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By J. E. Howard

On Aug. 25, 1911, a rail failed on the Lehigh Valley Railroad, causing a disastrous wreck. The surface of the fracture was in a plane at right angles to the length of the rail. There was a dark-colored, oval spot on this surface, located on the gage side of the head, representing the part of the rail which was the first to fracture. The nucleus of this spot showed that the fracture had an interior origin. Other fractures of this kind, the peripheries of which had not reached the surface of the rail, presented surfaces having a (silvery luster. The darkened surface of the present fracture was caused, doubtless, by the air having had access to it. This fracture was recognized as a fatigue fracture, of a modified type, its interior origin having been due to a component in the rail which is not usually present in cases of fatigue fractures. The metal next the running surface of the head of the rail was in a state of internal compression, this being the component not commonly met with in other cases, and which caused the fracture to have its interior origin. For the purpose of giving this modified type of fatigue fracture a specific name, for identification, the term "transverse fissure" was applied. No mystery was thought to attach to its formation, or to its development. The explanation of its occurrence seemed obvious in the light of common knowledge upon the behavior of steel under repeated alternate stresses.' By reason of the state of internal compression at the running surface, the maximum tensile stresses in the head, ander bending loads, were along an interior element. Here the tensile strains were higher than in the fibers more remote from the neutral axis. Under such conditions the fracture of the rail would be expected to have an interior origin. A discussion of the subject of transverse fissures essentially becomes a discussion of fatigue fractures, since they are believed to be identical. The descriptive term employed, merely for the identification of this type of fatigue fracture, had the appearance of creating alarm. Apprehensions arose that a new phenomenon in the physical properties of steel had presented itself, the explanation of which was sought in every

Jan 1, 1918

By Herman Van Fleet, Frederick W. Neil, O&apos

The object of this paper is to describe the present status and possil~ilities of liquid oxygen as an explosive based upon the investigations, research and practical work of the Ingersoll-Rand Co., and of the Air Reduction Co., from early in 1922 to date. The following work was done. 1. A study of the history and physical theory of L. 0. X. as an explosive. (No attempt will be made in this paper to give the history or theory, as this has already been covered by the literature on the subject.) 2. An investigation of the use and the practice with L. 0. X. in the iron mines of Lorraine where L. 0. X. has its largest application in Europe. Although L. 0. X. is extensively employed in the iron mines of Lorraine, many of the mines using it exclusively, and blasting with it a total of approximately three million tons of iron ore per year, the fact that the mining practice in Lorraine1 is to drill comparatively shallow holes and blast only a few holes at a time, renders the data obtained there of very little value in estimating the possibility of replacing dynamite with L. 0. X. in American mining methods. In fact, in the iron mines in Lorraine, L. 0. X. replaced black powder, or its equivalent. 3. Laboratory research work on properties of absorbent materials. 4. Work in the Bureau of Mines explosive laboratory at Pittsburgh, Pa., on the properties of L. 0. 3. cartridges. 5. Practical work underground with L. 0. X. cartridges in the Kitherbee-Sherman iron mines at Mineville, N. Y. 6. Practical work in the quarries of the Calcite Quarry Co., Myers-town, Pa. 7. Practical blasting in several quarries and open-pit mines.

Jan 1, 1927

By H.E. Brauer

Among the zinc base alloys used for casting in metal moulds, pnrticularly die casting, those alloys containing aluminum usually together with copper, are probably the most widely used. The reason lies in their desirable mechanical properties and the fluidity and absence of hot shortncss which facilitate ca,sting. Objection to the use of these alloys may be raised on account of the rather frequent instances of failure of a type variously described as disintegration, exfoliation and intererystalline corrosion. In all cases which have come to our kno~vlcdge where the conditionsof service were known, failure has occurred upon cxposurc to moisture and heat varying from a hot moist atmosphere to lligh pressure steam. RIoreover, the alloys described in all such roses contain impurities or alloying metals which the present authors have found to have enormous accelerating effects on intererystalline oxid:~t'ion in zinc-aluminurn alloys. Thus Williams1 experimented with an alloy containing a large percentage of tin exposed in Cuba. Baucr2 reports failure of a boiler plug containing over 1 per cent. of impurities, doubtless lead for the must part, and Rawdon's3 examinations were madc on an alloy containing 0.1 per cent. lead also exyosctl to thc Tropics. No thorough investigation of the nature and cause of this type of failure has been made heretofore, so far as the authors are aware, although Rawdon correctly classified it as internal oxidation. We have, therefore, carried out this investigation in order to det'ermine the exact nature of this phenonienon and the effect of other metals present as impurities or intentional additions in accelerating or retarding it. In the appendix we include a considerable amount of data which may be valuable in selecting an alloy combining good physical properties with high resistance to oxidation. At the time this work was undertaken the best available equilibrium *Investigator, Metal Section, Research Division, The New Jersey Zinc Company. 'H. W. Williams—Jour. Am. Inst. of AIet,als, Vol. 11, p. 221 (1917). 2o. Bauer—ZeiL, fiir i'vletall Kunde, Vol. 12, .No. 7, pp. 129-31 (1920). 3H. S. Rawdon—Trans. Am. Elcctrochcmic.al Society (1921).

