sizes. This series of specimens is designated B. The impurities in the specimens of titanium, determined by chemical analysis, are given in Table 1. Oxygen and nitrogen which Were not determined by analysis, are probably present although in small quantities in view of the ductility of the material.

Jan 1, 1949

By Woolsey McA. Johnson

In metallurgical circles it is known widely, but somewhat vaguely, that the ease of reduction of metallic oxides depends largely on the way they hare been prepared. It is likewise known that different forms of carbon have different and greatly varying reducing powers. It is the purpose of this paper to show somewhat more definitely and scientifically these facts. Some years ago the writer published an account of pyrometric determinations of the reduction temperature of zinc oxides variously prepared and of several kinds.' In said paper it was shown that the temperature at which zinc oxide evolves zinc according to the equa-tion ZnO + C = Zn + CO depends upon the nature of the two reacting bodies. The determina-tions had a range of accuracy of from 2° to 6°C., whereas differences were found to amount to an extreme of 90' C. So the differences are real ones and must have a definite cause. The equation of boiling water, (H2O)4 D 4 (H2O) has a fixed temperature for equilibrium of 100° C. at 760 mm. pressure. In general, all equations reacting in the liquid or the gaseous phase have well-defined constant physical conditions which govern the equilibrium point and reaction velocities. In a reaction where we have one or more solid phases, the tempera ture conditions requisite for the unbalancing of the stable system are found to vary. These variations are due to the fact that in a solid there is a very complex molecule and it is not a question solely of the tearing away of two interlocked atoms, but also of the destruction of a complex molecule containing hundreds, or possibly thousands, of smaller molecules. In other words, there are two forces to be overcome: a certain

Jan 1, 1914