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By T. H. Alden

T. H. Alden (General Electric Research Laboratory)—This paper as well as earlier ones of Dr. Wood represent an important contribution to the experimental description of fatigue fracture. The mechanism of fracture proposed by the authors, however, is not established by this data nor supported by other data existing in the literature. Although taper section metallography provides a rather detailed picture of fatigue crack geometry, photographs so obtained must be interpreted with care. The narrow bands revealed by etching, frequently associated with surface notches, are labeled by the authors "fissures". Measurement shows, taking into account the 20 to 1 taper magnification, that the depth of these structures is at most 2 to 3 times the width. This distinction is important in the conception of a mechanism of crack formation. It is difficult, for example, to imagine a deep, narrow fissure arising from a "ratchet slip" model. A surface notch, on the other hand, may form easily by this mechanism. The notches observed in the present work are the subsurface evidence of the surface slip bands or striations in which fatigue cracks are known to originate.4-6 It is clear that an understanding of the structure of these slip bands is of key importance in understanding the mechanism of fracture. The evidence presented shows that these regions etch preferentially, possibly because they contain a high density of lattice defects, or as the authors state equivalently, because they are "abnormally distorted." However, it is not possible to conclude that the distortion consists of a high density of vacant lattice sites. The fact of a high total shear strain in itself does not assure a predominance of point defects as opposed to other defects, for example, dislocations. Other evidence in the literature which suggests unusual densities of point defects formed by fatigue7-' refers not to the striations or fissures, but to the material between fissures (the "matrix"). If a choice must be made, the preferential etching would seem to be evidence for a high dislocation density, since dislocations are known to encourage chemical attack in copper;g no such effect is known for the case of point defects. A third alternative is that the slip bands are actually cracked, but that near its tip the crack is too narrow to be detected by the authors' metal-lographic technique. In this case the rapid etching can be readily understood in terms of the increased chemical activity of surface atoms. Unless a vacancy mechanism is operative, the motion of dislocations to-and-fro on single slip planes will not lead to crack growth. Point defect or dislocation loop generation are the principal non-reversible effects predicted by this model. In any case, the nonuniform roughening of the surface in a slip band6 requires a flexibility of dislocation motion which is not a part of the to-and-fro fine slip idea. The same is probably true of crack growth by a shear mechanism. Either some dislocations must change their slip planes near the end of the band and return on different planes,'0 or dislocations of opposite sign annihilate." The mechanism by which these processes occur in copper at room temperature or below is that of cross slip. Thus cross slip appears to be essential to fatigue crack growth.6'10"12 The fact that a tensile stress opens the slip bands into broad cracks does not indicate the structure of the bands or the mechanism by which cracks form. The charactersitic concentration of slip into bands during fatigue shows a low resistance to shear strain in these regions. (This fact in itself may be inconsistent with a high concentration of vacancies.) The authors contend also that continuing shear produces an additional mechanical weakening so that the bands fracture easily (are pulled apart) under the influence of the superimposed tensile stress. It is equally possible that the only weakness is a weakness in shear, that the crack propagates by a shear mechanism, and that subsequently the tensile stress pulls the crack apart. Even the direct observation of bands opened by a tensile stress would not be conclusive since, as argued above, they may be fine cracks. The same argument applies to internal cracks, their existence in the presence of a tensile stress not indicating the mechanism of formation. Internal cracks originating in regions of heavy shear have also been seen following tensile deformation of OFHC copper,13 so that this mode of fracture is not unique to combined tensile and fatigue straining. The authors point out in their companion report14 that 90 pct of the cracks formed during pure tor-sional strain were within 8 deg of the normal to the specimen axis. If the tensile stress were an important factor in crack propagation, it is surprising that the cracks cluster about the plane in which the normal stress vanishes. Similarly, a study of zinc single crystals showed that for various orientations the life correlated well with the resolved shear stress on the basal plane,'= and was not dependent on the normal stress across this plane. W. A. Wood and H. M. Bendler (Authors' reply) -Dr. Alden's discussion emphasizes the essential point in the relation of slip band structure to

