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By S. R. Seagle, R. Schuhmann, N. A. Parlee

Rates of CO evolution and CO absorption were measured for liquid-iron alloys containing from 0.15 to 4.4 pet C, using a modified Sieverts apparatus. The alloys were held in alumina crucibles, so that both crucible-metal and gas-metal reactions occurred simultaneously. The data are interpreted on the hypothesis that the C-O reaction rate is controlled by oxygen diffusion across the boundary layers at the gas-metal and crucible-metal surfaces. CARBON-monoxide evolution from liquid Fe-C-0 alloys is a key reaction in steelmaking processes, both in the steelmaking furnace and in the ingot mold. Also, this reaction probably is an essential step in the desulfurization of iron under blast-furnace conditions, for which carbon is the principal reducing agent or deoxidizer present in the iron. The thermodynamic properties of the solutions of C and 0 in Fe and the equilibria of these solutions with gaseous CO and CO, have been investigated in some detail and are reasonably well understood. However, while these equilibrium data have accumulated in the laboratory, other data have accumulated to show that equilibrium conditions are often not achieved under plant operating conditions. Thus, an understanding of the rate and mechanism of the carbon-oxygen reaction not only has theoretical interest, but ultimately may assume considerable practical importance. Reaction Mechanisms and Rate Equations The over-all reaction under consideration is C (in liquid Fe) + 0 (in liquid Fe) + CO (gas) [I] Although this appears to be a straightforward heterogeneous reaction, involving just two phases (liquid metal and gas), a wide variety of reaction mechanisms has been proposed. Different authors have expressed divergent views as to the nature of the rate-controlling steps. Accordingly, a brief discussion of the possible reaction steps will be given. 1) Homogeneous Reaction Within Liquid Iron— Feild' and Jette2 have applied chemical reaction-rate theory as if the C-0 reaction were a homogeneous, second-order reaction occurring within the liquid-metal phase. This mechanism necessarily produces CO "molecules" dissolved in liquid iron. In order to yield CO gas, the dissolved CO must nucleate CO gas bubbles, and the dissolved CO also must be transported to the bubble surface where it enters the gas phase. However, this mechanism is inconsistent with present concepts of the structure of liquid-metal solutions. 2) Reaction at Gas-Metal Interface—At the surface of contact between gas and metal, a second-order reaction between dissolved C and 0 may occur to produce a CO molecule which enters the gas phase. This reaction presumably involves an "activated complex" structure in the interface. Some such surface mechanism appears essential because the carbon and oxygen do not occur in the same species in the two phases and therefore must react in some way at the surface. At liquid-iron temperatures, calculations based on reaction-rate theory indicate that the surface reaction must proceed extremely rapidly and thus cannot be a rate-determining step in the C-O reaction under ordinary conditions.3 ccordingly when the over-all reaction is measurably slow, the surface reaction may be considered at equilibrium; that is Cc* Co* = m'Pco [2] in which Co* and Co* are the concentrations of carbon and oxygen (weight per unit volume of metal), respectively, in the liquid-metal phase at the interface, Poo* is partial pressure of CO in the gas phase at the surface (atmospheres), and m' is the mass-action constant for Reaction [I]. Since activities of C and 0 are not strictly proportional to concentrations, m' is not a true thermodynamic equilibrium constant but varies with carbon content.' 3) Mass Transport—If the reaction is to proceed at the gas-metal surface, as described above, dissolved carbon and oxygen in the liquid iron must come to the surface and gaseous carbon monoxide must move away from the surface. Details of the mass-transport mechanisms depend on the kind of system under consideration. For a stirred metal bath in contact with a CO gas phase, the transport of C and 0 to the surface can be described by 1 Do Mols CO evolved per sec = — 1/16— Do/do Agm (CO-Co*) = 1/12 Do/do Agm *(Co-Co*) [3] In this equation, Do and D, are the diffusion constants for oxygen and carbon in liquid iron, 6, and 6,. are the boundary-layer thicknesses, A,,,, is the