Jan 1, 1923

By H. E. Brauer

Among the zinc base alloys used for casting in metal moulds, pnrticularly die casting, those alloys containing aluminum usually together with copper, are probably the most widely used. The reason lies in their desirable mechanical properties and the fluidity and absence of hot shortncss which facilitate ca,sting. Objection to the use of these alloys may be raised on account of the rather frequent instances of failure of a type variously described as disintegration, exfoliation and intererystalline corrosion. In all cases which have come to our kno~vlcdge where the conditionsof service were known, failure has occurred upon cxposurc to moisture and heat varying from a hot moist atmosphere to lligh pressure steam. RIoreover, the alloys described in all such roses contain impurities or alloying metals which the present authors have found to have enormous accelerating effects on intererystalline oxid:~t'ion in zinc-aluminurn alloys. Thus Williams1 experimented with an alloy containing a large percentage of tin exposed in Cuba. Baucr2 reports failure of a boiler plug containing over 1 per cent. of impurities, doubtless lead for the must part, and Rawdon's3 examinations were madc on an alloy containing 0.1 per cent. lead also exyosctl to thc Tropics. No thorough investigation of the nature and cause of this type of failure has been made heretofore, so far as the authors are aware, although Rawdon correctly classified it as internal oxidation. We have, therefore, carried out this investigation in order to det'ermine the exact nature of this phenonienon and the effect of other metals present as impurities or intentional additions in accelerating or retarding it. In the appendix we include a considerable amount of data which may be valuable in selecting an alloy combining good physical properties with high resistance to oxidation. At the time this work was undertaken the best available equilibrium *Investigator, Metal Section, Research Division, The New Jersey Zinc Company. 'H. W. Williams—Jour. Am. Inst. of AIet,als, Vol. 11, p. 221 (1917). 2o. Bauer—ZeiL, fiir i'vletall Kunde, Vol. 12, .No. 7, pp. 129-31 (1920). 3H. S. Rawdon—Trans. Am. Elcctrochcmic.al Society (1921).

Jan 1, 1923

By Shun-ichi Satoh

The electric arc welding of cast iron has been studied by Braune Lamberton, Schimpke, Kenyon, Gale Manufacturing Co., Wedemeyer Candy, Neese, Miller, Carter, American Welding Society, Namack Lebrun, Achenbach, Jansson, Xochendorffer and others.' The write of this paper has been able to obtain a series of cast irons, from gray tc white, without using cast-iron electrodes but by coating on wrought-iron bars mixtures of carborundum (Sic) and graphite (C). In this work, he found the curious phenomenon of barium carbonate.

