Search Documents

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

Hydrogen forms a beta-stabilized system with titanium, with a beta eutectoid at about 300°C and 44 atomic pct H2. 'The solid solubility of hydrogen in alpha decreases from about 8 to about 0.1 atomic pct from 300°C to room temperature. Hydrogen has little effect on tensile properties, but decreases notch-bar toughness to a large degree. This latter effect appears to be the result of increased notch sensitivity. PRIOR to this investigation, only a small amount of information was available on the effect of hydrogen on the mechanical properties of titanium. The effects of the other interstitially soluble elements, carbon, oxygen, and nitrogen, had received detailed study. Jaffee and Campbell1 indicated that hydrogen up to 1 atomic pct did not affect tensile properties deleteriously. Pitler' indicated that 1 atomic pct H, in titanium reduced the impact strength appreciably, but his alloys contained appreciable amounts of oxygen, and it was difficult to attribute the embrittlement entirely to hydrogen. The high temperature portion of the equilibrium diagram for the Ti-H system was established by McQuillan," and his data generally corresponded with the results of Kirschfeld and Sieverts," Gibb and Kruschwitz," Bevington, Martin, and Mathews," and other investigators. The lower concentration limit of the hydride phase varied considerably among investigators, and Gibb and Kruschwitz9 ad shown that small amounts of contaminants in either titanium or hydrogen caused considerable variation in this lower limit. In view of this pronounced effect of contaminants, the extrapolated value of McQuillan's, about 48 atomic pct at the 325°C eutectoid, appeared the most reasonable. McQuillan's lowest experimental value was 54 atomic pct at a temperature of 450 °C. The density of titanium had been shown to decrease with increasing hydrogen content, but discrepancies were noted among the various investigations. The best values indicated that the density was decreased from 4.56 grams per cc at 0.27 atomic pctl to 3.84 grams per cc at 61.3 atomic pct? This investigation was conducted to determine the effects of hydrogen on a titanium, both in high purity and commercially pure metals, and on high purity a titanium alloys. Material and Fabrication The literature indicated that impurities in either the hydrogen or the titanium must be kept to a minimum. For this reason, the initial studies were made with high purity iodide-refined titanium. The vendor's analysis of the iodide titanium and the hydrogen content of the as-fabricated Y4 in. diameter rods are shown in Table I. Two 1 lb ingots were prepared by arc melting under argon in a water-cooled crucible, using a water,cooled tungsten electrode. This equipment has been described.' As-cast Brine11 hardness numbers of 88 and 58 for these ingots were low enough to insure that the high purity of the metal was maintained during arc melting. The ingots were hot forged to % in. diameter rods at 800°C, cleaned by grit blasting, and then cold swaged to Yz in. diameter rods. The rod was then air annealed at 725 "C, ground to remove scale, and cold swaged to Y4 in. diameter (75 pct reduction in area). The material was then annealed for 1 hr in argon at 800°C to develop an equiaxed a grain size of about 0.05 mm. Micro tensile specimens and microimpact specimens were machined from this rod prior to treatment in the Sieverts-type absorption apparatus. Two lots of commercially pure RC-55 titanium were also used in this investigation to determine the effects of hydrogen and the normal impurities on mechanical properties. The commercially pure RC-55 alloy was obtained in the form of % in. diameter rod. The analysis of this material is also given in Table I. The % in. diameter rods were hot swaged

Jan 1, 1955

By A. Raman, P. P. Singh

The constitution of the La-Rh system was studied by powder X-ray diffraction, metallopaphic, and differential thermal analysis techniques and an equilibrium diagram is presented. Eleven intermediate phases occur in the system and the crystal structural data for nine of them were determined. La3Rh crystallizes in an orthorhombic structure of undetermined type, whose unit cell is obtained by doubling the 'a; and 'c,,' edges of an FesC type unit cell. The other intermediate phases of the system are LarRh-3( undetermined structures also occur in the system. LaRh, undergoes a polymorphic phase transformation at 1240°C. LaRh3 and La2Rh7 also exhibit polymorphisnz. The phases Laah and LazRh7 melt congruently. The latter undergoes a eutectoid transformation into LaRh, and Rh at 1205°C. Laah3 is formed by a peritectoid reaction between Laah and La,Rh,,. The other Phases result from peritectic reactions between the liquid and the adjacent rhodium-rich phases. The intermediate Phases of the La-Rh system are compared with those of the La-Co and La-Ni systems. DURING the course of a detailed investigation to study the occurrence of CrB, FeB, A1B2, and related structures in the rare earth alloys it was found that much information is lacking for the rare earth noble metal systems. Although the structures of several rare earth alloys containing the noble metals at the AB and AB2 stoichiometries have been reported, the occurrence of related structures at other stoichiometries has not been studied. We have initiated a project to study the crystal structural features of selected rare earth-rhodium alloys and to map the equilibrium diagrams of representative systems with conventional methods. The results of our investigation in the La-Rh system are presented in this paper. Two phases were known in the La-Rh system. LaRh has the CrB-type structure.' LaRhz is a MgCu2-type Laves phase.z EXPERIMENTAL PROCEDURE Alloys weighing less than 1 g were prepared from commercially pure lanthanum (99.9 pct +), supplied by Lunex Company, Pleasant Valley, Iowa, and rhodium (99.92 pct +), supplied by Engelhardt Industries, Newark, N.J., in a conventional arc melting furnace under argon atmosphere. The buttons were turned upside down and remelted three times to insure homogeneity in the samples. Since negligible loss of material was encountered during melting, a chemical analysis of the alloy buttons was not undertaken. Powder specimens for X-ray diffraction studies in the as cast state were then prepared. The buttons were wrapped in thin molybdenum foils and homogenized by heating in vacuum at suitable high temperatures for more than 1 week. They were then broken into three or four pieces for annealing experiments. The pieces were wrapped in molybdenum foils and annealed at various temperatures in evacuated quartz capsules. The annealing was carried out for 2 hr at or above 1200°C, 1 day at temperatures close to llOO°C, 2 days at 1000°C, and for 1 week at temperatures below 1000°C. After annealing the alloy pieces were again broken and powder specimens for X-ray diffraction were prepared. The powders of the lanthanum rich alloys with more than 80 at. pct La were prepared by filing. The filings were sealed in molybdenum tubings and stress-relieved at 600°C in vacuum. It was not deemed necessary to stress-relieve the powders of the other alloys, since the alloys were very brittle and were ground easily. POWDER X-RAY DIFFRACTION X-ray diffraction photographs of powders (-325 mesh size) of the alloys in the as cast and annealed states were prepared in a Guinier-de Wolff focussing camera with copper K, X radiations. These patterns were studied to identify the stoichiometries and the crystal structures of the intermediate phases. The lattice parameters of the phases were calculated after minimizing the differences between the observed sin2 6 values, calculated from the diffraction angles 8, and the sin2 8 values, calculated using approximate lattice constants obtained from a few lines. These differences were minimized manually to less than 0.0005. The latLice constants are judged to be accurate to *0.005A for values less thp about 10A and to k0.01~ for values greater than 10A. The relative intensities of the lines were calculated using a computer program written by Jeitschko and Parthk.~ No attempt was made to refine the atomic positional parameters in the phases. METALLOGRAPHY The phase equilibria in the investigated alloys in the as cast and annealed states were also studied by metallographic examination. The polished specimen surfaces were etched with 10 pct picric acid in alcohol (alloys up to 25 pct Rh), concentrated picric acid (from 25 to 37.5 pct Rh), 2 pct nital (40 to 50 pct Rh), 10 pct nital (from 50 to 66.7 pct Rh) and with concentrated 48 pct HF for the other rhodium-rich alloys. Selected microstruture~ were then photographed using a Po-laroid Land camera. THERMAL ANALYSIS Differential thermal analysis of the alloys was carried out in DTA-668 Stone differential thermal ana-