Jan 1, 1963

By C. M. Tucker, K. R. Van Horn, W. P. Sykes

Recent investigations of the molybdenum-carbon alloys have been reported by Becker and Ebertl,‡ Westgren and Phragmén2, T. Takei3, and H. Tutiya4. Takei3 studied the Mo-C system by employing metal-lographic and X-ray methods, and the other publications described the determination of the crystal structure of the molybdenum carbides. In exploring this system by a technique previously applied to the tungsten-carbon series5, the results of Takei were confirmed with two definite exceptions; i.e., first the composition of the eutectic, and second the nature of the carbon-rich intermediate phase. Consequently, a more thorough examination of the molybdenum-carbon constitution was initiated in an effort to correlate the data supplied by the microstructures, diffraction patterns and chemical analyses. Metallographic Investigation A briquette of molybdenum powder when heated in a carburizing atmosphere at 1500" to 1600" C. for several hours develops the carbon-rich layer shown in Fig. 1. The carburization was accomplished by placing the briquette in a carbon tube, which was heated in the hydrogen atmosphere of an alundum muffle wound with tungsten resistor. While the macrostructure indicates two distinct shells, and suggests the possibility of two carbon-rich phases, no evidence of this condition could be detected by the microscope, which revealed but one high-carbon constituent. This carbide forms next to the molybdenum as a relatively dense, light-colored zone (Fig. 2) which passes abruptly into an outer layer of spongy texture. As will be noted later, only one intermediate phase was observed in the X-ray photograms prepared of different locations in the carburized zone. The metallographic structure at the inner border of the shell, reproduced in Fig. 3, shows a marked porosity accom-

Jan 1, 1935

By C. M. Tucker, K. R. Van Horn, W. P. Sykes

Recent investigations of the molybdenum-carbon alloys have been reported by Becker and Ebertl,‡ Westgren and Phragmén2, T. Takei3, and H. Tutiya4. Takei3 studied the Mo-C system by employing metal-lographic and X-ray methods, and the other publications described the determination of the crystal structure of the molybdenum carbides. In exploring this system by a technique previously applied to the tungsten-carbon series5, the results of Takei were confirmed with two definite exceptions; i.e., first the composition of the eutectic, and second the nature of the carbon-rich intermediate phase. Consequently, a more thorough examination of the molybdenum-carbon constitution was initiated in an effort to correlate the data supplied by the microstructures, diffraction patterns and chemical analyses. Metallographic Investigation A briquette of molybdenum powder when heated in a carburizing atmosphere at 1500" to 1600" C. for several hours develops the carbon-rich layer shown in Fig. 1. The carburization was accomplished by placing the briquette in a carbon tube, which was heated in the hydrogen atmosphere of an alundum muffle wound with tungsten resistor. While the macrostructure indicates two distinct shells, and suggests the possibility of two carbon-rich phases, no evidence of this condition could be detected by the microscope, which revealed but one high-carbon constituent. This carbide forms next to the molybdenum as a relatively dense, light-colored zone (Fig. 2) which passes abruptly into an outer layer of spongy texture. As will be noted later, only one intermediate phase was observed in the X-ray photograms prepared of different locations in the carburized zone. The metallographic structure at the inner border of the shell, reproduced in Fig. 3, shows a marked porosity accom-

Jan 1, 1935

By William Fink

THE constitution of the aluminum-cobalt alloys has been the subject of relatively few investigations. Brunck1 analyzed the residue which remained after treating the 17 per cent cobalt alloy with dilute hydrochloric acid. The results of the analyses indicated the existence of a compound Co3Al13. Guillet2 published a liquidus for the aluminum-cobalt system which contained two maxima corresponding to CoAl6 and CoAl2 and two eutectic points at 30 and 74 per cent Co. The most extensive investigation of the system was carried out by Gwyer,3 whose results are summarized in Fig. 1. It will be noted that at the aluminum end there is a suppressed eutectic at 644° C. By extrapolation of the duration of the eutectic arrest to zero, the composition of the compound was placed at Co3Al13. Another thermal arrest was noted at 550° C., which Gwyer attributed to a peritectic reaction. The present investigation of the aluminum end of the aluminum-cobalt system is the eleventh of a series dealing with the constitution of aluminum; rich alloys prepared from electrolytically refined aluminum.4 Preparation of Alloys.-The alloys used in this work were all prepared from electrolytically refined aluminum, the analysis of which is shown in Table 1. In preparing some of the alloys, metallic cobalt (98 to 99 per cent) was used either directly or in the form of an intermediate alloy, the composition of which is given in Table 1. In order to obtain alloys of higher purity, cobalt was introduced into some of the alloys by means of chemically pure cobaltous chloride which was readily reduced by the aluminum. A small electric furnace with nickel-chromium heating elements was used in the preparation of the alloys.