Jan 1, 1959

By T. L. Joseph, G. Bitsianes

The gaseous reduction of dense iron ore is a topochemical process in which reduction takes place at distinct interfaces between solid phases or layers. Under normal conditions, these interfaces remain parallel to the exterior surface of the ore body as they move inward. Certain conditions, such as cracking, high porosity, impurities, entrapped residual oxides, may cause departures from normal topochemical behavior. THE gaseous reduction of dense iron ore proceeds at interfaces between several solid phases or layers.',' Under normal conditions, these interfaces progress inward and remain parallel to the exterior surface of the ore body. This topochemical behavior is clearly illustrated in Fig. 1 which shows partially reduced specimens of natural and synthetic hematite. Using a coordinated sequence of macro, micro, and X-ray examinations, the authors1-'2 found that the number of interfaces and participating phases was in agreement with the Fe-0 system. Above 570°C, reduction of the ore involved a maximum of three common boundaries between four solid phases: iron, wiistite (Fe,O), magnetite (Fe,O,), and hematite (Fe,O,). Below 570°C, reduction proceeded through two interfaces between three phases: iron, magnetite (Fe,O,), and hematite (Fe,O,). The decrease in the number of phases below 570°C was due to the instability of wiistite below this temperature. The sequence of phases was also consistent with the equilibrium requirements. For example, the layers of iron oxides that were formed in topochemical fashion were always orientated in the order of increasing oxygen content. Thus, in Fig. 1 an outer layer of metallic iron is followed in turn by a thick intermediate band of black wiistite, by a thin layer of light magnetite, and finally by a relatively large core of hematite. This arrangement of the oxide layers was due to restrictions in reducing conditions which were imposed by the physical structure of the solid. The highly reducing gas on the outside of the particle gradually lost its reducing power as it penetrated into the specimen. On a macro scale, the layers of the various oxides appeared to be sharply defined and uniform in composition. Microexamination of the sections, however, revealed that the interfaces did possess measurable widths which varied with the porosity and chemical activity of the oxide phase undergoing reduction. For example, Fig. 2 shows three interfaces in a dense hematitic ore which was partially reduced at 850°C. At the iron-wiistite interface where the greatest porosity developed, the reaction proceeded over a zone 25 to 30 microns in width. Toward the interior, the interfaces became progressively narrower until at the magnetite-hematite boundary the reaction zone was about 1 micron wide. In this region the structure was exceedingly dense; the hematite possessing a porosity on the order of 3 pct. A careful micro study across polished layers of the various oxides revealed generally homogenous and single-phase structures. As reported in a previous paper,' the wiistite layer was characterized by an increase in oxygen content with depth of penetration. The topochemical behavior of reduction was studied in six types of ore of different origin, composition, and physical structure. In most cases, reduction proceeded at the boundaries of well defined layers or phases, and this behavior may be regarded as normal for most dense fine grained ores. Deviations from Ideal Topochemical Behavior A number of deviations from the normal topochemical behavior were noted. In these cases, the continuity of the reduction interfaces was disrupted in one of four ways: 1—Cracking of the specimen interrupted the geometric configuration, and the interfacial advance was no longer parallel to the exterior surface. 2—As a result of high porosity, the interfaces were spread over an appreciable distance and all but obliterated. 3—Impurities in the ore promoted a variety of deviations, including cracking. 4—A residual oxide phase was entrapped in the reaction product and left behind the advancing macro interface. Results from Cracking: A crack leading into the interior of an ore specimen presents a path of least resistance for the counter-flow of reducing gases and gaseous reduction products. Higher reducing conditions can be maintained along such cracks and reduction accordingly will propagate well ahead of the normally advancing reduction interfaces. Cracking was caused by a number of factors, one of which was the thermal spalling of impurities in the massive form. A more general type of cracking was due to reduction and was found in all dense varieties of natural and synthetic hematite, particularly in the temperature range of 500" to 700°C. The effect is shown clearly in Fig. 3. In this case, a dense sphere of pure hematite was partially reduced at 650°C for 100 min. The macrosection shows that one large reduction crack had penetrated the specimen and disrupted the normal topochemical advance of the interfaces. The outer layer of iron was only slightly affected but the thin dark layer of wiistite, adjacent to the ferrite, had widened perceptibly as it progressed along the crack. Farther inward, the magnetite layer was greatly disrupted and had penetrated irregularly to form islands of unaltered white hematite. A great deal of internal cracking is evident in the magnetite phase. From a practical point of view, the cracking of dense ores in the blast furnace could lead to desirable as well as undesirable effects. The general result

Jan 1, 1956

By Paul A. Beck, M. N. Parthasarathi

By determining the (220) pole figure for OFHC copper rolled to 96 pct R. .A., the occurrence of four texture components of the type (135) [211] was confirmed. It was found that the total volume fraction of material close to the four symmetrical orientations of this type is larger than the volume fraction of the other components put together. THE rolling texture of copper was described by early investigators1'" as a mixture of components of the (110)[l12] and (112) [11l] types. Other studies, still using the qualitative photographic method of texture determination arrived, instead, at orientations of the type (135) [533] or (135) [211] for copper3'4 and at the closely related "Z-texture" for a fee nickel-iron alloy.5 The prevalence of this type of orientation, near (123) [412], in the rolling texture of aluminum and of copper was later confirmed by means of quantitative diffractometer methods.' However, in a recent paper7 Jones and Fell stated that the (110) [112] and (112) [111] double texture was in better agreement with the measurements of Young's modulus for cold-rolled copper.' These authors also expressed their belief that the "roll texture" can be determined by means of two photographic quasi-fiber texture patterns taken with sheet specimens rotated around the rolling direction and the transverse direction, respectively. Jones and Fell found7 that the results obtained from such patterns for cold-rolled nickel did not agree with any of the orientations mentioned above, but they suggested that the observed diffraction spots may have been brought about by the overlapping of reflections due to the (110) [112] and (112) [11l] double texture components. Jones and Fell concluded that the (123) 14121 type orientation is inconsistent with their patterns. They also stated, without offering any supporting evidence, that this orientation is inconsistent with the (220) pole figure. "Ideal orientations" are often used for a very rough description of the principal orientations encountered in a texture, It is, however, well to remember the fact that, no matter how "accurate", these ideal orientations are only schematic representatives of a continuous distribution9, which often (as in the case of rolled copper) includes extensive orientation spreads. The attempt by Jones and Fell7 to use elastic modulus data in deciding between various ideal orientations in the rolling texture of copper neglects this fact. The inadequacy of two-dimensional "axis density figures" in describing orientation distributions in sheet textures was previously discussed.9 It was also pointed out9 that there is no reliable evidence to prove that orientation distributions derived by the "quasi-fiber method" from rotated sheet specimens are fully equivalent to the corresponding information obtainable from quantitative pole figures. The view that a sheet texture could be adequately determined by means of two photographic quasi-fiber texture patterns is obviously erroneous9. The question as to the consistency with the (220) pole figure of ideal orientations derived from the (111) and (200) pole figures is, on the other hand, certainly very relevant. Since no quantitative (220) pole figure for cold-rolled copper appears to be available in the literature, the following work was undertaken. EXPERIMENTAL METHOD An extruded rod of OFHC copper, 1 in. in diam, was given alternate rolling (30 to 35 pct R.A.) and