Jan 1, 1970

By P. Shahinian, R. L. Stegman, M. R. Achter

Creep strength has been determined as a function of oxygen pressure for nickel at 510" and 600°C. Creep-rupture life drops from its highest value at the ultimate vacuum of 10-7 torr to a high pressure plateau of nearly constant life which, at 600°C, commences at torr. This behavior is described in terms of a model that relates surface gas adsorption and the generation of fresh crack surfaces. In a calculation based a this model the predicted pressure beyond which the creep strength should not decrease further has been found to agree well with the observed value. The introduction of oxygen during creep in vacuum was found to cause a prompt rise of the creep rate. The magnitude of the environmental effect was much less than generally observed in fatigue and this is attributed to the diffarent crack morphologies in creep and fatigue. GASEOUS environments are known to affect creep resistance adversely1-5 but the effects have received less attention than the much larger ones in fatigue. At low temperatures it has been shown for nickel that the creep rates are faster and the rupture lives are shorter in air than in vacuum and that these environmental effects can be correlated with faster crack growth rates in the reactive environment.' In support of a mechanism of gas adsorption at the crack tip to explain the above effects, a calculation based on kinetic gas theory showed that surface coverage by gas was not as rapid as the exposure of fresh metal at the crack tip in the ultimate vacuum but was in air.7 In fatigue a number of investigations have demonstrated that the reduction of life with gas pressure usually follows a step curve with most of the reduction occurring in a transition range at intermediate pressures and little or no change at high and low pressure.8 There have been no studies, however, in which creep strength has been determined as a function of reactive gas pressure to see whether similar effects would be found. This investigation was undertaken to study the kinetics of the environmental effect in the creep of nickel. EXPERIMENTAL PROCEDURES The environmental creep apparatus was constructed to minimize many of the experimental conditions which can cause scatter in data. Dead weight loading is employed and weights are contained within the environmental chamber to eliminate bellows and the necessity for compensation for gas pressure changes. Elongation over the specimen gage length is recorded from a Riehle Model DV Controlled Environment Extensometer which provides readout to 2.5 x 10- in. Temperature is monitored and controlled from a thermocouple at- tached to the specimen gage length to +0.5oC or better. The freon trapped oil diffusion pump vacuum system included an auxiliary liquid nitrogen trap and, with a wide range variable conductance leak valve, pressures from the ultimate vacuum of 10"7 to l03 torr of any desired gas are obtainable. Pressure is measured by means of a hot filament ionization gage below 10"3 torr and a NRC Model 530 Alphatron Vacuum Gauge above 10-3 torr. The oxygen, which was leaked into the environmental chamber, was an Aviator's Grade of 99.5 pct purity with a dew point of -80°F. Analysis of the nominal 99.8 pct Ni showed the following percentages of major impurities: 0.02 C, 4.01 Mn, 0.005 Si, 0.01 Cu, 0.02 Fe, and 0.034 Mg. Cylindrical specimens were machined with a 0.180

Jan 1, 1970

By George Hallerman, R. J. Gray

In the customary method of studying age hardening, the process of aging is interrupted by cooling the specimen and measuring its room-temperature hardness. However, the aging process may be conveniently measured while it is occurring at an elevated temperature by a series of hardness measurements at suitable time intervals. The latter method gives data void of complications that might result from processes occurring during the quench, and the data may be more indicative of the alloy's properties at elevated temperatures. The elevated-temperature hardness tester1 used in the present study employed a dead-weight loading system with a synthetic sapphire Vickers-type in-denter mounted in a molybdenum holder. The tests were performed in a vacuum of l0 to 10 torr. Hardness impressions were made by applying a 2-kg load for 15 sec. Although the hardness impressions made in the tester at elevated temperatures were measured at room temperature, the correction for thermal contraction during cooling was insignificant and therefore neglected. The two methods of obtaining age-hardening data were compared using eighteen samples of Haynes alloy No. 25* which had been annealed for 2 hr at 2250°F (1232°C). The test surfaces of the 1 by 1 by 1/4-in. samples were ground and then polished on vibratory polishers2 prior to testing. Three groups of five samples were aged at 1400°, 1650°, and 1800°F (760°, 899", and 982°C) for 4, 16, 32, 64, and 100 hr and then water-quenched. Room-temperature hardness as a function of aging time for these samples is shown in the broken lines of Fig. 1. Only one sample for each of the three temperatures was necessary to determine the hardness of the alloy at the aging temperatures with the elevated hardness tester. The specimens were heated isothermally and hardness impressions were made after various time intervals up to 100 hr. The results of these determinations were represented by solid lines in Fig. 1. Comparison of the two sets of curves shows, as expected, the hardness values determined at the aging temperatures are lower than the room-temperature hardness of the quenched specimens and the hot-hardness values reflect a strong tempera-

