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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 Kenneth S. Ritchie

The natural emulsion samples used in this study were shipped directly from twelve California oil fields, through the courtesy of the superintendents of the main producing companies in those fields. Representative parts of each sample were chosen for the slides. Preparation of the slides was generally made in less than two minutes, including time of exposure; in a few cases, about five minutes was required. The short time was intended to minirmize the changes in conditions. Whenever comparison was of value, standard conditions were established. Spreading by gravity was adopted instead of smearing. Cover glasses were not allowed to rest on the films. General Characteristics of Emulsions The main purpose of the general views (Figs. 1-16) is to illustrate the general characteristics of the dispersed droplets together with any other constituent or impurity that may be found in each emulsion. The magnification is given so that dimensions could be measured from the plates. The slides used for these views had spherical recesses; they gave the best light. Where crystals were intended to be shown in the picture a filter (green was the best') was usually used. Emulsions that showed a tendency to move by concentrated light were pictured without a condenser.

Jan 1, 1931

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

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 W. E. D. Jr. Stokes

THE application of aviation to mining and petroleum operations, on the basis of economy and attainment, has become a demonstrated fact. According to Dominion Government records, 30. Canadian companies engaged in air transportation with northland mining camps, carried 13,000 tons of freight in 1935, and in 1936 carried 16,000 tons. In addition, many mining companies used planes to transport prospectors with canoes, outboard motors, gasoline drums and supplies to remote locations, and one company maintained a plane to take radium-bearing ore from its mine on Great Bear Lake nearly 1000 miles south to the rail-way at Waterways, Alberta. Heavy pieces of mining machinery weighing 2 tons are being carried by Ford trimotor planes over the Andes, at an altitude of not less than 15,000 feet. At Bulolo, New Guinea, 17,500 tons of disassembled gold-dredging equipment has been flown over inaccessible terrain, while supplies and building materials for a, community of 1000 whites have been transported by airplane. A 31..4-ton shaft was carried on one notable trip, while at another time an automobile, 2 tons of rice and a large safe went over the mountains in one plane. Fig. 1 shows an electric generator that was carried by plane to Bulolo. Many large American oil companies operated fleets of planes during 19:36, ranging from fast, luxurious air liners for executives to elaborate geological prospecting units, ambulance planes, freight carriers and pipe-line repair crews. According to the U. S. Geological Survey, commercial firms photo-graphed 16,291 square miles during 1935, while the Government compiled from aerial photographs by the Geological Survey in the United States 85,544 square miles. It was found that information could be determined in a fraction of the time required by surface methods.

Jan 1, 1937

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 L. D. Rickets

The principles on which an art is founded are usually few and necessarily basic in nature, but he who wishes to achieve the power to select his aides and give success to important undertakings that may be entrusted to him in the future must ordinarily undergo years of drudgery in order to gain the experience that will enable him to distinguish such fundamentals through the haze of reenforcing detail that clothes and tends to disguise them. This especially applies to those who would dream dreams that may come partly true. Professor Henry B. Cornwall of Princeton was a graduate of Freiberg with mining experience in Mexico. He was my friend and mentor during my college life. In 1883 I finished my postgraduate course and had two offers of work to consider. His advice is very clear in my mind today. It was essentially as follows: I know something of the mines of Mexico and have crossed through the mountains of the West. The West possesses a vast area of mountain and valley. California has long had its gold mines, the Comstock and Gilpin County followed and now comes the discovery of Leadville. I believe the West, will become a great mining country. You can choose now to teach here or go to the mountains. Were I in your place I would go West and identify myself with mining.

Jan 1, 1932

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 H. F. Yancey

Various criteria for evaluating the performance of coal washeries are discussed critically, with particular reference to ideas developed at the First International Conference on Coal Preparation held in Paris in June 1950. Criteria that relate only to the sharpness with which a cleaning unit separates coal from impurity are compared with those that reflect loss of coal or quality of products.