Jan 1, 1929

By R. K. Datta

Eluropium -activated yttrium vanadate, excited by short- and long-wavelength ultraviolet radiations, shows enzission lines near 6100A, the principal ones correspondirzg to transitions of EU+3 ions from 5Do to the F2 energy level. The ~neclmlallistns of absorption and etnissiorz of this phosphor have been empirically studied. The absorption is caused by two separate processes in the matrix. The phosphor YVO4:Eu and tlie matrix YVO, haue essentially the same resectance spectra in the region 2500 to 4000if. There are two broat ah~o?~ption bands: natnely, around 2600 and 3600A regions. Whet? compared with the reflectance spectra of the constituent oxides, namely, Y2O3, V205, Eu2 03, the absorption bands of the tnatvix and the phosphor in the short- and long-wavelength ultraviolet regions can be interpreted as due to charge-transfer processes involving i) Y-O and ii) 17-0, respecti~~ely. The excitation spectrum' of the phosphor has two broad bands with peaks at about 2600 and 3600A regions. U can be postulated that enevgy absorbed under short- crud long-wavelength ultraziolet excitatzon, respectzcely, by Y-0 and V-O parts of the niatrix is transferred by radcatio~zless process to EU+3 ions. Thzs postulate can empirically be proved on the basis of the spectra of the systems (YVO4,-YPO4,):Eu. PO? ~ons do not have' any appreciable absorption in the short or long uv regions. When P0't3 ions are substitlited for v0i3 ions in YVO,:Eu phosphors, the absorption and excitation in the lo~zg uv region are gradually reduced. Ailoreover, the £«+3 emission under 3650A excitation is decreased zuitlz increase in PO^ content, lt~lzereas the emission under 253711 excitation remains esserztially constant with as IILUCIL as 60 mole pct of YPO, in YVO,:En. EUROPIUM-activated yttrium vanadate (YV04:Eu) is a well-known phosptor.'-3 When excited by cathode rays, 2537, or 3650A radiations, YV04:Eu emits typical narrow-band spectrum of EU'3 fluorescence in the region of 5900 to 7100A, a very strong maximum occurring at about 6190A. This emission is considered to be due to 5Do — 7F2 transition of excite: EU*3 in 4f state. Moreover, the emission under 3650A excitation increases with temperature markedly. Because of these properties, YV04:Eu phosphor finds wide application in industries, namely, in color television tube, laser, and high-pressure mercury-vapor lamps. It is the purpose of this paper 1) to present the empirical study of the mechanism of absorption and excitation of YV04:Eu phosphor by ultraviolet radiation, and 2) to offer an explanation for the process of emission. It should be mentioned that a theoretical discussion on the mechanism of absorption in terms of the crystal or ligand field theory is beyond the scope of this paper. Empirical studies presented here are based primarily on spectroscopic and crystal-chemical investigations. EXPERIMENTAL i) Preparation of Materials. The synthesis of vanadate phosphorinvolves preparation of (Yi-.tEuj^Oj, blending the mixed oxide with an oxidic compound of vanadium, such as V205 or NH4V03, and firing the mixture at about 1000°C for several hours when YVO4:Eu forms as a primary phase. (Y1-xEux)203 compositions are prepared by coprecipitation of oxalates, and igniting them at about 1000°C. The vanadium compound is added in excess of the stoichiometric proportion for fluxing purposes. The charge is cooled, ground, and the excess of vanadium is removed by a hot wash (-80°C) of alkali or ammonia. Y(VP)04:Eu samples are prepared by mixing (Yi-xEux)203 with stoichio-metric proportions of (NH4)2HP04 and the vanadium compound. The mixtures are prefired at 700" to 800°C for 1 or 2 hr, then ground and refired at 1150°C. The firings of the phosphors are done in silica crucibles, and the homogeneity of the final products checked by X-ray diffraction analysis. ii) Spectroscopic Measurements. Diffuse reflectance sqectra of the samples within the range 2500 to 7000A are obtained by using CaF2 as standard in Cary Recording Spectrophotometer, Model No. 14. The emission spectra from phosphor plaques, excited under different ultraviolet sources, are obtained by a direct-recording spectroradiometer4 adapted with a grating monochromator with nearly constant dispersion. Maximym sensitivity in the spectral region from 2500 to 7000A is obtained with a quartz-windowed, S-20 response p$otomultiplier. The total' band pass is kept about 30A. The spectra are calibrated against the light from a standard tungsten filament lamp reflected from a magnesium-oxide plaque. Brightness data given throughout this report $re measured from the height of the main peak (6190A) of the emission spectra. The excitation spectra are measured using sodium salicy-late as standard. RESULTS AND DISCUSSION The diffuse reflectance spectra of both pure and activated YV04, along with their constituent components, are shown in Fig. 1. YVO4 shows two broad absorption bands, namely, around 2500 and 3600A, respectively. Since there is little difference between the reflectance spectraoof YVO4 and YVO,:Eu in the uv region (2500 to 4000A), it can be postulated that excitation of the phosphor is mainly due to absorption by the matrix, i.e., YVO4. The question, now, is whether the matrix (Yv04) is excited as a whole, or different components are responsible for the two absorption bands. The characteristic absorption spectra of molecular ions involving transition metal ions, both in aqueous solutions and in crystals, are due to electronic transi-

Jan 1, 1968

By A. Perry Thompson

I- GeneRal Distribution, AppeaRance, and Relations ........ 563 11. Data fRom MicRoscopic Examination............... 568 1. Criteria for Distinguishing Primary from Secondary Minerals...... 568 2. The Leonard Vein Filling..................... 574 Quartz............................ 575 Pyrite............................ 575 Enargite............................ 576 Covellite............................ 578 Bornite............................ 581 Chalcocite........................... 583 Chalcopyrite.......................... 586 3. The Fault-Vein Covellite..................... 587 The Speculator Ore........................ 587 The East Gray Rock Ore.....,.............. 589 4. Other Occurrences of Covellite.................. 591 111. Conclusions........................... 592 1. The Replacement of Minerals..................592 2. The Character of Mineralizing Solutions .............. 594 I. General Distribution, Appearance, and Relations Mining in Butte has seldom encountered covellite in commercial quantities. The notable occurrences, extending vertically and laterally perhaps several hundred feet, presented scattered, bladed lenses of this mineral in a matrix of quartz, pyrite, enargite, bornite, and chalcocite. But under the microscope covellite is seen to be widespread in the Butte ores, though in such small quantity that megascopic examination will not discover it. In early mining operations covellite was found in the Gray Rock vein, a member of the Blue vein system. As described by Sales,' it persisted as an occasional ore mineral, associated with quartz, pyrite, tetrahedrite, bornite, chalcocite, and minor amounts of sphalerite, from the 700-ft. to the 1,200-ft. level of the East Gray Rock and Diamond mines. Crushed quartz-monzonite and later quartz completed the vein filling between