Jan 1, 1932

By Nicholas J. Grant, Robert F. Wilde

TAYLOR and Floyd's"" work in establishing phase diagrams based on the elements Ni-Cr-Ti-A1 has led to an understanding of the precipitation hardening mechanism in alloys based on these elements. Nordheim and Grant4 concluded that in simple alloys, and where the aluminum to titanium atomic ratio was such that less than three out of five aluminum atoms were replaced by titanium, the precipitate on aging is the face-centered-cubic Ni 3A 1 phase, called They further found that increasing amounts of hexagonal ? phase, Ni3Ti, precipitated from these alloys when the titanium content exceeded the solid solubility of both matrix and Ni3A1. For alloys of Ni-Cr-Ti-Al, in which the titanium and aluminum contents each ranged from 0 to 4 wt pct, the titanium-rich was superior for strengthening to either pure ?' or 7. It was also noted that the combined titanium plus aluminum content (atomic pct) was a direct measure of the high temperature strength and overaging temperatures for these alloys.4 The present investigation was undertaken to extend existing data on precipitation hardening in the more complex commercial alloys containing higher titanium plus aluminum, and with significant quantities of cobalt, molybdenum, and carbon. Experimental Procedure Reforging of As-Received Bar Stock—The alloys were received as ground, forged bar stock. Chemical analyses and the as-received bar diameters are shown in Table I along with the ASTM grain size after the various treatments. All stock except the Waspaloy was reforged to % in. diam to gain material and to facilitate machining of stress-rupture specimens. Forging was carried out at 2100°F, and discontinued when the bar temperature fell to 1800°F. Heat Treatments—For experixental simplicity it was desirable to heat treat all of the alloys at, the

Jan 1, 1958

By S. G. Dixit, A. K. Biswas

The flotation and adsorption behavior of ilmenite, monazite and zircon have been studied with sodium oleate as the collector and pH as the principal variable. The maxima in the flotation and adsorption properties of any of the above minerals fall within similar pH ranges. The bell shaped pH versus adsorption magnitude (r) curve is explained on the basis of collector concentration (Co and the concentration of hydroxyl ion (COH-) acting as the depressant. An equation of the type: 1 =KiCor~K2 Coh-/Coi-is proposed to account for the experimental data. The beach sand deposits along the sea coast in Southern India contain ilmenite, monazite, zircon, rutile and sillimanite as valuable minerals while quartz, garnet, shells and traces of hornblende form the gangue. A typical composition of the deposits is reported to be as follows:' Ilmenite 75%, Zircon 4-6%, Rutile 3-4%, Monazite 2 - 4%, Garnet 2 - 5% and the rest 8 -10%. Selective flotation of beach sand constituents has been reported by many workers.2-4 The fatty acid soaps have been invariably used as collectors. It is seen that all the valuable constituents of the beach sand are efficiently floated by soap collectors such as sodium oleate. In order to selectively float the beach sand constituents, it is necessary to use some depressants such as sodium silicate.3 The physicochemical parameters that govern the flotation of these minerals are yet to be studied in detail. In the present article, the findings on the parallel studies on the flotation and adsorption of the systems — ilmenite-sodium oleate, monazite-sodium oleate and zircon-sodium oleate — are being reported. In these correlative studies on adsorption and flotation of beach sand minerals, ilmenite (FeTiO3), monazite (Ce, Dy, Nd) PO4 and zircon (ZrSiO,) have been selected because they represent three important

Jan 1, 1970

By J. A. Ede

The property of the Spring Valley Coal Company, situated in Bureau county, Ill., comprises something more than 30,000 acres of coal-lands, on which have been opened four mines, designated as Nos. 1, 2, 3 and 4. Figs. 1, 2, 3 and 4 are plans of the first three; and Fig. 7 is a view of the surface-plant at No. 4, the workings of which it is not necessary to illustrate, as this mine has been practically merged in No. 2. No. 4 shaft is only 500 feet from No. 2, and both are ventilated by the same fan, and are in the same circle of air-supply. In speaking of No. 2, we now include No. 4. The system pursued in all the mines is " long-wall advancing," and the shafts are all vertical. The seam worked is locally and commercially known, in the Illinois series, as No. 3; but its position in the geological series is that of No. 2. It averages in thickness about 42 inches, arid has no partings, but mines in rectangular lumps, which stand a large amount of handling before breaking. An analysis made from Colliery No. 1 gave the following : Per cent. Moisture,.......... 1.45 Volatile combustible matter,.47.27 Fixed carbon,.........41.97 Sulphur,.........2.46 Ash,....... .. .. .. 6.85 Plate 6 shows a photographic view of this seam. The staff seen in the view is 37 inches long. The table on page 188, recorded in my office, which I presume to be correct, may be of interest. The bottom is fire-clay, varying in thickness from 6 to 24 inches. It affords what is considered good mining-ground. The roof immediately above the coal is a dark shale, lying in small bands, from 4 to 9 inches in thickness. Between the