Jan 6, 1951

By Chas Dobbel

THE Chief Consolidated properties are situated in the Tintic mining district of Utah, being included in Juab and Utah Counties, about 70 miles south of Salt Lake City. The drilling referred to in this paper has been carried on in the Chief Consolidated No. 1 mine, the Gemini mine, and the Eureka Hill mine at Eureka, the Grand Central mine, above Mammoth, and the Apex Standard mine just south of Dividend. The occurrence of ore through the district is typically in lenses on bedding or breaks, and in connecting pipes, without accurate geometrical trend so that the ratio between the total length of development in drifts and crosscuts to the square feet of ore exposed is very high. A section of one of the western channels (Fig. 1) through the Tintic district, shows, roughly, the irregularities calling for excessive development work, so typical of the Tintic mines. This irregular trend of the ore constantly calls for excessive cutting up of the whole area for offshoots and the connecting links always present.. In the planning of prospecting and development, no regular system may be laid out without overlooking some orebodies or segments of orebodies. It was with these facts in mind that Cecil Fitch, the general manager of the Chief Consolidated Mining Co., decided that some method of drilling was the more feasible way of successfully cutting up and bringing about the discovery of ore believed to exist; yet this drilling had to compete with a great. margin of cost over crosscutting, as a crosscut in the Tintic district, even though barren, brings out geologic facts that, in many cases, are worth the price of the working itself. Diamond drills met with the success that might be expected in a district that has a reputation for the wear and loss of diamonds; after 6 or 8 months, this method was discarded on account of the high costs. Simultaneously, a small churn drill outfit was set up underground but a few shifts proved its inapplicability. At the same time, the ordinary hammer drill was usd to drive prospect holes with jointed steel.

Jan 9, 1925

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 Maurice Grieves

The great majority of shafts constructed today are still excavated by drilling and blasting, a method which changed very little in over 100 years until the introduction of the mechanical lashing unit and cactus grab by the South Africans, which enabled muck to be removed as fast as massive hoisting systems could handle it and resulted in very rapid rates of sinking. Record breaking month's performances were achieved at -Hartebeestfontein No. 4 shaft, October 1960-337.1 m; Western Reefs No. 4 shaft, October 1961-340.7 m; and Buffelsfontein eastern twin shaft, March 1962-381.2m. The method was very labor-intensive, requiring a crew of over 60 workers at the shaft bottom during the drill cycle. Safety precautions were strict, but in the drive to achieve rapid advance, cases of personal injury were still somewhat high because of the large number of people engaged in this potentially hostile environment. The South African method, as it came to be referred to throughout the rest of the world, was adopted in the United Kingdom in the late 1950s in a modified form with greatly reduced manpower and nonsimultaneous sinking and lining, which was insisted on by the British Mines Inspectorate. In that instance, it was successfully used to sink the 7.3-m-diam concrete-lined shafts at Kellingley to 770 m depth, with rates of advance of over 90 m/month achieved, a British record at that time. During the sinking of the 1.15-km-deep twin shafts at Boulby potash mine in the UK in 1970, the method was again used, but for the first time ever in Britain exemptions from the mining code permitted the use of crash beams, crash doors, jack catches, and semi-simultaneous sinking and lining techniques. New British shaft sinking records of over 120 m/month were achieved in both shafts. Similar equipment and techniques were used in the early 1970s to sink several deep shafts in Canada, notably Creighton #7 and the Con zinc mine at Yellowknife in the NW Territories. Today, this equipment is standard for deep shafts in the US and the rest of the world. However, with the tremendous escalation in mining labor costs, the impact of health and safety legislation, and environmental regulations, coupled with a very real shortage of miners willing to work in this exposed situation it was apparent that an alternative to the labor-intensive conventional method of shaft construction had to be found. Recognizing the trend is inevitable, one or two major German shaft sinking contracting firms began to take a fresh look at full face boring techniques applied to tunnels and raise bored shafts. The results were most encouraging. Tunnel drivage techniques using moles had developed considerably from Colonel Beaumont's original channel tunnel machine circa 1880 to the superbly engineered Priestley machine selected to cut the British side in 1975 and the double shielded Robbins Grandori borer on the French side of the English Channel. Full face tunnel machines were being successfully used to drive uphill in inclined shafts in Austria and Switzerland. At Mapprag in Switzerland, the Demag mole drove the first (intentional) vertical transition and curve, and then went on to successfully complete the 730-m-long penstock shaft at an inclination of 35°. In Austria, the Wirth mole drove the Kaprun Glacier ski-lift railcar tunnel at record breaking rates of 457 m/MONTH (best 30 m/d) through green schist at an inclination of 29° for a distance of 3.35 km while the Hydro tunnel at Sarrelli in Switzerland was being driven by the Robbin's mole at an inclination of 35°. Simultaneously, extremely promising results were obtained using large assemblies of cutter discs on raise borer heads, such as the 4.87-m-diam X 460-m-deep shaft raised by Teton for Jim Walter Resources Inc. Bearing in mind that most mine shafts in the future (unless in exceptionally competent rock) will require some form of lining, and the trend will be toward deeper shafts as the more easily accessible mineral deposits become exhausted, it was seen that normal raise boring had definite limitations in vertical accuracy, in the limitation imposed by the drill string on the available torque that could be applied to the cutter head, and in the risk of collapse of the unsupported shaft rock wall in friable or jointed and fissured ground, since it is not possible to apply any form of temporary support until the permanent lining is being installed. A further problem was the economics of installing a subsequent lining, necessitating setting up a headgear and hoisting arrangement approaching in size that required for conventional drill and blast sinking and lining. Because of the economics, German contractors opted for a phased transition from drill and blast to the full face, rodless, out of the solid shaft mole, by starting off with a down-the-hole shaft boring machine -without a drillstring-but using a pilot hole to get rid of the muck.