Jan 1, 1916

By B. H. Caudle, L. G. Davies, I. H. Silberberg

This paper presents a method of predicting the recovery and performance of a five-spot steam injection project, in which a realistic approach to pattern sweepout efficiencies is made. Published methods for radial systems were modified for the five-spot pattern by approximating the stream lines with straight lines radiating from the injection well and then converging to the producing well. In each radial segment, the position of the steam front and the temperature profile ahead of the steam front were determined by heat balance equations, which included an estimation of heat losses to surrounding formations. The location of the saturations behind the cold water front was determined from a Buckley-Leverett solution to the material balance equation. Results from this program show steamflood recovery in a five-spot pattern to be considerably less than that predicted for true linear or radial flow systems. For a specific reservoir containing 900-cp oil, a steamflood in a purely radial flow system was predicted to recover more than 75 percent of the original oil in place when 2 PV of water had been injected as steam. A five-spot steamflood with otherwise identical properties was predicted to recover 10 percent of the original oil in place when 0.15 PV of water had been injected as steam and to recover almost no oil thereafter. A cold water five-spot flood in this system was predicted to recover approximately W percent of the oil in place with I PV of water injected. For a five-spot pattern in an example reservoir with 10-cp oil, steam injection similarly showed lower ultimate recovery than water injection but no improvement in recovery rule. Introduction The thermal recovery method considered in this study is steam injection in a five-spot pattern. Pattern steam injection has been given little attention in the past, possibly because of some rather obvious disadvantages. Unless steam temperature is maintained throughout the entire swept area, the process will revert to simple waterflood with all heat being lost prior to reaching the oil bank. Also, the oil viscosity reduction takes place near the steam front and not around the producing wellbore, so that low producing rates must still be endured. This is the reason for the success of the steam stimulation, or cyclic injection, in which the fluids are produced from the same well used for injection. On the other hand, steamflooding can offer some advantages. Oil displacement is by four methods: (1) mechanical displacement by the condensed water, (2) viscosity reduction of the crude oil, (3) swelling of the crude oil, and (4) distillation of the crude oil in the steam zone. Although dependent upon the crude, laboratory experiments have shown displacements up to 80 percent by steamflooding. In addition, steam is a good heat transport medium, since it is cheap and has a high heat content. Previous Investigations Previous publications have reported methods for predicting recovery in a steamflood for linear and radial systems. Since no pattern sweep efficiency is taken into consideration, the recovery even from a radial system must be greater than from more realistic geometries such as the very common five-spot patterns. Probably the broadest coverage is given by Willman who reported experimental results and offered a method of predicting recovery for a radial flow system. They concluded that both hot water and steam injection recover more oil than an ordinary waterflood, and that steam injection could yield recoveries "as much as 100 percent greater than by water flood." They also concluded that both the heat requirements for a reservoir and the residual oil remaining in the reservoir after steam injection were independent of the amount of oil originally in place, that short exploitation times were desirable, and that a high percentage of net sand in the reservoir with a high initial oil saturation was desirable. The method assumes that the flood occurs in three concentric cylindrical zones: (1) an inner steam zone, (2) a central hot water zone, and (3) an outer cold waterflood zone. Displacement in the steam zone is based on laboratory-determined residual oil saturations while the hot water and cold water zones use the conventional Buckley-Leverett equations. Although the results shown by Willman et al. are for a radial system flowing out from the well to an assumed external circular boundary, their equations did

Jan 1, 1969

ALABAMA Aldrich.-Lloyd, T W Anniston.-Carrington, F G Gerber, A B Heimrod, A A. White, H E Ashland.-Barton, J C Sturdevant, J C Bessemer.-Abbott, C E Ball, T L Hines, H K Hodgkin, W -0. Salmon, H S Thompson, N E Birmingham.-Adams, J H Adler, J. E Aldrich, T H Aldrich, T H, Jr. Ball, E M

Jan 1, 1923

ALABAMA Aldrich.-Lloyd, T. W. Anniston.-Carrington, F. G. Klugh, B. G. Bessemer.-Abbott, C. E. Dobbs, G. G. Ferguson V. Salmon, h. S. Stuart, Q. W. Birmingham.-Adams, J. H. Aldrich, T. H. Aldrich, T. H., Jr. Allen, A. W. Armstrong. W. D. Ball, E. M. Bonnyman, J. Bush, M. W. Carter, E. Crawford, G. G. Davis, C. B. Dryer. T. B.