Jan 1, 1900

By H. M. Howe, A. G. Levy

§ 1 Introduction.—This paper gives the results of our micro-graphic determinations of the position of Ae3 in a series of 14 hypo-eutectoid steels of varying carbon content, one of them very rich in phosphorus, and of SEe for one hyper-eutectoid steel. We have proceeded chiefly by noting the temperature at which the reabsorption of the pro-eutectoid element is found to be complete after a 30-min. holding, but in part also by noting the temperature at which its precipitation begins. Observations on these same steels by Messrs. Burgess, Crowe, and Rawdon, of the United States Bureau of Standards, are given in a paper1 issued simultaneously with this, while in a third paper2 one of us compares these data with those of earlier observers. These three papers are treated as one whole by numbering their sections, tables, and illustrations continuously, and by setting the folding plates of micrographs at the end of the last paper. The Composition of the Steels Experimented On is given in Table I. § 2. Notalion and Definitions.—Following Osmond's development of Tschernoff's notation, in which " Ac3 " is the upper limit of the hypo-eutectoid part of the transformation range as observed in heating up, and " Ar3 " is that same limit as observed in cooling down, and following the usual custom of calling the upper limit of the hyper-eutectoid part of that range " SE," we may go farther and call this latter limit " SEc" when observed in heating up and " SEr " when observed in cooling down. Further, we may call the equilibrium position of these lines, i. e., the position which they would have in pure iron-carbon alloys if all

Jan 1, 1914

By S. Le Fevre

THE application of electricity to the mining and beneficiation of the magnetic iron ores of the Mineville, N. Y., district, on Lake Champlain, has resulted in economies and enhanced quality of product, without which only a comparatively small quantity of the present output could be marketed. The output of the Witherbee, Sherman & Co. mines is about 700,000 tons per annum, and of this about four-fifths is treated by magnetic separation to increase the iron content and reduce the phosphorus. The use of electricity for the magnetic separation of the ore from the gangue is therefore of primary importance, and makes possible the application of electric power for mining and preparing the ore for concentration: The fact which speaks loudest in favor of the application of electricity is this: It is possible for about 25c. per ton of shipping ore to furnish all the power required to put the ore on cars. This includes mining a hard ore underground, from a depth of 900 ft., hoisting to surface, crushing to 4 or s in. in size, and separating from the gangue. This also includes lights about the works, and all miscellaneous power, such as about the shops. The first plant for the generation of electric power for use at Mineville was completed in 1903, and was one of the first for the application of electricity to mining iron ore. This was a Nordberg compound condensing steam engine, direct connected to a 750-kw. alternating-current generator, 3,300 volts, 3 phase, 25 cycles. All the plants added later use the same-current but with higher voltage. The map, Fig. 1, shows the power plants and the transmission system; Figs. 2 and 3 are views of the shaft houses and the mills.

Jan 6, 1914

By Perry G. Harrison

The first autlientic description of an iron bath for the deposition of iron is probably that of Bottger in 1846, who used a bath containing ferrous sulfate and ammonium chloride. In 1861, Kramer deposited iron from ferrous chloride solution. Electrolytic iron was produced in 1869 by Bietz, who used it for making some magnetic tests. In the same year, Klein is. said to have worked out his process. Jacobil in 1869 described the results obtained in electroplating with iron on copper for making dies and plates for bank notes, by Klein's process. A letter from Klein to Jacobi describes the bath more fully. It consisted of FeS04 + (NH4)2SO4. Lenz2 described some properties of electrolytically precipitated iron. He used Klein's bath, FeS0, + MgSO4 + MgCO3, to neutralize and obtained fine-grained and hard iron. His conclusions were as follows: 1. Electrolytic iron and copper contain gases, notably hydrogen. 2. The volume of gas absorbed by iron varies within wide limits, but it is easy for iron to take up very considerable quantities of gas. 3. The absorption of gas is principally in the first formed layers of iron. 4. When iron is heated, gas begins to come off below 100°, principally hydrogen. 5. Heated to redness, reduced iron oxidizes in water, in part at least at the expense of the oxygen of the water, decomposing it and setting free hydrogen, which is partly or wholly absorbed. Siemens,3 in 1889, was the first to propose a general process embodying a step for leaching a sulfide mineral with ferric chloride or sulfate and a step for regenerating the leach and depositing iron on a cathode in a diaphragm cell. So far as is known, Siemens did not carry out his patent