Jan 1, 1964

By Tracy Jarrett

THE alloying of various elements with gold to produce different colors is an old art, but the effect of each element or combination of elements is not generally known. Investigations have been made in this field by F. E. Carter,1 E. M. Wise,2 and L. Sterner-Rainer.3 It is the intent of this paper to present in schematic diagrams the effects of various ele¬ments upon the color and the melting point of gold alloys. In this investigation 2-oz. melts made in a high-frequency induction furnace were used for all tests. The melting points were determined by the use of a calibrated chromel-alumel thermocouple sealed in a thin-walled alundum tube. The couple was then submerged in the molten metal and the freezing and melting points were determined by using a Leeds and Northrup potentiometer. By checking several melts using copper, zinc and gold, it was found that the accuracy of determining the melting point was within ± 5° F. To determine the differences in colors and to classify them, a wet tissue paper was placed over the polished samples and examined under a uniform white light. The 2 by ½ by 0.045-in. samples were cut from 50 per cent cold-worked strip. The original ingot was 3 by ¼ by ¾ in. This visual comparison, although not scientifically exact, served as a quite satisfactory means for determining and classifying these differences. The base alloys, or "hardeners," were first made up and analyzed, after which the gold and silver were added. This method of making up the alloys was chosen so that the same base alloy could be used for the gold alloys of different karats. The first series consisted of gold, copper, zinc and nickel, the copper comprising from 85 to 65 per cent of the content of the "hardener" and the zinc and nickel replacing copper. The second series consisted of gold, silver, copper, zinc and nickel, the copper comprising from 85 to 65 per cent of the content of the hardener with the silver, nickel and zinc replacing copper. There was no particular reason for choosing these combinations, except that they gave a color range from red-pink to white.

Jan 1, 1939

By William L. Batt

IT IS becoming increasingly evident to management that it has other obligations than merely to earn dividends for stockholders. The head of one of America's largest organizations has stated it in these words: "There rests upon them a far broader responsibility than the mere production of goods and services, or solely the interests of their stockholders. They must assume the important obligation, through proper policy, of attuning industry to a rapidly changing world, from social as well as economic standpoints." Stockholders might as well reconcile themselves, therefore, to the fact that management cannot always put their interests first in the obligation of business enterprise: and that the legitimate requirements of customers and employees have acquired a new significance which must be recognized if the business of today is to prosper.

Jan 1, 1938

By Orson Cutler, Shepard

THE OBJECT of this paper is twofold: (1) To analyze the forces that cause air bubbles to spread on mineral surfaces in the flotation process; and (2) To develop a rational expression that will serve as a criterion of the floatability of minerals, to the end that the efficiencies of various flotation reagents can be accurately compared. Heretofore, the subject of the spreading of air bubbles has been dismissed with the statement that the surfaces of minerals on which bubbles spread are water-repellent. Imperfect understanding of the forces involved has led to the use, hitherto, of various erroneous formulas for the calculation of the comparative effectiveness of flotation reagents.

Jan 1, 1932

BROWN iron ore reserves of Franklin county are being proved economical by Heavy-Media separation at the Blackburn mine of the Shook & Fletcher Supply Co. about 120 miles north-west of Birmingham. The ore occurs under a cover of ferruginous chert and gravel and these materials are also disclosed as streaks in the ore body as it is mined. Previous methods of jigging and hand sorting the ore became too expensive because of rising wages but the use of Heavy-Media separation has proved economical and is making Franklin county the most promising source of additional reserves of brown ore.

Jan 12, 1950

NEW YORK SECTION ALLEN H. ROGERS, Chairman, H. C. PARMELEE, vice-chairman, FOREST RUTHERFORD, Vice-chairman, W. S. DICKSON, Secretary, 71 BROADWAY, NEW YORK, N. Y. J. E. JOHNSON, JR. F. T. RUBIDGE, Treasurer, P. G. SPILSBURY A meeting of the New York Section was held at The Machinery Club on Friday evening, Oct. 4, 1918, The Chairman, Allen H. Rogers, presiding. The CHAIRMAN.-MOST of us, I suppose, have been affected more or less by The request of The Fuel Administration that we leave our automobiles standing in The garages on Sundays. We shall all be interested in hearing about The situation that has called forth This, request, and The Oil Administrator, Mr. Requa, has kindly come from Washington to Tell us about it. MARK L. REQUA.-I am very glad To Tell you about the oil problem during This war period. The United States is supplying by far The greater part of all The petroleum products consumed in Great Britain, France and Italy. In addition To This, we have had To supply a marked increase in our domestic consumption, not only of The refined products, but of fuel oil as well. The combination has put a strain on The oil industry, which it is very difficult To meet. The oil companies, being under contract, had no option as To who should get Their oil first, and They were delivering pro rata To everybody; manufacturers of furniture were getting oil with The same regularity as Those who were making aeroplanes or munitions, and The oil companies felt that something should be done. The first order with which I had. anything To do was The priority list for The delivery of fuel oil. That list contained 12 classifications, beginning with bunker fuel and railroads, and you will realize The complexity of The situation when you hear that munitions plants are in class 11. The priority list held during The winter, but transportation became so bad, because of The number of ships that were Taken for trans-Atlantic use, that some of The oil companies were not able To deliver more Than about 60 per cent. into class 5, and nothing beyond that point. To add To the Troubles, the Tank-car mileage fell off. The average for 1917 was about 36 miles per car per day. in January, 1918, it dropped To about 8 miles, and it must have been nearly zero in The early part. of February. Because of The extremely severe winter, furthermore, pipe lines were not delivering anywhere near Their normal capacity. A new priority list has recently been promulgated, introducing a few slight changes. Natural gas has been brought under its provisions, and it has been extended To include The Pacific Coast, which was not considered necessary last winter. The situation in The gas industry is not satisfactory; it is estimated that There will be a decrease of 10 To 20 per cent. in The quantity of natural gas available This winter, as compared with last winter.