Jan 1, 1923

CONTENTS PAGE ZAPFFE, CARL.-Manganiferous Iron Ores of the Cuyuna District, Minnesota. Discussed by A. K. Knickerbocker 1 MCCORMACK, C. P.-Economics of the Cuyuna Manganiferous Iron Ores. Dis-cussed by T. L. Joseph, J. Wilbur Van Evera, C. P. Perin, T. T. Read, L. E. Ives 4 READ, T. T.-Probable Error in Blast-furnace Records and Calculations Therefrom. Discussed by C. H. Herty, Jr., T. T. Read, T. L. Joseph, Ralph H. Sweetser 8 SCHWARTZ, H. A. and HIRD, (Mrs.) ANNA NICHOLSON.-Chemical Equilibria During Solidification and Cooling of White Cast Iron. Discussed by N. B. Pilling, Ralph H. Sweetser, H. M. Boylston, Albert Sauveur 10 HERTY, C. H., JR., BELYEA, A. R., BURKHART, E. H., and MILLER, C. C.-Some Factors Affecting the Elimination of Sulfur in the Basic Open-hearth Process. Discussed by Henry D. Hibbard, L. F. Reinartz,. C. H. Herty, Jr., Ancel St. John, A. L. Feild, C. R. Hayward, Ralph H. Sweetser, C. D. King, Haakon Styri, George A. Orrok 12 HIBBARD, HENRY D.-Finishing Melting Temperatures of Simple Ingot Steels. Discussed by Haakon Styri, George V. Luerssen, A. G. Zimermann, A. L. Feild, George A. Orrok, Albert Sauveur, R. F. Harrington, Henry D. Hibbard, I. A. Billiar, William J. Priestley, H. W. Gillett, W. P. Barba, Jerome Strauss, Harry H. Smith, H. LeChatelier, L. F. Reinartz 19 HERTY, C. H., JR., and TRUE, O. S.-The Reaction between Manganese and Iron Sulfide. Discussed by A. L. Field, H. S. Rawdon, C. H. Herty, Jr., T. L. Joseph, Haakon Styri 37 KAMURA, HEIHACHi.-Reduction of Iron Ores by Carbon Monoxide. Discussed by T. L. Joseph, R. Franchot, Ralph H. Sweetser, C. H. Herty, Jr 43 JOSEPH, T. L.-Effect of Sulfur on Blast-furnace Process. Discussed by R. Franchot, C. A. Meissner, T. L. Joseph, C. H. Herty, Jr., Ralph H. Sweetser, I. E. Waechter, F. N. Speller, T. T. Read 45 GOOSTRAY, JOB, HARRINGTON, R. F., and HOSMER, M. A.-Brief History of Metallurgical Practice in Cannon-making with Particular Reference to the Cast-iron Gun. Discussed by A. G. Zimermann, Geo. A. Orrok, Chas. Me-Knight, Jr., F. Brauer 51 Manganiferous Iron Ores of the Cuyuna District, Minnesota Discussion of the paper of CARL ZAPFFE, presented at the New York Meeting, February, 1925, and issued, as Paper No. 1390-I, with MINING AND METALLURGY, December, 1924. A. K. KNICKERBOCKER,* Virginia, Minn. (written discussion).¬The author makes a broad distinction between the "black" ores (the

Jan 6, 1925

By Albert J. Phillips

The effect of impurities on the flowsheet in the smelting and refining circuits for copper, lead and zinc is reviewed and the interflow of by-poduct metals from copper, lead and zinc plants is pointed out. The principal points of separation of all impurities in the circuits are indicated and the additional steps added to these circuits in order to effect impurity separation me shown. In this day and age, when difficult metallurgy is mentioned, one thinks of the extraction of more refractory or possibly the alkaline earth or rare-earth metals. It is true that the extraction of metals having a high affinity for oxygen and deleterious solubility for that element in the liquid metal, affords some of the most difficult extractive metallurgy problems. When this is coupled with an affinity for hydrogen, nitrogen, and carbon a devious approach is required that sometimes rivals the complexity of the metallurgy with which this paper deals. However, in all such cases the aim is for a simple

Jan 1, 1962

By Reno Sales

INTRODUCTION. THE geology of Butte possesses especial interest on account of the magnitude of the ore deposits, their extraordinary richness and persistence in depth. Since its discovery in the early 60's the district .has yielded, in round numbers, 6,000,000,000 lb. of copper, 260,000,000 oz. of silver, 1,250,000 oz. of gold, and a large but not definitely known number of pounds of zinc. This enormous metal production has been derived from an ore tonnage estimated roughly at 65,000,000 tons. At the present day, most of the important mine shafts have reached a depth of. 2,400 ft., while several are more than 3,000 ft., deep. At these-great depths rich bodies of copper ore are being exploited, showing no diminution in metal content as compared with the ores of the higher levels. The present (1913) daily rate of production is approximately 14,000 tons, of which 13,250 tons may be regarded as copper ore, although a small percentage of this is minable only because of the presence of