Jan 1, 1930

By Claude H. P. Lupis, John F. Elliott

The classic Siez~erts' technique has been employed to determine the solubility of oxygen in liquid pure silver and the effect on the oxygen solubility of solute metal additions to liquid silver. The results indicate that oxygen deviates slightly from Sieverts' law in pure silver as = 3.9. Gold, platinum, md palladium decrease the solubility of oxygen in silver. First-order free energy, enthalpy, md entropy interaction coefficients are determined from the data. An important aspect in the establishment of the formalisms to be applied to represent the thermody-namic behavior of components of solutions is the accuracy of the experimentally determined thermody-namic properties. Wagner developed the first-order free energy interaction coefficient.' Recent papers2'3 extend the treatment formally to other thermodynamic properties and define the second- and higher-order interaction coefficients. A current communication4 considers in some depth the requirements and limitations imposed because of experimental error on the use of several formalisms now under active consideration in the field. This communication reports the results of an experimental study of the behavior of oxygen in liquid silver alloys that was carried out concurrently with the development of Refs. 2 and 3 with the hope of providing sufficiently precise information so that enthalpy and entropy interaction coefficients could be determined. THE EXPERIMENTS The Sieverts technique was employed using an improved design of the reaction bulb over that developed originally by Humbert5 and subsequently improved by pehlke6 and Weinstein.7 The Vycor reaction bulb as shown in Fig. 1 was air-cooled and contained a port for the thermocouple angling off to one side and a vertical port for connections to the gas supply and

Jan 1, 1969

By E. Posnjak

IT is rather the general belief that acidified, solutions of ferrous salts are readily oxidized when in contact with air, and often elaborate pre-cautions are taken to prevent it. This, however, is not the case and several statements may be found in the literature expressing surprise at the extreme slowness with which oxidation takes place when air or oxygen is bubbled through such a solution. Thus C. Baskerville and R. Stevenson1 "observed with surprise" that no oxidation apparently took place, as shown by titration with 0.5 N KMnO4, when a stream of air was passed for 3 hr. through an acidified solution of ferrous ammonium sulfate or ferrous sulfate. The same authors state that even the presence of salts such as. cobalt, chromium, copper, manganese, etc., which usually act as oxygen carriers, had "no effect upon the oxidation as was observed by passing air for 3 hr.. through solutions of Mohr's salt acidified with sulfuric acid." While this statement will bee proved further on to be at least partly incorrect the slowness of the oxidation of ferrous salts alone has been previously established by McBain.2 His investigation also showed that the rate of oxidation increases markedly with an increase in the concentration of ferrous sulfate as well as that of oxygen; the concentration of free acid had a comparatively small influence, which in the case of sulfuric acid was to retard slightly the rate of reaction. More recently R. Thomas and E. T. Williams3 investigated the catalytic effect of nitric oxide on the oxidation of ferrous salts, which had been earlier patented by McCulloch.4 They found that the probable mechanism of the catalytic action was the oscillation of the catalyst between two stages of oxidation and its interaction alternately with the oxygen and the ferrous iron.

Jan 12, 1926

By B. H. Bergstrom, A. P. Cohen, D. W. Fuerstenau

B.H. Bergstrorn (Research Div., Allis-Chalmers Mfg. Co., Milwaukee, Wis.) — Fuerstenau and Cohen have concluded from our study of single particle crushing, which had suggested that the size moduli of the crushed specimens were determined by the specific energy expended independent of feed size, that the same independence with respect to feed size exists for the specific energy-product size relationship for rod mills. They present data supporting this conclusion. Our single particle crushing experiments were on single spheres of soda-lime (type of glass was not given in our study) glass for which the feed size can truly be neglected. However, the feed size cannot be neglected in any case where the effective size modulus of the feed is not too much coarser than the size modulus of the product. This can be illustrated in the second experi- ment of Fuerstenau and Cohen where the feed is considered to be the original -6 +%mesh material. However, one can also consider the product from the 7.5-min grind to be the feed for the 10, 15, 20, 25-min grinds, and the 10-min product to be the feed for the 15, 20, 25-min grinds, etc. If the specific energy-product size moduli curves are drawn for these other feeds, as shown on Fig. 3, the new curves (and some curvature is apparent) are much steeper than the -6 +%mesh feed line. The slopes of these new curves are about -1.5, —1.8 and -3.0. This observation is in accord with the observation by Bond, who states that the net specific energy input to a grinding mill is equal to the specific energy represented by the product less the specific energy represented by the feed. Bond presents, on a diagram similar to Fig. 3, a series of curves which illustrate the effect of