Jan 1, 1962

By G. C. McCartney, S. J. Kidder

The Helen Mine, of the Algoma Steel Corporation, in the Michipicoten district, Ontario, Canada, has produced more than 6,240,290 tons of iron ore. Prior to and during World War I, 2,823,369 gross tons of brown ore were shipped, and from 1939 to the end of the 1944 season, 3,416,921 gross tons of siderite ore were produced from open-pit operations. Brief descriptions are given of the nature of the ore, the mining methods employed and the manner of treatment of the ore. Shipment of the finished product, known as Algoma sinter, is made to blast furnaces in both Canada and the United States. The iron-ore bodies—i.e., the oxide ores of the Old Helen and the siderite of the New Helen—are a part of a tabular shaped area of iron formation that extends over a length of more than 100,000 ft. and has a maximum width of 1000 ft. The ores are considered to be a product of introduction of iron-bearing material accompanied by replacement of the rocks already present. It is shown that introduction took place subsequent to the development of the major folded structures. It is believed the iron-bearing material emanated from an igneous source. Introduction The Michipicoten mining district derives its name from the Indian word1 meaning "place of bold promontories" or "region of big places," and anyone who has visited this part of Canada will agree that the district is well named. In 1897, there was active prospecting for gold in the district and the Ontario Bureau of Mines2 opened a recording office at the Hudson's Bay post at Michipicoten River. In the summer of 1897, Ben Boyer, probably searching for gold, discovered an outcrop of brown iron ore at the east end of a small lake, less than 8 miles, in an air line, northeast of the nearest point on Michipicoten Harbour. In the following year, extensive surface exploration and diamond drilling disclosed a commercial body of nonbessemer brown ore, possibly 700 ft. long and 200 ft. wide, of about the following analysis:3 Fe (natural), 57.15 per cent; S, dried at 212°F.. 0.113; SiO2, dried at 212°F., 4.00; P, dried at 212°F., 0.125. The property (Figs. 1-3) was taken over by E. V. Clergue and ultimately was transferred to the Algoma Steel Corporation. The Algoma Central Railway shortly afterward built its line from Michipicoten Harbour to the mine, together with an ore dock at the Harbour. Thus, within three years of its discovery, the mine had adequate shipping facilities and a market for its ore. Production of Brown Ore and Pyrite The first shipment of brown ore was made in July 1930. By 1939, the mine was shipping at the rate of 170,000 long tons

Jan 1, 1949

By S. J. Kidder, G. C. McCartney

The Helen Mine, of the Algoma Steel Corporation, in the Michipicoten district, Ontario, Canada, has produced more than 6,240,290 tons of iron ore. Prior to and during World War I, 2,823,369 gross tons of brown ore were shipped, and from 1939 to the end of the 1944 season, 3,416,921 gross tons of siderite ore were produced from open-pit operations. Brief descriptions are given of the nature of the ore, the mining methods employed and the manner of treatment of the ore. Shipment of the finished product, known as Algoma sinter, is made to blast furnaces in both Canada and the United States. The iron-ore bodies—i.e., the oxide ores of the Old Helen and the siderite of the New Helen—are a part of a tabular shaped area of iron formation that extends over a length of more than 100,000 ft. and has a maximum width of 1000 ft. The ores are considered to be a product of introduction of iron-bearing material accompanied by replacement of the rocks already present. It is shown that introduction took place subsequent to the development of the major folded structures. It is believed the iron-bearing material emanated from an igneous source. Introduction The Michipicoten mining district derives its name from the Indian word1 meaning "place of bold promontories" or "region of big places," and anyone who has visited this part of Canada will agree that the district is well named. In 1897, there was active prospecting for gold in the district and the Ontario Bureau of Mines2 opened a recording office at the Hudson's Bay post at Michipicoten River. In the summer of 1897, Ben Boyer, probably searching for gold, discovered an outcrop of brown iron ore at the east end of a small lake, less than 8 miles, in an air line, northeast of the nearest point on Michipicoten Harbour. In the following year, extensive surface exploration and diamond drilling disclosed a commercial body of nonbessemer brown ore, possibly 700 ft. long and 200 ft. wide, of about the following analysis:3 Fe (natural), 57.15 per cent; S, dried at 212°F.. 0.113; SiO2, dried at 212°F., 4.00; P, dried at 212°F., 0.125. The property (Figs. 1-3) was taken over by E. V. Clergue and ultimately was transferred to the Algoma Steel Corporation. The Algoma Central Railway shortly afterward built its line from Michipicoten Harbour to the mine, together with an ore dock at the Harbour. Thus, within three years of its discovery, the mine had adequate shipping facilities and a market for its ore. Production of Brown Ore and Pyrite The first shipment of brown ore was made in July 1930. By 1939, the mine was shipping at the rate of 170,000 long tons