Jan 8, 1913

By W. H. Bassett, C. H. Davis

The late J. P. Sparrow, chief operating engineer of the New York Edison CO., carried out a series of practical tests on condenser tubes of several copper alloys and reported on the results to the Association of Edison Illuminating Companies at its meeting in September, 1913. In the preparation of these tubes the senior author had the pleasure of cooperating. Copper-zinc alloys in the proportions of 60-40,70-30,80-20, 90-10, and Admiralty metal, which is in effect 70-30 with 1 per cent. of tin, were tried. Monel metal and several copper-nickel alloys, and 8, 5, and 3 per cent. aluminum bronze were also tried. At the time of this report, the aluminum bronze had been in service for 4 1/2 years and seemed to be giving especially good results but later it began to fail and showed no substantial improvement over Admiralty metal. Monel metal was unsatisfactory and the nickel alloys apparently did not give better service than the Admiralty alloy. Previous to the publication of the report, and after considerable discussion, it was agreed that a test where tubes of different kinds could be under laboratory observation would be advisable, so the apparatus described here was set up in The American Brass Co.'s Waterbury Laboratory. This was fitted with tubes of copper, brass, bronze, nickel silver, cupro-nickel and other alloys, and the test started on Oct. 11, 1912. Salt water from East River, New York harbor, was barrelled and transported to the laboratory for the test. A fresh supply, completely replacing the water in service, was obtained at the end of each six months period. Plan of Procedure In general, the procedure was to inspect the tubes at short intervals and to remove those that had begun to leak. The tubes removed were carefully examined and a photographic and microscopic record of the

Jan 1, 1925

By B. E. Sundquist

The various methods based on solution models for obtaining free energies of mixing from miscibility-gap data have been applied to a number of binary-alloy systems. For nine of these systems there exist experimental thermodynamic data that permit a comparison of the results to experiment. It was found that the method of van der Toorn and Tiedema almost invariably leads to results that are physically unacceptable and that vary drastically with small changes in the miscibility-gap parameters. The subregular solution model is found in all cases, except the Al-Zn, Fe-Cr, and Cu-Pb systems, to exaggerate the free energy of mixing by 30 pct or more. The model developed by Lumsden is found to give results that are often in excellent agreement with experiment and which exaggerate the free energy of mixing by no more than 30 pct. These results and others give evidence that the Lumsden treatment of the effect of unequal atomic sizes and of imperfect configurational randomness due to deviations of AB bond energies from the mean of AA and BB bond energies is adequate for most systems. ANALYTIC expressions are frequently proposed for the dependence on composition of the activities of the components of a solution. Because the development of solution theory is incomplete, these expressions contain parameters which must be determined by experiment. The measurement of activities is often difficult and consequently such measurements are less readily available than are measurements of phase equilibria which, under certain conditions, can also be used to evaluate these parameters. For example, suppose it is known that two structurally dissimilar phases, each of known composition, in an n-com-ponent system are at equilibrium at a given temperature and pressure. n equations can be set up in terms of these parameters expressing the equality of the chemical potential of each component in the two phases. In addition, one can write the Gibbs-Duhem equation for each phase that also contains these parameters. Thus, if these n + 2 equations contain n + 2 parameters, these parameters can be determined (at the temperature in question) from the phase diagram alone. If the average number of parameters in each expression for the activity of a given component in a given phase is V then there will be 2nV parameters involved. Equating 2nV to n + 2 shows that, for n + 2, V = 1. If the temperature dependence of each parameter were to be expressed in some explicit form one could use equilibrium conditions at a number of temperatures to increase V. The situation is much improved when the two phases in equilibrium are structurally similar. It can then be assumed that, stably or metastably, two phases will become one at higher temperatures. Thus the number of parameters involved becomes nV instead of 2nV. Hence, V = 2 for n = 2 using only one temperature. (It is implied here that the activity expressions used are valid over the entire composition range.) In this investigation only the equilibrium of two structurally similar, two-component phases (miscibility-gap systems) will be considered. The various proposed solution models will be applied to a number of these systems and the results compared with available experimental results. All of the analytic expressions that have been proposed for the free energy of mixing of a two-component system are of the form where ?Gmix is the free energy of mixing per mole of solution, N1 and N2 are the mole fractions of components 1 and 2, respectively, and f(Ni, T) is some function of composition and temperature. In the "ideal" solution model f = 0. In the "regular" solution model f = a constant. Since these two models permit only a symmetric equilibrium diagram they will not be considered further here. The simplest model that permits a nonsymmetric miscibility envelope is the so-called "subregular" solution model proposed by Hardy.1 This model gives where the Ci(T) are functions of temperature only. The same expression for f is obtained from the "linear a function" model proposed by Darken and Gurry2 and applied to miscibility-gap systems by Wriedt.3 This model requires that the a function defined by be a linear function of composition (yi is the activity coefficient of component i). This model is not purely hypothetical for it has been found2 to hold true for a number of systems. It is readily shown3 that the f(Nl, T) obtained from this model is of the form given in Eq. [2]. It will be noted that the subregular solution model contains only two parameters and hence both of them can be determined at any desired temperature below the critical temperature, Tc, for a miscibility-gap systems in the manner described previously. At T, the two constants can be determined by equating the second and third derivatives of ?Cmix with composition to zero. Another two-parameter model was proposed by Lumsden4 who set