Jan 1, 1963

By W. F. Carew, F. A. Crossley

The stress for rupture in 500 hr at 1000° F has been reported to be about 13,000 psi higher for Widmanstitten than for equiaxed microstructures for the Ti-7A1-3Mo alloy.1,2 Also, limited data indicated Widmanstatten and equiaxed micro-structures to have approximately the same creep resistance at 1000°F.' Recently, data have been obtained which show Widmanstatten structures to be significantly more creep resistant than equiaxed structures at 1000°F, see Fig. 1. These data represent several ingots and several heat treatments of the solution treat and age type. The thermal history and tensile properties corresponding to the creep data are given in Table I. The creep data were taken from creep-rupture tests. The associ- ated rupture data are given in Table 11. It may be noted that total creep deformations are considerably greater for equiaxed structures. Previous evaluations of stability indicated that all of the structures tested are stable with respect to exposure to stress at elevated temperature.1,2 For a minimum creep rate of 10-4 in. per in. per hr the difference in stress levels is indicated to be about 17,000 psi. Holden,et found an irreversible contraction upon heating three a-ß titanium alloys in the equiaxed condition above their ß-transus temperatures. The alloys were: Ti-6Al-4V, Ti-155 A (5Al-1.3Cr-1.5Fe-1.2Mo), and C-130 AM (44-4Mn). The net contractions in length between the original equiaxed and the final Widmanstatten structures measured at room temperature were: 0.4, 0.4, and 0.7 pct, respectively. The greater creep and rupture resistance of the WidmanstStten structure of the Ti-7Al-3Mo alloy may be associated with the phenomenon

Jan 1, 1959

By F. J. Williams

BARITE, naturally occurring barium sulphate, is the chief barium mineral that is produced commercially. Barite is also called "barytes," "heavy spar," sometimes "baryta" and, locally in Missouri, "tiff." Pure barite is white, opaque to transparent. It crystallizes in the orthorhombic system, frequently with twinning. Impurities cause a wide variation in color, commonly buff, gray and white with irregular reddish iron stains. Less frequently found are shades of yellow, green, blue, brown, and black. The rock is brittle and breaks with an uneven fracture, although specimens from some of the residual deposits, particularly in Missouri, appear to have a cleavage due to the separation of the different layers of deposition. The hardness varies from 2.5 to 3.5 on Mohs' scale and different localities are said to produce either "hard" or "soft" barite. This generally refers to the ease of grinding of the product. The specific gravity of pure barite is 4.5 and this will vary downward, depending on the impurities present. The mineral has a white streak and a pearly to vitreous or sometimes stony luster. Pure barite contains 65.7 pct BaO and 34.3 pct SO3. Witherite, native barium carbonate, is not mined in the United States at the present time although a number of occurrences have been reported. A small quantity of witherite has been removed from a mine at El Portal, California, but the area high in witherite was small and soon depleted. The bulk of the deposit is predominantly barite. Great Britain is the world source of witherite and small quantities are imported into the United States. DISTRIBUTION OF DEPOSITS Occurrence of barite is widespread; it has been reported on all the continents and in all the major countries of the world. Deposits vary from those containing millions of tons down to scattered rock fragments

Jan 1, 1949

By Robert Pike

THE first authentic description of an iron bath for the deposition of iron is probably that of Bottger in 1846, who used a bath containing ferrous sulfate and ammonium chloride. In 1861, Kramer deposited iron from ferrous chloride solution. Electrolytic iron was produced in 1.869 by Bietz, who used it for making some magnetic tests. In the same year, Klein is said to have worked out his process. Jacobi1 in 1869 described the results obtained in electroplating with iron on copper for making dies and plates for bank notes, by Klein's process. A letter from Klein to Jacobi describes the bath more fully. It consisted of FeSO4 + (NH4)2S04. Lenz2 described ?some properties of electrolytically precipitated iron. He used Klein's bath, FeSO4 + MgSO4 + MgCO3, to neutralize and obtained fine-grained and hard iron. His conclusions were as follows: 1. Electrolytic iron and copper contain gases, notably hydrogen. 2. The volume of gas absorbed by iron varies within wide limits, but it is easy for iron to take up very considerable quantities of gas. 3. The absorption of gas is principally in the first formed layers of iron. 4. When iron is heated, gas begins to come off below 100°, principally hydrogen. 5. Heated to redness, reduced iron oxidizes in water, in part at least at the expense of the oxygen of the water, decomposing it and setting free hydrogen, which is partly or wholly absorbed. Siemens,3 in 1889, was the first to propose a general process embodying a step for leaching a sulfide mineral with ferric chloride or sulfate and a step for regenerating the leach and depositing iron on a cathode in a diaphragm cell. So far as is known, Siemens did not carry out his patent