Jan 11, 1918

By R. L. McCarron, G. R. Belton

The diffusivities of oxygen and sulfur in liquid iron have heen determined hy a capillary technique in which the surface concentrations of the solutes were established by means of appropriate H2/H2 and H2S/H, gas mixtures. Total diffusate and concentration profile results are shown to be in good accord, yielding for- 1560 and Supporting results at 1660°C are also presented. The conditions necessary to avoid gas transport control in this type of experiment are discussed. IN spite of their importance in understanding the kinetics and mechanisms of refining reactions, the dif-fusivities of oxygen and sulfur in liquid iron are not well established. Accordingly, as a first step in studies of rates of solute absorption from the gas phase into liquid iron, new measurements of these diffusivities have been made and are presented in this paper. The only published results for the diffusion of sulfur in pure liquid iron are those of Kawai.' He used a diffusion couple technique in which two cylindrical specimens, one containing sulfur and the other with negligible sulfur concentration, were joined together and held in a refractory capillary. After an experiment, the sample was quenched and the concentration distribution of the solute determined. Kawai recognized that significant changes in solute distribution occurred during melting and freezing and he attempted to correct the concentration profiles for these effects to give a sulfur diffusivity of 4.6 x 10-6 sq cm per sec at 1560°C. The method of correction, however, was not rigorous and the uncertainty in this result cannot be easily assessed. Koslov et a1.2 have reported the diffusivity of oxygen in iron as 7.8 x 10"3 sq cm per sec at 1660°C. This value appears to be unreasonably high but, unfortunately, details of their experiments are not available. Shurygin and Kryuk have used the rotating disc method for a study of oxygen diffusion in liquid iron. In their experiments a silica disc was rotated in liquid iron containing oxygen, and the rate of formation of liquid iron silicate was determined by measuring the decrease in weight of the disc. On the assumption that the rate of dissolution was controlled by the diffusion of oxygen in the iron, the diffusion coefficient was computed to be 5.2 x sq cm per sec at 1550°C. However, the Levich equation, which was used to interpret the rate data, was originally de- rived for the case of mass transfer between a solid disc and a single-phase liquid. The hydrodynamic and diffusion boundary layers in the iron stirred by a disc, via coupling of the silicate melt, may be appreciably different from those predicted by Levich's equations. Recently, Novokhatskiy and Ershov, using an identical experimental method to that of Shurygin and Kryuk, obtained a diffusivity for oxygen in liquid iron of 1.22 x 104 sq cm per sec at 1550°C: no reasons were offered for the disagreement. Schwerdtfeger5 has also recently studied the diffusivity of oxygen in liquid iron. He reacted shallow melts of liquid iron, 0.5 to 1.0 cm deep and contained in high-purity alumina crucibles, with appropriate H20-HZ-He mixtures. The total sample was analyzed, without sectioning, to obtain the average concentration of diffusate. A value at 1610°C of D = 12(3) x 10-5 sq cm per sec was obtained from the results of twenty experiments.= Oxygen profile measurements, which were carried out in three additional experiments using long capillaries and the semiinfinite boundary conditions, indicated a diffusivity about half that computed from the shallow bath experiments. Possible sources of error in Schwerdtfeger's study will be discussed later in this paper. EXPERIMENTAL TECHNIQUE The essential arrangement of the diffusion cell is shown in Fig. 1. The liquid iron was contained in an alumina capillary, 3 to 4 mm diam and 3 to 9 cm long, which was supported by a hollow alumina pedestal and this whole assembly was held within a movable alumina reaction tube. This tube, which was about 7 mm in bore

Jan 1, 1970

By Robert B. Kistler, Ward C. Smith

The borate industry is one of the few sectors of the mining and mineral-processing industry which the United States still dominates. Since about 1927, the United States has supplied over half of the world's total boron and borate raw materials, and many of the chemical derivatives as well. Chiefly responsible for this record are companies producing sodium borates from two large deposits in southern California, at Boron (Kramer) and Searles Lake. The sodium borates, or products derived from borax and borax-containing brines, are the preferred borates for industry because they are soluble in water and combine readily with most other chemicals. Calcium borates are required for certain end uses, and these are produced from smaller colemanite-ulexite-probertite bodies. Sodium-free borate compounds also are produced from boric acid, which can be manufactured from either sodium or nonsodium borate minerals. During the past hundred years, the use of boron compounds throughout the world has risen from a few tons per year to the equivalent of over a million tons of B2O3. Leadership in supplying borates shifted from country to country and from region to region during this period, generally as the result of the development of newly discovered deposits that were better in quality, more accessible, or more economically exploitable than previous sources (Table 1). Primary Products and End Uses The principal borate products offered by primary producers in the United States are listed in Table 2. In general, these products are utilized worldwide by almost all consumers, regardless of the original source of the primary borates, In the United States, the primary borates all originate in southern California. Colemanite is produced as crude or processed crude ore from the Death Valley area and is utilized by the fiber glass and ceramic industries without further treatment. Production from Searles Lake, CA is from brines that are processed in chemical plants where borax and other compounds are recovered and the principal borate products are produced. At Boron, CA, the world's leading producer is mining a deposit of mineral borax and operating a chemical refinery. The mineral borax is mined together with included clay, and refined borax or "10-mol" is one of the refinery products. The mineral and the chemical compound are identical, Na2B4O7 • 10H2O. In addition to ship¬ping all major refined borate products from [ ]