Jan 1, 1967

By J. H. Nead, T. S. Washburn

The grades of commercial steel produced in large quantities can be divided into two general types from the standpoint of ingot structure— killed and rimmed. Killed steel covers a wide variety with carbon contents throughout the range of the steel portion of the iron-carbon diagram, and is the kind usually used in the production of alloy steels. Rimmed steel is normally associated with carbon ranges under 0.30 per cent, and is not yet used to a large extent in alloy practice, except for copper-bearing steels. The fundamental differences in the ingots made from these two types of steel can be seen most easily in Figs. 1 to 7. In the rimmed ingot shown in Figs. 5 to 7 there are two lines of blowholes approximately parallel to the sides and coming together at the top and at the bottom of the ingot. In the killed ingots shown in Figs. 1 to 4 these blowholes arc not present. Also, the rimmed ingot has no well defined pipe, as compared to the deep pipe on the killed ingots, and there are numerous primary blowholes in the lower portion of the rimmed ingot perpendicular to the surface and close to it, while on the killed ingot there are no blowholes of this type in the ingot shown in Fig. 1 and very small ones close to the surface in the lower part of the ingot shown in Figs. 2 to 4. With respect to the presence of pipe and the primary blowholes, the structure may vary considerably in both rimmed and killed ingots, therefore these cannot be considered as fundamental structural characteristics differentiating the two types of steel. The primary blowholes in rimmed ingots may be much less pronounced than those in the ingot shown in Figs. 5 to 7—as, for example, in "ingot iron," which is entirely free from them. An example of a cross section of an ingot-iron ingot is shown on page 16 of "Research and Methods of Analysis of Iron and Steel," published by the American Rolling Mill Co. (1920). A certain amount of pipe may also occur in rimmed ingots, though it is normally porous and not as well defined [or deep as in the killed ingot of Fig. 1. In killed ingots, primary blowholes may occur near the surface, as in Figs. 2 to 4, and

Jan 1, 1937

ALABAMA Aldrich.-Lloyd, T. W. Ashland.-Downs, F. G. Geary, E. S. Auburn.-Brown, R. L. Bessemer.-Abbott, C. E. Ball, T. L. Ferguson, V. Salmon, H. S. Stuart. Q. W. Birmingham.-Adams, J. H. Aldrich, T. H. Aldrich, T. H., Jr. Allen, A. W. Armstrong, W. D. Ball, E. M. Bonnyman, J. Bush, M. W. Crawford, G. G. Davis, C. B. Ellis. E. E.

Jan 1, 1923

By H. D. Strain

Potash is a generic term used to describe a number of compounds containing the element potassium (K), which is one of the three major plant nutrients. Potash content of these compounds is commonly expressed as percentage potassium oxide (K20), and the market value of the products is usually dependent on contained K20. Most of the potash produced (approximately 95%) is used in agriculture as fertilizer. Potash products today are shipped by producing countries all over the world to meet the need for increased food production. WORLD POTASH RESERVES Apparent world potash reserves are shown in Table 15.2B.1 and total some 96 billion mt of recoverable potassium oxide. The Canadian reserves account for approximately one-half the known world reserves. The reserves shown represent the potassium oxide content of a variety of potash-bearing ores. The major ore is sylvinite (a mechanical mixture of KC1 and NaCl) from which KC1 or sylvite is recovered (63.2% K20 equivalent). Other ores, such as langbeinite (potassium, magnesium sulfate-22.7% K20) and carnallite (potassuim magnesuim chloride-17.0% K20) are also mined in various parts of the world, mainly for the potassium content. Theoretically, potassium is available in almost unlimited qualities from brines and saline waters. To date, the cost of recovery from salt brines has been greater than the costs by mining operations, but new technology could make brines and seawater an increasingly important source. POTASH PRODUCTION Potash production dates back to the 1860s in Germany, which was the only recorded producing country until 1912. By 1912 Germany was producing approximately 1 million tpy of K2O equivalent. Production began in France in 1913 and in the United States in 1915. World potash production and consumption are shown in Table 15.2B.2 for the years 1950-51 through 1967-68. In 1967 and 1968 the major potash-pro¬ducing countries in order of importance were those listed in Table 15.2B.3. By 1972 Canadian production had outstripped U.S. production. WORLD CONSUMPTION World consumption of potash for the years 1950-51 through 1967-68 is shown in Table 15.2B.2. Table 15.2B.4 shows total world consumption of potassium materials in 1967-68 by country. More than 70% of the world's potash is