Jan 1, 1930

By T. P. Floridis

It was deemed desirable to obtain an understanding of the vacuum desulfurization process. McKechnie1 has reported that the sulfur content of nickel- and cobalt-base alloys is reduced in vacuo. Keverian and Taylor2 have observed that vacuum melting causes desulfurization of iron-carbon-silicon alloys. Garnyk and samarin3 have desulfurized transformer steel by vacuum treatment. Experiments were conducted in order to investigate the desulfurization of liquid iron under reduced pressures, and to establish the effect of some alloying elements, and various crucible materials. A vacuum-induction furnace of 50-lb capacity was used. The charge was Armco iron. Silicon was added as 90 pct ferrosilicon, carbon as electrode graphite, and aluminum as high-purity aluminum metal. Magnesia and silica crucibles were used, their inside diameters were 5 1/2 and 5 3/8 in., respectively. The temperature was measured with an optical pyrometer and it was held at 1600 1 15°C. Samples were withdrawn with quartz tubes of 6 mm ID, without disturbing the furnace atmosphere. Pressures were measured with an alphatron gage. The experimental results are shown in Fig. 1. They indicate that: 1) Sulfur can be removed from liquid iron alloys by vacuum treatment; 2) The desulfurization is enhanced by the presence of silicon, carbon, and aluminum, all these elements increase the activity of sulfur dissolved in liquid iron;4 3) The pronounced effect of silicon indicates that probably a volatile silicon sulfide is formed, Alcock and Richardson5 have observed a similar phenomenon; 4) The same rate of desulfurization was obtained when the metal was contained in either magnesia or silica crucibles. Dr. J. Keverian has contributed many discussions and recommendations. M. S. Sutliff has helped in conducting the heats. The permission of General Electric Co. for this publication is gratefully acknowledged.

Jan 1, 1960

By A. S. Yue

It was deemed desirable to obtain an understanding of the vacuum desulfurization process. McKechnie1 has reported that the sulfur content of nickel- and cobalt-base alloys is reduced in vacuo. Keverian and Taylor2 have observed that vacuum melting causes desulfurization of iron-carbon-silicon alloys. Garnyk and samarin3 have desulfurized transformer steel by vacuum treatment. Experiments were conducted in order to investigate the desulfurization of liquid iron under reduced pressures, and to establish the effect of some alloying elements, and various crucible materials. A vacuum-induction furnace of 50-lb capacity was used. The charge was Armco iron. Silicon was added as 90 pct ferrosilicon, carbon as electrode graphite, and aluminum as high-purity aluminum metal. Magnesia and silica crucibles were used, their inside diameters were 5 1/2 and 5 3/8 in., respectively. The temperature was measured with an optical pyrometer and it was held at 1600 1 15°C. Samples were withdrawn with quartz tubes of 6 mm ID, without disturbing the furnace atmosphere. Pressures were measured with an alphatron gage. The experimental results are shown in Fig. 1. They indicate that: 1) Sulfur can be removed from liquid iron alloys by vacuum treatment; 2) The desulfurization is enhanced by the presence of silicon, carbon, and aluminum, all these elements increase the activity of sulfur dissolved in liquid iron;4 3) The pronounced effect of silicon indicates that probably a volatile silicon sulfide is formed, Alcock and Richardson5 have observed a similar phenomenon; 4) The same rate of desulfurization was obtained when the metal was contained in either magnesia or silica crucibles. Dr. J. Keverian has contributed many discussions and recommendations. M. S. Sutliff has helped in conducting the heats. The permission of General Electric Co. for this publication is gratefully acknowledged.