Jan 1, 1983

By A. Simkovich, R. W. Lindsay

The possibility of using sodium sulfide slags to remove copper from ferrous alloys has been investigated by Jordan1 and by Langenberg.2, 3 In these studies, such slags were determined to be capable of removing copper and sulfur from the melt. The present work represents additional effort to clarify the effects of temperature on copper removal. The experiments were performed in a 17-lb induction furnace. Graphite crucibles contained the melts and kept the baths saturated with carbon. Temperatures were measured with a calibrated optical pyrometer and were controlled by manipulation of power input to the furnace. Estimated accuracy of temperatures in this investigation is ± 10°C (18°F) for measurements prior to slag additions, and + 20°C (36°F) after slag formation. The procedure consisted of melting 800 g of electrolytic iron. During this step, powdered graphite covered the exposed iron surface. After a predetermined temperature was reached, copper shot was added. A sample of the molten alloy for chemical analysis was then aspirated into a silica sheath. Next, a slag-forming mixture of sodium sulfite and graphite was added instantaneously to the melt. The sodium sulfite amounted to one-tenth the charge weight of iron; sufficient graphite was added to combine with oxygen in the sodium sulfite, assuming formation of carbon monoxide and reduction of the sulfite to sulfide. Subsequent to the slag addition, the molten alloy was sampled periodically, with the exception of heat A in which no intervening samples were taken between the slag addition and the end of the run. The iron was poured into a graphite mold, and the ingots sectioned and drilled for samples. Results of selected heats are presented in Table I. Analyses of samples drawn from the iron prior to slag addition are listed under zero time. Two samples from heat D were reported with copper contents greater than the initial concentration in the bath. Owing to the gradual but complete disappearance of slag during this heat, it is believed copper momentarily became more concentrated in the upper portion of the bath while reverting from the slag. This is the region from which samples were drawn. It should be noted that analysis of the ingot was equal to the copper content at the time of slag addition. The terminal temperatures of heats D and E, and the initial sulfur content of heat A are also to be noted. Because of the large temperature drop which occurred when slag was formed in heat D, power input to the furnace was increased in heat E after the slag addition, causing a higher terminal temperature. In heat A, the initial sulfur concentration was relatively high as compared to heats B through E owing to contamination by some slag remaining in the crucible from a previous heat. It is evident from Table I that copper was removed at the onset of slag formation. Roughly 30 pct of the copper was taken into the slag, with the exception of heat D, which had approximately 50 pct removed. For a comparatively short time of slag-metal contact, it appears that no gain is to be made in copper removal through use of high or low temperatures. If the slag initially formed remains in contact with the iron for an extended period, temperature has a marked effect upon copper removal, as can be seen by studying results for the two extremes in temperature. At about 1425°C, the copper level remained relatively constant after the initial removal by the slag. However, in the region of 1670°C, a definite reversion of copper occurred. Reversion was incomplete in heat D, and complete in heat E. The final temperatures of heats D and E differed by about 75°C. This temperature difference is thought to be the reason for only partial copper reversion in heat D. It is believed the effects of temperature noted above are related to the evolution of a white fume, which appeared in every run except heat A. (In the case of heat A, the fume was practically indiscernible.) After each slag addition, a yellow flame formed for about 5 sec. When the flame subsided, a white fume appeared. Upon contact with surrounding cooler surfaces, this fume deposited as a white solid. In the experiments made at 1425°C, evolution of fume continued unchanged to the end of the runs. However, heats D and E exhibited a different behavior. A very noticeable decrease in fume evolution from heat D was observed. Furthermore, this heat had much less slag remaining than did runs A through C when the experiments were terminated. No slag remained at the end of heat E; evolution of fume from this heat ceased prior to pouring. Spec-trographic analysis of the white deposit indicated sodium to be the major metallic element, with the maximum concentration of iron and copper as 0.1 and 0.01 pct, respectively. It is supposed the white fume observed in these experiments is principally sodium oxide (Na2O), formed by oxidation of sodium in the slag and subsequent sublimation. (Sodium oxide is a white to gray substance in the solid state; at 1275oC, it sublimes.4) According to this mechanism, elevated temperatures would accelerate removal of sodium from the slag, sulfur pickup by the

Jan 1, 1961

By George A. Roche

Investment in growth stocks is the most assured way of achieving superior, long term investment accomplishment. There are many criteria used to select growth companies but the most important is a combination of superior management operating in an industry with above average growth potential. This growth stock approach is the cornerstone of investment strategy for two of the three mutual funds sponsored by the Price organization and for its private clients. However, during the past five years inflation has accelerated due to a variety of factors including the inability of government to meet seemingly unlimited needs with limited revenue sources.

Jan 4, 1972

By G. G. Brown

Enthalpy-entropy diagrams are presented for natural gases of 0.6, 0.7, 0.8, 0.9, and 1.0 gravity over the pressure range of 5 to 10,000 Ib. per sq. in. and temperature range of 32º to 700°F. The charts indicate directly the work requirement and temperature rise for adiabatic compression or temperature change for free emansion of natural eases. Computation and Uses of Charts The Mollier diagram (Fig. 4), in which the enthalpy (heat content) is plotted against the entropy with lines of constant temperature, pressure,, and in some cases volume, has been found most convenient when dealing with the compression, expansion, and flow of fluids. In dealing with the flow of fluids, the sum of the increase in the enthalpy, AH, plus the increase in kinetic energy, AM —, plus the increase in potential energy, ?MZ, representing the total increase in energy of the fluid in flow, is equal to the sum of the heat q, and work added, —w, to the fluid while flowing between the entrance and exit of the flow system. AH + AM— + ?MZ = q-w [1] In cases where there is no significant change in potential energy or in kinetic energy (velocity), it follows that the increase in enthalpy is equal to the total energy supplied to the fluid. Under such conditions' the changes in the property of the fluid as it flows through a throttling valve, choke, or any other similar arrangement, may be read directly from the enthalpy-entropy diagram by following a horizolltal line between the known pressures' When compressing Or expanding a gas by means of a Or or engine in which no heat is added to or subtracted from the gas, but only work done, the changes in the properties of the gas may be determined along a vertical line of constant entropy between the entering and exit pressures. The power required for the compression of the gas may be readily determined by converting the increase in enthalpy into the desired units. The enthalpy-entropy diagram for natural gases is to the gas engineer what the steam diagram is to the steam-power engineer. For this reason it would be extremely convenient if a reasonably satisfactory enthalpy-entropy diagram could be prepared as a function of the gravity of the gas. A careful study of the known properties of natural gas indicate that this is possible. The effect of temperature upon the enthalpy at constant pressure is expressed as the "heat capacity" or "specific heat" of the gas. The best available data for natural and petroleum refinery gases indicates the relationship shown in Fig. I. From this it is clear that the specific heat of natural gases is a function only of the gas gravity and the temperature at atmospheric pressure. The effect of pressure on the enthalpy of natural gases is dependent upon the pressure-volume-temperature relationships,