Jan 1, 1976

By Werner Engelmaier

Constant-strain rotating-bending fatigue tests were conducted on 2024-T3 aluminum alloy constant-strain McAdams-type specimens in ultrahigh vacuum, 10-lo Torr, and in atmospheric air. In the elastic strain range the ratio of vacuum-to-air fatigue life varied from about 10 at a maximum bending stress of 37 ksi to near unity at the endurance limit. After 10 pct of the fatigue life, intergvanular microcracks appeared on the surface which did not appreciably propagate further until the last 5 pct of the fatigue life, where trans-granular cracks propagating first in slip-plane cracking and then in the stress-dominated mode led to failure. No reduction in residual tensile strength resulted from the fatigue of the specimens short of fracture. The mechanism governing the fatigue life operates between the occurrence of the intergranular microcracks and the initiation of the trans granular cracks. MORE than forty years ago, Mc Adam' and Haigh2 published the first systematic studies showing that the fatigue properties of metals were greatly affected by environments. Gough and sopwith3 found in a later study that the fatigue life of metals subject to corrosion can be substantially increased by reducing the atmospheric pressure. This and their later work4'5 was, however, done in a vacuum of only 10~3 Torr. Subsequent studies6-' at a vacuum of 10- Torr showed that water vapor is the primary agent affecting the fatigue properties of aluminum alloys. Only recently was ultrahigh vacuum used for fatigue studied.l Various theories have been put forward to explain this phenomenon. Wadsworth and Hutchings12 postulated that cracks form very early in the test and that the chemical attack by the corrosive components of the atmosphere at the root of the cracks enhances the speed of the crack propagation. They also noted that chemisorbed layers of gas on the fresh crack surfaces prevent cold welding of the crack and make the separation irreversible. Ham and Reichenbach, on the other hand, reported that their specimens showed no cracks after a run in vacuum, even though the runs were long enough to have caused the specimen to fracture in atmospheric air. They also reported that in argon at 0.14 Torr the fatigue life was about 5 times longer than at 7 X lo-' Torr. Jacisinll reported that fatigue tests in dry nitrogen showed results close to those obtained in ultrahigh vacuum. The present experiment was designed to determine the extent to which cumulative fatigue damage, i.e., the accumulation of length of fatigue cracks, reduces the residual static tensile strength of an aluminum alloy in both ultrahigh vacuum and atmospheric air and to obtain fatigue-life data for this aluminum alloy at various strains. It was also hoped that information ex- tracted from these data might support one of the previously mentioned theories. 1) EXPERIMENT Test Specimens. The material tested was commer-cial 2024-T3 aluminum alloy. In addition to aluminum, this alloy contains approximately 4.4 pct Cu, 0.5 pct Fe, 0.5 pct Si, 0.6 pct Mn, 1.5 pct Mg, plus smaller amounts of other elements.13 Some typical mechanical properties of this aluminum alloy are listed in Table I.'~ The material was used in the as-received condition, i.e., solution-treated and cold-worked. Mc Adam-type1' constant-stress specimens and notched fatigue specimens were machined from 4 -in. -diam rods, Fig. 1. The critical section of the McAdam-type samples was polished with a 45-deg spiral motion to a No. 8 microfinish. The notch in the notched specimens was machined on a lathe with a forming

Jan 1, 1969

By Charles Hart

THE-report of the advisory committee to the U. S. Bureau of Mines, on the use of oxygen in metallurgy, brings to the art of steelmaking a radical change in the method of operation of the many processes of this widely diversified industry. When completed, the improvements suggested by the use of oxygen will be far-reaching and revolutionary. As to its effect upon the iron blast furnace, the use of oxygen should be as important as any of the improvements in the art of iron smelting and should take its place beside the German "Hochofen" which was the first attempt to use a shaft for preheating the stock, and beside the hot-blast stove which heated the blast before entering the furnace. The former initially produced molten iron and the latter made unbelievable economies in fuel consumption. It would seem that a discussion of this paper would be best served by following the conclusions on page 17 of the report and analyzing them seriatim. 1. (a) A decrease in costs, due to higher smelting heats is only attainable by taking full advantage of these heat units. This is affected by, adding additional ore to the burden which in turn increases production and yields a larger tonnage upon which to figure costs. These economies appear in decreased cost per ton of iron for coke and limestone consumed, and a proportionate reduction in all items entering the cost above materials. We can take no exception to these. premises. It is a well-known fact that silicon in the iron and sulfur removed" are the result of hearth temperature, other matters remaining constant. To a practical furnaceman the most satisfactory manner of controlling a furnace is by increasing the burden. It is not necessary, therefore, to consider the question of refractories, for this discussion presupposes that the temperatures in the furnaces will be kept practically where they now stand for making the various grades of iron. The same situation obtains in regard to the height of the furnace, which, as intimated, was one of the great strides forward in this art, and its abandonment at this time, is inconceivable. The shaft prepares the stock so that at each succeeding step we have exactly the proper conditions. All the stock entering the furnace is dried and preheated. The limestone is calcined by sensible heat practically at no cost, for this is sensible heat which otherwise would pass from the top with the gases. Under normal conditions, external calcination has been attempted without tangible results. Under normal average furnace operation, limestone requires about 760 B.t.u. for calcination and the loss of sensible

Jan 11, 1924