Jan 1, 1949

H. H. Bleakney (Dept. of Mines and Technical Surveys, Ottawa, Canada)— The work of Dr. Machlin and his colleagues at Columbia University is so scholarly that one hesitates to take issue with them. Nevertheless the writer feels compelled to enter a demurrer to the mechanism of intercrystalline cracking proposed in this paper. The principal obstacle to its acceptance is found in its preoccupation with purely mechanical influences and its disregard for the chemical effect of impurities. The writer believes that the destruction of metallic cohesion by concentration of impurities at the grain boundaries is a necessary and sufficient condition for the development of intercrystalline cracking; and he believes that discussion of the numerous mechanical explanations proposed should wait until some valid objection to the chemical hypothesis has been advanced. It is nearly twenty years since Gillett" drew attention to the possibility that the chemical influence of precipitation might be the cause of intercrystalline cracking. As early as 1935, Greenwood'" remarked that grain-boundary precipitation of impurities in lead appeared to promote intercrystalline cracking. Again in 1939, Scott commented as follows on a paper by Thielemann and Parker:'" "There are at least two familiar phenomena that can influence grain-boundary cohesion: 1) intergranular oxidation; and 2) grain boundary precipitation. An important consideration in this work, therefore, is to determine which, if either, of these factors is responsible for the low values of cohesive strength observed." In 1952. the writer presented evidence," some original and some abstracted, which indicated that in copper, silver, aluminum, lead and iron, intergranular cohesion was a function of the purity of the metal. In 1954 Glen, discussing a paper by Ridley and Tapsell14 indicated his belief in a precipitation mechanism for the intercrystalline embrit-tlement of molybdenum steel and suggested that with an absolutely pure metal it would be almost impossible to obtain an intercrystalline crack. This suggestion has

Jan 1, 1959

By R. L. Wiegel

The generation of operating information for mineral beneficiation processes has become more sophisticated as a result of the use of improved laboratory analytical techniques, some of which provide multiple component assays, as well as the introduction and gradual industrial acceptance of process sensors for the measurement of flow, density, size, and chemical composition. In general, however, the mineral processing engineer's ability to tie together this wealth of information has not kept pace with these developments. In fact, in almost all existing plants, the metallurgical inflow-output balance, wed to indicate current process performance, is still being calculated from only a small portion of the information routinely available. There is substantial activity in the development of techniques for using all available process information to significantly improve the reliability of the metallurgical balance. While the use of these improved techniques does require access to computing facilities and a slight change in perspective on the part of the mineral processing engineer regarding the inviolability of process information, there are numerous practical benefits to be derived from their application. In addition to summarizing some of the concepts basic to these techniques, this paper describes the experience of the author in applying one of these advanced metallurgical balance techniques to a variety of pilot plant and commercial plant flowsheets during the past eight years.

Jan 1, 1983

By L. D. Godshall

The latest revised edition of Mr. C. A. stetefeldt's book on the Lixiviation of Silver-Ores, which appeared very recently, contains no mention of the volatilization of silver in chloridizing-roasting—an omission which is the more remarkable in view of the fact that in former editions of the work this important subject was noticed. Moreover, Mr. Stetefeldt has discussed it to some extent in his paper on " The Stetefeldt Furnace," * in which he criticised certain statements made by me before the Colorado Scientific Society in May, 1893, in a paper entitled " A Review of the Russell Process;" ? and Mr. Morse, in his paper on " The Lixiviation of Silver-Ores by the Russell Process at Aspen, Colorado," $ has given statistics showing the loss of silver by volatilization (including the dustloss, which Mr. Morse estimates at not more than 1 per cent.) on more than 30,000 tons of ore roasted, to have been 9.16 per cent. The matter must certainly be deemed important enough to warrant me in returning to it, and offering, with the aid of the figures made public since my first paper, a reply to the criticisms of Mr. Stetefeldt. The passages of my paper which he deemed to be " ques-

Jan 1, 1897

By Frank A. Hill

A visitor to the Northern anthracite coal-field in 1844 wrote: " History and song have hallowed the valley of Wyoming, and everything pertaining to it seems wrapped in an atmosphere of romance." Song and history have since been almost forgotten in the rush of enterprise and business energy, while the invested capital which has built 160 colliery plants, producing last year 17,031,826 tons of coal and giving employment to 50,000 men and boys, lends an atmosphere the inspiration of which is the very sustenance of prosperity and progress. The fundamental cause of this great valley's financial strength, however, rests on the fulness of its mineral wealth. Its mountains surround and its cities are built upon anthracite coal. Its foundation, physically, financially and socially, is coal. Its geology has governed its growth and developed its greatness. In 1768, ten years, prior to the celebrated Wyoming massacre, two Connecticut Yankees, named Gore, settled near Wilkesbarre, Luzerne County, and, burning Pennsylvania anthracite in their blacksmith's forges, were the first to utilize it as a fuel. Its first use in the household was also at Wilkesbarre, where, in 1808, Judge Fell burned it in an open grate. Carbondale, Wilkesbarre, and Scranton were early recognized as the coal centers of the field.

Jan 1, 1887

By Edgar T. Wherry

EDGAR .T. WHERRY,* Washington, D. C. (communication to the Secretary ?).-Dr. Pogue's presentation of the facts concerning the emerald deposits is very clear and convincing, and the only addition that I can suggest is a summary of previous theories of origin. He makes it evident that the pegmatite theory is the only one capable of explaining the existing relations, but upon certain details there may be some difference of opinion. If I understand the term pneumatolytic, it does not imply that all the elements concerned in a given deposit were transported as gases, but rather that the crystallization of these elements into the various minerals was favored by the presence of certain gaseous substances, notably H20, C02 and HF. It is highly improbable that the oxides of glucinum, aluminum, chromium, and silicon, which enter into the composition of the mineral emerald could have been transported in the gaseous form. The same is true of the metallic constituents of the parisite and other associated minerals. The explanation suggested, that solutions separated into liquid and gaseous portions, the latter ascending and forming the emerald in the upper portions of the rock only, therefore, seems to me untenable. When two formations exist side by side and one, A, is mineralized while the other, B, is barren, the possible explanations may he classed as (1) chemical, and (2) physical. 1. Some chemical feature of A not found in B might have caused crystallization of certain minerals in the former, which did not appear in the latter. In the present instance both rocks appear to be so similar chemically that no such effect can be looked for. Pogue mentions carbon as a possible precipitating agent, but describes both formations as carbonaceous, so that the difference in the minerals of the two can not be thus explained.