Jan 1, 1945

By W. A. Dunkley, W. W. Odell

The sulfur content of coal is perhaps more important in the manufacture of illuminating gas than in any other coal-using industry. Whether the gas is made by the distillation of coal in retorts or ovens or by steaming incandescent coal or coke in the water-gas process, a portion of the sulfur present in the fuel always passes into the crude gas. Practically all the sulfur that remains in the finished gas is transformed into sulfur dioxide (SO2) when the gas is burned. Sulfur dioxide is a pungent suffocating gas and, if present in the air in any perceptible amount, is deleterious to health and comfort and damaging to house furnishings. SO universally is this recognized that laws regulating the amount of sulfur that may be permitted to remain in the gas are very generally in force. The capacity of a plant to purify gas frequently limits the selection of coal for gas making. This condition may arise from different causes. Some plants were originally designed to handle a certain grade of low-sulfur gas coal, and very little leeway was allowed for growth or for the use of inferior coals. Other plants, when built, had ample capacity to purify gas from relatively higher sulfur coals, but their output has grown so rapidly that their purifying capacity is now limited and only the low-sulfur coals can be handled. There is a great quantity of coal in the United States that would satisfy the requirements of the gas manufacturer, were it not for the high sulfur content. The coals containing less than 1 per cent. sulfur are becoming scarcer year by year and, in time, the gas industry will probably be compelled to use coals that are now considered out of the question. Sulfur Compounds in CRude Gas Sulfur exists in unpurified illuminating gas in a variety of compounds; chief of these are hydrogen sulfide (H2S) and carbon disulfide (CS2). In crude coal gas H2S is usually present to the extent of 0.5 to 2.0 per cent., by volume, equivalent to about 300 to 1200 gr. per 100 cu. ft. of gas. In carbureted water gas, the amount of sulfur compounds depends not only on the sulfur content of the coal or coke used, but also upon cite

Jan 1, 1920

By Gordon H. Geiger, J. Bruce Wagner

Electrical conductavity and therrnoelectvic nzeasuretnents on synthetic hematite slabs with 0.01 to 0.90 at. pet Ti and with 0.30 at. pet Ca were made. Additions of titanium and of calcium both increased the electronic conductivity with titanium yielding greater n-type behavior and calciurn p-type behavior. Reduction studies of hematite to magnetite in CO-CO2 atmospheres between 600° and 900°C initially exhibited linear kinetics. These linear rates were increased by additions of titanium and decreased by calcium. IN recent years many studies have been reported in the literature on the kinetics of the reduction of hematite and magnetite to iron. In addition, Hansen and Josephl and Schenck and Schultz2 have reported studies on the reduction of hematite to magnetite, the first step in total reduction to iron. In order to evaluate the results of the studies of over-all reduction in terms of the actual mechanism of the reaction and to define further the important factors in the rate- controlling mechanism of the magnetic roasting reaction, the following experiments were undertaken. Specimens of undoped hematite and hematite containing titanium or calcium in solution as doping agents were reduced to magnetite in CO-CO2 mixtures. In addition, electrical-conductivity measurements were correlated with the reduction kinetics using concepts of defect solid-state chemistry. EXPERIMENTAL Fisher certified Fe2O3 powder was used to make specimens for both the electrical and kinetic studies (see Table I for analysis). Doping with titanium and calcium was accomplished by adding TiO2 and CaO powders to the Fe2O3 powder. The powders were mixed in a Waring blender for minimum times of 1/2 hr. Satisfactory blending was achieved based on comparison of analyses of individual specimens af- ter reduction. The specimens were formed in a steel die using opposed punches with a rectangular opening 10.0 by 40.0 mm. The Fe2O3-TiO, platelets were pressed cold at 16,000 psi. They were sintered for approximately 16 hr at 1075°C in air, in accordance with information in the literature3, 4 on the time and temperature needed to obtain solution of the titanium in the hematite. The Fe2O3-CaO mixtures were first cold-pressed at 20,000 psi and sintered for 3 hr at 1225°C to insure solution of CaO. This material was then ground to -325 mesh in a 6-in. ball mill and the resulting powder was used to make platelets in the same manner as above. The sintered platelets were usually between 1/16 and 1/8 in. thick. They were ground on a carborundum wheel and polished on 2/0 paper. Typical dimensions of the kinetic-study specimens were 1.6 by 0.8 by 0.05 cm, and a typical weight was 0.3 g. Conductivity and thermoelectric specimens were approximately the same size, but were subjected to further sintering in order to ensure maximum densification. Finally, all specimens were measured to the nearest 0.0005 in. and weighed on a Mettler H-15 balance to the nearest 0.0001 g and the density calculated. The average density of the specimens used for the reduction studies was 4.87 g per cc, or 7.1 pet total porosity. The standard deviation ranged from 0.14 to 0.063 g per cc within a composition group. In the present study, the apparent surface area as measured with a micrometer was taken as the true surface area. The chemical analyses for calcium and for titanium within a group showed maximum variations of 50.04 pet from the average values used in Figs. 9 and 11. In order to suspend the specimen from the balance for the kinetic studies, a hole, 0.03 in. in