Jan 1, 1982

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

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 J. Chipman, N. J. Grant, H. L. Bishop

Lime and dicalcium-silicate crucibles were equilibrated with molten iron and liquid slags containing iron oxide and small amounts of sulfur. The oxygen content of metal, iron oxide activities, and desulfurization values of the slags were determined in the temperature range 1530 to 1700°C. The influence of magnesia in the slag and the temperature dependence of the solubility of lime in liquid iron oxide and the ferric oxide content were established. The temperature contour of the liquidus surface of iron-silicate slags saturated with lime and dicalcium silicate was also established at 1600°C. THE importance of the role that slag composition plays in the refining of steel has been known for many years. Numerous studies have been made using actual plant data in order to establish the relationship between the composition of the slag and metal during the refining of a heat of liquid steel. These results rarely represent equilibrium conditions since completion of the various chemical reactions involved in steelmaking is seldom realized. In order to establish quantitatively the equilibrium conditions existing between the slag and metal, several laboratory studies have been conducted in the past 20 years to determine the reactions important in slag control. These investigations have included studies of simple liquid basic and acid slags as well as more complex slag systems which approach those commonly found during the refining of a heat of steel. Since most of the previous studies of simple basic iron-oxide slags equilibriated with molten iron were made in magnesia crucibles, it was not possible to establish the distribution of sulfur and oxygen between molten iron and slags consisting only of the three essential components, lime, silica, and iron oxide. This investigation was undertaken to establish the equilibrium conditions for simple lime-iron oxide and lime-silica-iron oxide slags. Accordingly, it was expedient to prepare crucibles both of lime and dicalcium silicate to establish the equilibrium conditions between molten iron and iron-oxide slags saturated with the refractory materials and free from other components. The only other studies of the equilibrium between molten iron and lime-saturated slags are those of Fischer and vom Ende, 1, 2 in which the solubility of oxygen was determined in an air atmosphere. The

Jan 1, 1959