Jan 10, 1916

By E. B. Swanson

There is only one way to transport natural gas and that is by pipe lines. In the past few years, these lines have been extended rapidly into areas which previously had been served mainly by solid and liquid fuels. In the subject given me, this extension is referred to as an invasion, which implies a rather forceful entry. Whether or not such an implication may be applied to recent natural-gas developments is unimportant. It is the fact of the extension, not its definition, which is important. For centuries, natural gas has been utilized for various purposes in many parts of the world. It was the foundation of fire worship at Baku. The Chinese used it for the evaporation of brine in salt manufacture. In our country, its history seemingly dates back 110 years to the vicinity of Fredonia, N. Y., where seepage gas was assembled and used for lighting purposes. A few years later, a %inch pipe was laid to a lighthouse on Lake Erie, and the early records of the Lighthouse Service tell of the difficulties surrounding this use. With the discovery of oil in Pennsylvania, there followed further development; the town of Titusville was piped with natural gas and, some few years later, gas was made available for manufacturing plants adjacent to the oil fields. For more than a half century, the industry was concentrated in the

Jan 1, 1932

By C. A. Rowland, M. D. Flavel

There are seven basic comminution circuits that can be used to prepare beneficiation feed from the product of a primary crusher. This paper gives a comparison of these circuits based on average process and economical data. The paper is principally devoted to a discussion of the test work required to obtain the process data needed to evaluate each circuit. The results of the test work in conjunction with geographic and economic factors can be used to narrow down the choice of possible circuits to one, two, or three before making a detailed engineering study.

Jan 1, 1985

By G. Das, S. V. Radcliffe

The substructural features developed in tungsten as a function of annealing temperature (up to 2200°C) and type of material [undoped and doped powder metallurgy (PM) tungsten and electron beam melted tungsten] have been investigated by transmission electron microscopy. For doped PM tungsten wires, characteristic "par-ticulate" substructural features developed rapidly with increase in annealing temperature above 700°C. The features consisted of parallel rows of elongated or circular shapes (500 to 1000A diam) lying along the direction of the wire axis and were identified as internal voids by diffraction contrast experiments. In recrystallized doped PM rod, larger voids were observed and were identified by precision dark field analysis to be cubic in shape and bounded by (100) planes. In marked contrast with both the doped PM materials, recrystallized undoped PM rod exhibited only very occasional and randomly arranged voids. Furthermore, no voids were observed in either material after electron beam melting. The high concentration of voids in the doped PM materials is attributed primarily to vaporization of doping additions or their pvoducts situated at the original grain boundaries , whereas the few voids in undoped material are considered to be traces of microporosity which were not eliminated during sintering. A tentative mechanism is suggested for the dezlelopment of the voids in relation to the processing sequences (sintering and working) and to the subsequent annealing. In recent years, a characteristic substructural feature consisting of rows of small elongated or circular regions of light contrast lying along the direction of working has been seen in thin foil electron microscopy studies of annealed sheet, wire, and rod tungsten. These features were present in the published micrographs of sheet by Weissmann et al.1 and of wire by Meieran and Thomas2, although the authors did not draw attention to them. Wronski and Fourdeux3 observed similar features in sintered rod tungsten (it was not specified whether or not the material was doped*) and interpreted them on the basis of their ap- particles, based on extraction replica evidence from the fracture surface of the initial hot-rolled slab material from which the sheet was prepared. No diffraction contrast experiments on the features were reported in any of these studies. The present investigation was undertaken with the primary objectives of: a) identifying the nature of these substructural features in tungsten by electron diffraction contrast experiments, since the contrast for voids can be expected to differ from that for crystalline or glassy particles, and b) elucidating the origin of the features and their development. For the latter purpose, doped and undoped powder metallurgy tungsten was obtained as rod and wire to represent different stages of reduction during final processing. These materials were examined both in the as-processed condition and after annealing to successively higher temperatures. In addition, the same doped and undoped materials were examined after vacuum melting in rod form. I) MATERIALS AND PROCEDURE Doped powder metallurgy (PM) tungsten wire (commercial purity 99.9 pct W) was obtained in the as-drawn and surface ground condition (0.030 in. diam "ground seal rod"). Doped and undoped tungsten rod (0.075 in. diam) representing an earlier stage of final processing was obtained from the same commercial source (Refractory Metals Division, General Electric Co.). Lengths of both the doped and undoped rod materials were single-pass melted in an electron-beam zone refiner to examine the effect of vacuum melting on the substructure. Annealing was carried out in a tungsten crucible in a tantalum strip resistance furnace under a vacuum of l0-15 mm Hg. Longitudinal sections of the wire and rod materials were examined by light and electron microscopy. The preparation of thin foils suitable for electron transmission from 0.030 in. diam tungsten wire and the rod specimens was carried out by means of a high-precision microjet technique developed to provide lack of jet stability and precise control of the area thinned. The method is described in detail elsewhere.' The foils were examined in a JEM 6A electron microscope using a goniometer stage (±20 deg tilt, 360 deg rotation) and operated at 100 kV. To minimize contamination problems a 200 µ condenser aperture was used in conjunction with a useful beam current of 50 µA. II) RESULTS AND DISCUSSION A) Diffraction Contrast Analysis. In order to determine the optimum conditions for the development of the substructural feature, a series of isochronal 30 min annealing experiments were carried out on specimens of the doped PM tungsten wire. The transmission electron microscopy analysis showed that the as-drawn wire, Fig. 1(a), consists of 'fibers' whose long axis is closely parallel to the wire axis of (110). The fiber width averages some 0.5 µ. Dense disloca-