Jan 1, 1965

By W. T. Allan

Raw bituminous coal has been in general use as a blast-furnace fuel in Scotland for the last century, and although its use has now been largely abandoned and it has been replaced by coke in the majority of the few furnaces which are at present in blast in this country, coal-smelted pig iron is not yet a thing of the past; it is still being produced and marketed in competition with the more cheaply smelted product of the coke-fired furnace. Various factors have influenced this change in practice; the once plentiful deposits of coal of a suitable nature for the blast furnace are now not so easily obtainable; native blackband and clayband ironstones which are easily smelted in the coal-fired blast furnace, although still far from being exhausted, are not available except at a cost that is somewhat higher than that of imported ores, making them unattractive to the ironmaster that is compelled by circumstances to smelt his iron at the lowest possible cost. Within the last 15 years overproduction of synthetic nitrogen has led to progressive reductions in the price of sulphate of ammonia, the recovery of which together with the other by-products before that time materially assisted in reducing the working costs of the coal-fired furnace. Now the sale of the by-products recovered yields a diminished profit. When the cost of the product is the only consideration the small, s1ow-smelting, coal-fired blast furnace cannot compare with its large, modern, coke-fired competitor. Other considerations do not by any means all support the same side of the argument. In the smelting of pig iron to be used in the manufacture of steel where the quality of the final product depends so largely upon the control of the conversion process and so much less upon the physical quality of the pig iron used, the physical properties of the pig iron do not exert any appreciable influence upon the quality of the steel produced, therefore the methods employed in the smelting of the pig iron matter but little so long as the requisite chemical composition is reached. On the other hand, in ironfounding where the simple melting of the pig iron, which is the only treatment it receives before being cast into its final form, does little or nothing to modify its original charac-

Jan 1, 1937

By H. L. Luo, P. Duwez, C. C. Chao

BY rapidly cooling alloys from the liquid state, it is possible to obtain solid solutions beyond the equilibrium concentrations, provided that the components are miscible in the liquid state. Typical such cases include CU-Ag,1 Pt-Ag,2 CU-Rh,3 nickel-base alloys with silicon, germanium, and tin,4 and cobalt-base alloys with silicon, germanium, tin, aluminum, and gallium.5 In the present note it is shown that terminal solid solutions can be appreciably extended in A1-Mg alloys. The alloys whose compositions are given in Table I were prepared by induction melting in tantalum crucibles under an argon atmosphere. Both aluminum and magnesium were 99.99 pct pure. Weight losses after melting were less than 0.2 pct for the aluminum-rich alloys and less than 0.4 pct for the magnesium-rich alloys. From these weight losses it was estimated that the compositions of the ingots after melting were accurate within 0.3 at. pct for aluminum-rich alloys and within 0.5 at. pct for magnesium-rich alloys. As indicated in Table I, the compound AuCd10 in which there is an ionic contribution to the bonding. The authors thank Dr. J. H. Westbrook of the Research Laboratory, General Electric Co., for arranging the supply of materials and for his interest. This investigation was supported by the U.S. Atomic Energy Commission under Contract AT(30-1)-1002, Scope I. some of the alloys were also chemically analyzed and the results confirmed the limits of uncertainty based on weight losses. Rapid quenching from the liquid state was achieved by techniques previously described.8,7 The principle of these techniques consists of propelling a small globule of liquid alloy (about 20 mg) onto a copper substrate. The thin foils easily detached from the copper substrate were analyzed by X-ray diffraction using a Debye-Scherrer camera 114.6 mm in diameter and either nickel-filtered copper Ka or iron-filtered cobalt Ka radiation. Since the back-reflection doublets were resolved, the wavelengths used in the computatioas were CuKal = 1.54050A and CoKa1= 1.78892A. Lattice parameters were obtained by extrapolation of the Nelson-Riley function, and the tables compiled

Jan 1, 1964

By C. W. Kovach, A. Moskowitz

Studies were undertaken to investigate the effects of manganese content on the machinability and other Properties of a free machining martensitic stainless steel (AISI Type 416). Machinability was found to be significantly improved in steels of high manganese content, and a direct relationship was obtained between machinability and steel Mn:S ratio. As the manganese content of the steel increases, the sulfide Phase present changes from CrS to (FeMn)Cr2S4 to (MnFeCr)S, and finally to MnS. The average sulfide inclusion hardness decreases through the same range of increasing manganese content. The mechanism for machinability improvement is discussed in terms of a soft ductile sulfide affecting deformation in the secondary shear zone. Type 416 containing relatively high manganese for improved machinability shows good general properties. The effects of increasing manganese content on mechanical properties, cold formability, and corrosion resistance are described. THE addition of sulfur is commonly used to improve the machinability of stainless steels. However, little attention has been paid in the past to the composition and characteristics of the sulfur-containing phase or phases present in these resulfurized steels. Recent information on the properties of sulfide phases, and their role in metal cutting, suggests that variations in these phases could have critical effects on machin-ability, as well as important effects on formability and other properties such as corrosion resistance. Manganese, chromium, and iron are strong sulfide forming elements present in stainless steels! of these, manganese has the greatest sulfide forming tendency and iron the least.1"1 The manganese content of resul-furized 13 pct Cr steels, often about 0.5 pct, can be insufficient or only barely sufficient to combine with the sulfur that is present; thus, the precise level of manganese can strongly influence the nature of the sulfide phase. Sulfide phases which may be present in stainless steels have been reported to include CrS, a spinel-type sulfide, chromium-rich manganese sul-fide, and manganese Sulfide.5,6 Detailed phase relationships for the Fel3Cr-Mn-S system have been reported by the present investigators,7 and a portion of this work will be referred to subsequently in this paper. Recent work by Kiessling6 and Chao et a1.8 has shown that sulfide phases can display wide variations in hardness, and may undergo considerable plastic deformation under isostatic loading.9-12 Early theories of metal cutting attributed the influence of sulfur to a lubricating effect. It is now apparent that the influence of the nonmetallic inclusions and their properties on crack initiation, deformation in the shear zones, and boundary films must also be considered in relation to the machining process. This paper presents the results of studies conducted to relate machinability to the various sulfide phases which occur in stainless steels. This work has led to the development of alloys with improved machinability, and has generated information on the effects of inclusions on metal cutting processes. Effects of sulfide inclusions and steel composition on other important metallurgical properties are also discussed. MATERIALS For drill machinability and inclusion studies, 10 lb laboratory heats were melted in an air induction furnace. These heats were made with sulfur contents be tween 0.10 and 0.50 pct and manganese contents be tween 0.05 and 3.0 pct. Residual elements were added to the heats in amounts typical for commercial steels. The typical compositional range covered by the heats is shown below: C Mn P S Si Ni Cr Mo Cu N 0.10 0.05 0.007 (M0 0.40 0.40 13.0 0.20 0.10 0.03 3.0 0750 The laboratory ingots were forged in the temperature range of 1800" to 2100°F to 3/4-in. sq bars, and all bars tempered to a hardness aim of 200 Bhn prior to testing. Because of differences in composition and tempering response, the tempered bars showed some variation in hardness (175 to 275 Bhn) as well as variations in delta ferrite content (0 to 50 pct). Composition, hardness, and delta ferrite content were considered in the analysis of the machinability data. Additional tests involving tool-life evaluation and determination of other properties were conducted on materials from commercially melted and processed 15-ton electric furnace heats. TESTS AND PROCEDURES Machinability of the laboratory heats was evaluated in a drill test. In this test, 1/4-in. diam holes, 0.4 in. deep, were drilled alternately in a test bar and in a standard bar for a total of four holes in each. This sequence was repeated three times using a freshly sharpened drill each time. The average time required to drill a hole in the test bar was compared to that for the standard bar. A drill machinability rating was assigned to the test bar relative to a rating of 100