Jan 1, 1960

By W. J. Slatosky

W. 0. Philbrook (Cairiegie Institute of Technologyogv—Mr. Slatosky has presented an interesting and constructive paper that represents another step along the way of converting steelmaking from an art to a science. I am confident that his computer will be practical and successful and that with a very few months of experience it will provide a significantly better degree of control than his record of 65 pct of heats within range obtained with the slide-rule calculator . A paper such as this, with a lot of symbols and condensed mathematics, is difficult to comprehend quickly. Since I have had an opportunity to study it carefully, perhaps my evaluation of its validity and accomplishments will save time for others. Mr. Slatosky has correctly used standard principles of stoichiometry and heat balances, which are available to anybody, but he has also brought to them two original contributions: 1) He has developed from operating data some empirical relations for predicting the final FeO content of the slag (at 0.5 pct C end-point) as a function of slag basicity, lance height, and scrap, ore, and scale in the charge. This improves the accuracy of prediction of temperature or scrap requirement compared with assuming an arbitrary, constant FeO content at the end of each heat. There is no assurance yet that exactly the same relations will hold for other furnaces or practices, but similar correlations can be expected. 2) He has combined calculations that are ordinarily carried out laboriously as a number of individual steps into a single, simple linear equation that can readily be fed into a machine. This involved a tremendous amount of painstaking detail work as well as the imagination to see the possibility and work out the steps. While his particular Eqs. [3] and [6] are valid only for the furnace design, charge weight, and blowing time used at Aliquippa Works, only a few numerical values have to be changed to adapt it for other conditions. In order to arrive at a useable solution, Mr. Slatosky had to make some basic assumptions about the process that are similar to those used by others. He neglected variation in some process variables and assumed an arbitrary average value for waste gas analysis and temperature for want of more exact information at the present time. All of these judgments are clearly stated. In addition, some thermody-namic data presently available are not adequate for the job, notably in relation to heats of formation and sensible heat in slag, and some expedient has to be adopted to get around the difficulty. Other people might prefer slightly different judgments about these details and hence obtain somewhat different numerical solutions. This is not of serious importance, however, because the errors accumulate in the "heat loss" term and are largely self-compensating for a constant heat time. Although the extended Eq. l(a) in Appendix I was set up as a rate equation originally, for convenience in using an analogue computer as stated in the paper, the time dependence was removed by later mathematical manipulations and assumptions about the process. The final result is an integration of element and energy balances from initial to final states; this procedure is as legitimate here as in any other form of heat-balance calculation. The formal handling of stoichiometry and thermochemistry appears to be correct, and it is assumed that any arithmetical errors would have come to light in applying the calculations to furnace practice. Mr. Slatosky's approach is not necessarily unique, in that other people might start with apparently different equations or prefer another form of final equation for another type of computer. However, he has presented an accomplished result that appears to be a theoretically sound and practically useful way of applying scientific principles and rapid computation for better control of steelmaking. His success will undoubtedly encourage himself and others to improve on the mathematical model and its use as better informatioq becomes available. John F. Elliott (Massachusetts Institute of Teck-t2ology)-The last comment by Mr. Richards that a calculator is quite unnecessary for an L-D operation ?-equi??es a rebuttal. The L-D furnace is a very high capacity process which places a premium on close control. When one is making steel at rates between 100 and 200 tons per hr, one cannot afford the luxury of an extra 5 or 10 min at the end of a heat correcting for an error that should never have been made in the first place. Mr. Slatosky's paper is a very sound application of the simple principles of stoichiometry and the energy balance. It is a satisfactory and valuable start, but only the start of the development of methods of control for this process. An analysis of the process shows that it should be very suitable to control by a computer. This is especially the case when various grades of steel are to be made. In fact, it would seem that the organizations who are planning new and bigger installations of L-D vessels should consider carefully the advantages that would stem from computer control of a vessel with the operator present to do little more

Jan 1, 1962

By E. Posnjak

IT is rather the general belief that acidified solutions of ferrous salts are readily oxidized when in contact with air, and often elaborate pre-cautions are taken to prevent it. This, however, is not the case and several statements may be found in the literature expressing surprise at the extreme slowness with which oxidation takes place when air or oxygen is bubbled through such a solution. Thus C. Baskerville and R. Stevenson1 "observed with surprise" that no. oxidation apparently took place, as shown by titration with 0.5 N KMnO4, when a stream of air was passed for 3 hr. through an acidified solution of ferrous ammonium sulfate or ferrous sulfate. The same authors state that even the presence of salts such as cobalt, chromium, copper, manganese, etc., which usually act as oxygen carriers, had "no effect upon the oxidation as was observed by, passing air for 3 hr. through solutions of Mohr's salt acidified with sulfuric acid." While this statement will be proved further on to be at least partly incorrect the slowness of the oxidation of ferrous salts alone has been previously established by McBain.2. His investigation also showed that the rate of oxidation increases markedly with an increase in the concentration of ferrous sulfate as well as that of oxygen; the concentration of free acid had a comparatively small influence, which in the case of sulfuric acid was to retard slightly the rate of reaction. More recently R. Thomas and E. T. Williams3 investigated the catalytic effect of nitric oxide on the oxidation of ferrous salts, which had been earlier patented by McCulloch.4 They found that the probable mechanism of the catalytic action was the oscillation of the catalyst between two stages of oxidation and its interaction alternately with the oxygen and the ferrous iron.

Jan 1, 1927