Jan 1, 1969

By W. A. Backofen, G. Y. Chin, W. F. Hosford

The ductile fracturing process was studied in single-crystal and poly cvystalline aluminum deformed in tension over a temperature range from 295° to 4.2°K. At temperatures as low as 77°K, the fracture of "inclusion-free" material, including zone-refined aluminum, was by rupture (-100 pct RA). At 4.2 OK, fracture was brought on by adia-batic shear. Metallographic examination did not disclose any voids or slip-band microcracks, thus negating for inherently ductile metals any mechanism of void nucleation by vacancy condensation or of cracking due to dislocation pile-ups. In Izigh-purity aluminum not treated to be inclusion-free, fracture at temperatures as low as 45°K was of the double-cup type and a result of void formation. The reduction-of-area decreased as temperature was lowered, corresponding to the earlier appearance of voids. Such behavior was rationalized in terms of a larger increase, with decreasing temperature, in the .flow stress relative to the strength of the inclusion-matrix interface. Evidence for low-temperature adiabatic shear was found in discontinuous flow at 4.2"K, in the transition to a localized shear fracture at low temperatures, and in the suppression of shear fracture with an elastically hard pulling device. A simple analysis for the initiation of adiabatic shew permitted a general correlation of the various contributing factors. It has been pointed out that the duration of shear depends upon effective mass and elastic stiffness of the deformation system. IT has long been recognized that fracture* may Throughout this paper, the term "fracture" is taken to mean any process that results in the separation of a material into two (or more) parts. Thus rupture as it may be encountered in a tension test leading to 100 pct reduction-of-area is included in this category. occur in a ductile mode, and that the process can be of great practical as well as general interest. Much information about ductile fracture has also been accumulated over this period, but only recently has an understanding of mechanism begun to appear. Ludwik,' in 1926, first reported fracture in a tensile specimen starting with a central crack in the necked section. Since then, other studies have disclosed that such cracks may form by the coalescence of voids nucleated in this region where hydrostatic tension is highest.2-4 Rogers and Crussard et al.' have emphasized void formation and reori-entation along localized shear bands as a mode of crack propagation. pines6 has considered the tensile rod as a bundle of fibers joined by weak interfaces, which subsequently separate to allow individual fiber contraction. The notion of cavity growth and coalescence by purely plastic processes was discussed by Cottrell: who added that the tensile reduction-of-area ought not to be sensitive to temperature. On the other hand, it has been observed that the reduction-of-area is greatly increased if tests are carried out at high temperaturesa or under high hydrostatic pressure.' Fracturing anisotropy in wrought products lends support to the idea of void formation from preexisting flaws strongly aligned by earlier processing.''-l2 There is evidence that many voids result from the fracturing of inclusions or separation at the inclusion-matrix interface Another possibility is that voids grow out of pore volume produced in the initial solidification and never fully removed in later working. In general, a structure 3f particles, pores, and weak interfaces can be expected, at least in materials of engineering interest. Vacancy condensation has been suggested as an alternative mechanism of void formation for materials considered to be inclusion-free.13 Yet experience has shown that tensile reduction-of-area increases with purity, to the extreme of rupture as so often observed in single crystals. Adiabatic shear has an important bearing on ductile fracture. It occurs when the decrease of flow stress, as a result of local temperature rise from heat generated during straining, becomes larger than the increase due to strain and strain-rate hardening. As demonstrated by experiments on punching of plates,14 a large temperature rise may be brought about by rapid straining. Adiabatic flow as a result of the high strain rate reached in an ordinary tensile specimen just prior to separation may account for the cone formation in cup-and-cone fracture;14 evidence of such local heating has been presented.15 For geometrical reasons, however, pure sliding along the conical surfaces is unlikely, and separation under tensile forces is probably an important accompanying feature of the shear.7 In deformation processing operations, a high shear-strain rate may exist at boundaries between plas-

Jan 1, 1964

By John Gann

THE following investigation constitutes a brief resume of the more important binary magnesium alloys from the standpoint of metallographic technique, and the effect of heat treatment on structure and properties. The comparative newness of the subject justifies this procedure as a preface to a more detailed study of each individual series of alloys. The work was started with the idea of practical application in the industry rather than as a theoretical investigation. The alloy compositions studied were selected as those most likely to show whether heat treatment would produce beneficial results. Furthermore, it was considered satisfactory to use commercial 99.9 per cent. magnesium, the best commercial grade of alloying ingredients, and to limit the time of heat treatment at the expense of incomplete equilibrium. These facts must be kept in mind when examining the results obtained, and the conclusions drawn.