Jan 1, 1970

By E. Douglas Sethness

The uranium industry is booming. In Texas alone, there are about 22 different companies with active exploration programs. Twelve solution mines have been permitted; three surface mines have been authorized; and two mills are currently in operation. However, the industry also has a problem, and that is the disposal of radioactive wastes. Over the past several years, stories concerning nuclear wastes have appeared frequently in the news. One of the most frequently cited cases occurred in Grand Junction, Colorado. In 1966, after ten years of investigations, the U. S. Public Health Service (PHS) discovered that tailings from a uranium mill were being used as fill material and aggregate for local construction purposes. It was estimated that between 150,000 and 200,000 tons of material had been removed and used under streets, driveways, swimming pools, and sewer lines. In addition, tailings had been used under concrete slabs and around foundations of occupiable structures. Further studies prompted the Surgeon General to warn that the risk of leukemia and lung cancer could be doubled at the measured radiation levels. More recently, the L. B. Foster Company discovered that its building site in Washington, West Virginia, was radioactive. While digging a foundation, the ground erupted and a ball of fire 30 feet high shot out. Evidently, the dirt was laced with radioactive thorium and zirconium, a potentially explosive mixture contained in a Nigerian sand which had been used by the previous site owners in the manufacture of nuclear fuel rods. Just this month we have read about legal suits to stop exploration for a nuclear waste disposal site in Randall County, Texas. The U. S. Department of Energy is trying to locate a deep underground nuclear waste depository for final burial of over 76 million gallons of high-level wastes. The problem is acute, the wastes are accumulating at a rate of about 300,000 gallons per year. Nor do these numbers include the spent fuel elements from nuclear power plants that are in temporary storage facilities. Fortunately, public awareness of these and other related issues is high. Unfortunately, the differences in the waste products from the nuclear fuel cycle are not always apparent to the general public. There are two distinct types of radioactive wastes: "high-level", which consist of spent fuel or wastes from the reprocessing of spent fuel; and "low-level", which, in general, are by-product wastes. There are numerous non-technical definitions that can be applied to help the layman differentiate between high-level and low-level wastes. For this latter purpose, it is best to think of them in terms of what we can see and feel. In general, high-level wastes are physically hot and can cause acute radiation sickness in a short period of time. Low-level wastes are not hot, but may cause chronic health effects after long exposure. The wastes which we are concerned with in the uranium mining and milling industry are low-level wastes. As recently as ten years ago, there were very few controls or regulations governing tailings disposal methods. At the same time, mine reclamation was not enforced through either state or Federal laws and the long-term viability of abandoned tailings ponds was not assured. The regulatory climate has changed significantly in the last decade, however. The low-level radioactive wastes generated by uranium mining and milling are generally contained in a tailings pond. Approximately 85-97% of the total radioactivity contained in uranium ore is present in the mill waste that goes to such tailings ponds. The isotope Radium-226 is probably the most potentially harmful radioactive parameter in the ponds. Radium emits gamma radiation and is also an alpha particle emitter. Because gamma radiation is very penetrating, it presents a potential health problem when a source is located external to the body. Gamma radiation will go through the body, causing damage to each cell encountered on the way. Although alpha particles have very little penetration capability, they can cause extensive cell damage. For this reason, alpha particles are a problem after inhalation or ingestion. Radium creates a health hazard by both of these mechanisms. Radium decays to radon gas which can be inhaled and serve as an alpha particle emitter. Additionally, radium is very soluble and readily enters the natural hydrologic cycle if allowed to leach from a tailings pond. With a half-life of 1620 years, radium has plenty of time to be taken into the food chain and end up in our bodies, emitting alpha particles. Because the potential health problems are better understood today than ten years ago, and because the Nuclear Regulatory Commission (NRC) has developed increasingly stringent government regulations, the uranium mining industry applies a high level of technology to the disposal of nuclear wastes. In most cases, low-level radioactive wastes are disposed of at or near the site where they are produced. There are six commercial burial grounds for low-level wastes, but it would not be economical to ship all mine or milling wastes to these sites. The on-site disposal methods most often used are ponding

Jan 1, 1979