Jan 1, 1928

By R. H. Harrington

THE definition of precipitation-hardening is well understood and its principles have been subjected to study for some time. However, the variation of properties with double aging, combined with strain-hardening, gives promise of new and useful phenomena. Properly to understand these distinctions, definitions of these terms are necessary. Precipitation-hardening. This reaction usually depends upon an alloy having such a composition that it consists only, or in major part, of but one phase, a solid solution, at a high temperature, so that, upon slow cooling, this solution breaks down into two phases, the solid solution and a compound. By heating the alloy to the temperature for maximum solution of the compound, quenching, and reheating to a suitable lower temperature for critical dispersion precipitation of the compound, useful properties of the alloy may be developed to a maximum. Double Aging.-Dougle aging in part is similar to the process for precipitation-hardening, consisting of heating a precipitation-hardening alloy to the solution temperature, quenching, reheating to the suitable dispersion precipitation temperature, strain-hardening, and again reheat-ing to a suitable temperature to develop certain useful properties to a maximum. The strain-hardening may be induced by two methods: (1) a rate of cooling from the first reheat may suffice to strain the solid solution lattice of the alloy; or (2) the alloy may be cold-worked to a suitable degree between the two reheats.

Jan 1, 1936

By H. C. Howard

Reaction of oxygen and bituminous coal starts as soon as the coal bed is exposed to air and, with some coals, proceeds with significant velocity even at normal temperatures and at normal oxygen partial pressures of one-fifth of an atmosphere. At higher temperatures, the reaction is greatly accelerated and ultimately a condition is reached where the process is very rapid and we then speak of combustion. It is the purpose of the present paper to discuss the reactions of oxygen and coal at temperatures below those of active combustion. It is these low temperature oxidation reactions which are responsible for heating in storage and for marked changes in agglutinating proper-ties. These reactions may also be employed for the preparation of organic acids, which are of direct interest to the chemical industry. For convenience in discussion, the low temperature reactions of oxygen and bituminous coal can be roughly divided into three stages though there is, of course, overlapping. Stage I is a surface oxidation stage, characterized by the addition of oxygen, with the formation of oxygen containing groups some of which have acidic properties. Carbon dioxide, carbon monoxide and water may be formed con-comitantly and are always liberated at higher temperatures, and in cases where the oxidation is prolonged. Superficially, the coal is little affected by this primary stage of oxidation and usually only minor changes in ultimate composition result. There may be definite changes in coking and coking properties, and heat of combustion susceptibility to further oxidation. The presence of acidic groups can be demonstrated by specific reactions. These groups may show cation exchange properties like the mineral zeolites. The formation of oxalic acid has been reported. If the oxidation is continued, a large fraction of the organic material of the coal is converted ultimately into alkali soluble, acid insoluble products, which have been given the name "regenerated humic acids" and which are the characteristic products of Stage 2. These humic acids, in the solid stage, do not differ greatly in appearance from the original coal, but show large differences in chemical composition and chemical and physical properties. Along with the humic acids, carbon dioxide and some of the water soluble types of Stage 3, are also formed. If the oxidation is carried still further, the humic acids may be degraded completely to the simpler, lower molecular weight acids of Stage 3 which are characterized by solubility in acid as well as in alkaline media, and by their orange, yellow or white colors. Additional carbon dioxide is formed in the transformation from Stage 2 to Stage 3 and, for a number of American coals, a maximum yield of the water soluble types of acids is reached when about 50 pct of the carbon of the coal is converted to carbon dioxide. Primary Oxidation The initial step in the reaction of gaseous oxygen on coal, like that on carbon,

Jan 1, 1949

By T. A. Wright

THE SAMPLING of waste materials containing copper, lead and tin has taken on a new significance within recent years, and is of increasing importance, on account of the entry of some of the copper refineries into this field and the tendency towards consolidations among the smelters. In the past, such material was sold on the basis either of a rough or grab sample or of casual inspection of the lot. The two principal sources of this waste are the processes of fabrication and the scrapping of automobile, electrical, plumbing, railroad and other equipment. In both cases much material can be sorted, salvaged and sold by classification and grade to be melted "as is" or with the addition of new or virgin metal. The increasing care in classifying exercised in the large manufacturing plants tends to increase the proportion of this usable scrap; on the contrary, the increasing use of more complex and special non-ferrous alloys tends to make sorting and grading more difficult in turnings, borings, clippings, etc., and consequently is making sampling of more moment. In tin, lead, aluminum, and zinc furnace by-products such as ashes, drosses, skimmings, etc., the trade practice of evaluation has not varied much. For instance, tin drosses, battery lead, and aluminum skimmings are ordinarily sold on what is called "metallic button" or "metallic recovery" or "metallic yield." Copper and lead waste, however, is being sold more and more on actual copper and lead contents based on sample and chemical analyses. This paper will be devoted chiefly to the sampling of materials suitable only for refining and recovery of one or more of the metals present. The methods described are often based on the fact that but one metal, such as copper, is to be paid for. The loss of volatile constituents in melting does not appreciably affect the final copper result, as the "after-melting" assay can he readily calculated to the "before-melting" basis, but if smelter efficiency continues to increase, so that in time zinc, for instance, may be recovered on a paying basis, the method of sampling dirty brass, for example, will have to be changed also. As a matter of fact, we may expect that improved refining processes will make possible the partial recovery of lead and tin which are now lost.

Jan 1, 1928

By J. L. Wyatt

THE smelting of ilmenite to produce a slag rich in titanium, with pig-iron as a byproduct, introduces new concepts in electric smelting metallurgy. Titanium slags are characterized by low electrical resistance, thereby requiring a different type of electric furnace operation, and power supply sources substantially different from those encountered in normal steel melting and siliceous ore smelting furnaces. This paper describes special apparatus for determining specific electrical resistivity of titanium slags, and reports the values obtained on slags encountered in the process of smelting ilmenite ores. In an induction furnace under conditions approximating normal furnacing operation, 25 general heats and 6 special standardization and comparison heats were run. Results indicate relatively low resistivity. Resistivity depends primarily on slag composition, and, to a lesser degree, on temperature. During the summer of 1947 a cooperative project between the National Lead Co. and the Bureau of Mines was conducted at Boulder City, Nevada, in the Electrometallurgical Laboratories of the Bureau. The project involved smelting of ilmenite ores in electric furnaces, and has been reported in detail.' The author participated as a member of the staff of the National Lead Co. during the entire campaign. One outstanding characteristic of the titaniferous slags, their apparently excellent and variable electrical conductivity, was considered sufficiently important to warrant further study. Although little electric smelting of iron ores has been done in the United States, a certain amount of information is available for comparative purposes. Personal experience in smelting siliceous iron ores in electric furnaces furnished further information for comparison. In general, silicate slags are relatively poor conductors of electricity. Current flow during smelting operations may be maintained through a floating layer of coke on top of the slag bath, or through a bath of molten iron, beneath the slag. Silicate slags are not sufficiently conductive to furnish a path for current passage when normal furnace voltages are used. Experimental smelting of a silicate iron ore was undertaken for comparative purposes. A fluid melt was not obtained until the FeO content was reduced to 15 pct. The resistivity increased as the FeO content decreased, FeO compounds being the most conductive of the various oxides in such a normal slag system. The converse appears to be true in slags containing large percentages of TiO2. It has been found that titanium slags become molten with FeO percentages in excess of 30 pct, and that the conductivity becomes generally better as the FeO con-tent of the slag diminishes. This phenomenon was demonstrated in the furnacing operations at Boulder City. During the initial smelting period furnace electrodes could be held immersed several inches in the slag, with tap selectors set for a no-load voltage of 70 v. As the FeO content decreased, the furnace electrodes would "walk up," until at one point in the process the tips would break the surface and arc on top of the slag. This was undesirable since direct arcing caused losses of important flux additions. The slag compositions under study at that time were such that losses due to surface arcing sometimes caused viscous slags to be formed. Forcing the electrodes into the slag bath by manual control to prevent surface arcing resulted in excessive power input and lack of control. Suitable low voltages were not available. Measurement of the electrical resistivity of titanium slags at various operating temperatures and slag compositions was undertaken. It was believed that this information would be of use in the design of electric furnaces suitable for smelting ilmenite, with voltages, electrode sizes, and electrode spacing adapted specifically to titanium slags.

Jan 1, 1951

By Frank J. Markewicz, William Lodding

Greensand, greensand marl, and green earth are names given to sediments rich in the bluish green to greenish black mineral known as glauconite by the mineralogist. The word glauconite is from the Greek word glaukos, meaning bluish green. The term "greensand" as a rock name for a glauconite-bearing sediment is more appropriate than "greensand marl," a term that has been doggedly perpetuated in the literature. Because of its potash and phosphate content, greensand was dug and marketed as a fertilizer and soil conditioner for more than 100 years. The advent of prepared fertilizers with adjustable nutrient ratios led to the decline of green- sand for agricultural application. The material has since been recognized for use in water treatment. Unfortunately, in spite of large reserves and worldwide distribution, the mineral has not been utilized to any significant commercial extent because no major application has been found for a substance with its chemical composition and properties. This lack is probably due to a paucity of research on its potential commercial application. Extraction of potash received considerable attention during and just after World War I. Because of relatively high extraction costs and generally low potash content (up to 8%), glauconite lost its appeal as a source of this commodity. Historical Background Greensand was used as a fertilizer in New Jersey in the latter part of the 1700s. During the early 1800s its use became more common; applications of up to 100 tons per acre were sometimes made, although recommendations for agricultural use suggested 20 to 50 tons per acre (Tedrow, 1957). Many crops, especially the forage type, were said to improve with greensand application; however, because of slow release of potash, large quantities were required. Certain greensands that contain sulfur and sulfide minerals are harmful to plant growth, and these were classified as "poison," "burning," or "black marls." The availability of higher-grade potash salts from other mineral sources, and the manufacture of prepared fertilizers, displaced the agricultural use of green- sand during the later 1800s. During the mid-1800s the domestic greensand industry, centered in a small section of the eastern United States, grossed more than $500,000 per year. Toward the end of the century, annual production had dwindled to less than $100,000. By 1910 there were only six or eight greensand producers, grossing less than $5000 (Tyler, 1934). There was a small revival in the industry during World War I because of the curtailment of foreign potash, especially from Germany. During the later 1940s and early 1950s greensand was again recommended as a food nutrient for plants and farm crops. Agronomic studies discussed its potential as a soil additive that gradually releases potash and many trace- element nutrients essential for plant growth (Tedrow, 1957). Greensand was sold with the idea that it would condition soil and absorb and hold water while its base-exchange properties would release trace elements. For a short time glauconite was utilized in certain parts of New Jersey as a binding additive in the brick industry, and in the 1800s for making green glass (Cook, 1868). In the early 1900s the base-exchange property of glauconite was recognized for water treatment, and the mineral gained acceptance as a water softener. Mansfield ( 1922) does not mention base-exchange; however, the base ex-

Jan 1, 1975