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By Paul A. Flinn, Jean-Marie Robert Genin

The MCssbauer effect was used to study the distribution of carbon in Fe-C alloys of high carbon content during room-temperature aging. In freshly formed rnartensite the carbon distribution is approximately random; carbon clustering occurs dun'ng aging. In the retained austete the carbon atoms are isolated, suggesting an efiective repulsion; and no rearrangement during room-temperature aging is evident. The kinetics of the carbon clustering in martensite has been studied in detail at 0" . 10". and 20°C. The time and temperature dependence observed is sinzilar to that reported for a variety of other aging effects, such as resistance change, hardness increase, and recovery of internal friction. The stabilization of the martensite kransformation also appears to be related to the clustering effect. DESPITE extensive efforts since the early days of Reaumur, the mechanism which provides the strengthening of steel remains controversial in many cases for several reasons: 1) The structure of as-quenched martensite is not well-determined. 2) Experimental methods capable of distinguishing between various hardening mechanisms are not well-developed. 3) The temperature of formation of many low-alloy martensites is so high that the martensite formed during quenching may be already tempered to some extent before any observation. Among all the hardening phenomena, the most puzzling one occurs at room temperature, where no structural changes have been detected by the usual methods of X-ray diffraction or electron microscopy. However, a new and more sensitive technique became available with the discovery of the MBssbauer effect. This effect makes possible the detection of changes in the local environment of iron atoms in solid solution. It has been extensively used in the study of substitutional alloy systems, for example, Fe-Al,1 Fe-Si,2,3 Fe-Rh,4 and Fe-Ni.5 Making use of the possibility of obtaining new structural information, we undertook an investigation of the aging of high-carbon Fe-C martensite to follow the structural changes involved in the aging at room temperature. Preliminary results6 showed that a clustering of the carbon atoms occurs with time. A systematic study of the kinetics of the process showed a striking similarity to the kinetics of stabilization of the marten-sitic transformation, thus suggesting further investigation of the relationship. EXPERIMENTAL TECHNIQUE To eliminate difficulties with the aging of martensite prior to the first experimental measurements, we needed an alloy with an M, temperature not above room temperature. Other investigators7 were misled by results obtained on alloys which transformed above room temperature and underwent structural changes prior to the first Mossbauer measurements. Winchell and cohen8 dealt with this difficulty by using a third element, nickel, to depress the MS below room temperature. The presence of nickel did not seriously interfere with hardness or resistivity measurements, but it would complicate the interpretation of the Mossbauer data by increasing the variety of iron environments. We chose, therefore, to obtain the necessary lowering of the M, simply by increasing the carbon content. After the first quench to room temperature, our specimens are retained austenite, which we later quench into liquid nitrogen. The martensitic transformation takes place suddenly, so that the as-quenched condition of the samples is retained, since the temperature is low enough to prevent any carbon diffusion. A Massbauer spectrum at 77°K can be taken and analyzed; after an appropriate up-quenching to the aging temperature, a new Mossbauer measurement at 77°K can be made. Fig. 1 shows a typical cycle of experiments. The samples were foils 25 p thick of high-purity

Jan 1, 1969

By Robert M. Grogan

Fluorspar is the commercial name for fluorite, which is the mineral having the composition CaF2, calcium fluoride. Its valuable properties are due to its content of fluorine, and it is the only important commercial source of that element. The name is derived from the Latin fluere, to flow, because the mineral melts easily and is a good flux. History The mineral has been known since Greek and Roman times, when it was used for drinking cups and ornamental slabs. Various peoples including the Chinese and the American Indians have carved ornaments from large crystals. Its usefulness as a flux was known to Agricola, who wrote about it in 1546.1 Mining began in England about 1775 15 and at various places in the United States during the period 1820 to 1840.28 Substantial production was achieved first in the period 1888 to 1900 in consequence of the development and widespread adoption of the basic open hearth method of making steel, in which fluorspar is used as a flux. After that, production and usage was stimulated by growth in the steel, aluminum, chemical, and ceramic industries and accelerated by World Wars I and II. The organic fluorides called "Freons" entered the picture in 1931, and the use of anhydrous HF as a catalyst in the manufacture of alkylate for high octane fuel blends began in 1942. The development of the froth flotation process in the late 1920's, a differential flotation scheme for separating fluorspar from galena, sphalerite, and other minerals in the 1930's, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940's were outstanding technological contributions that enabled increased production of fluorspar concentrates. Composition and Properties Fluorite in its purest form contains 51.1 pct calcium and 48.9 pct fluorine. Substitution of small percentages of cerium and yttrium for calcium have been noted.4 Mechanical inclusions of gases and fluids such as petroleum and water, and of other solid minerals such as pyrite, marcasite, and chalcopyrite are common. The fluorspar of commerce contains attached and admixed mineral impurities, chiefly calcite, quartz, barite, celestite, and various sulfides. It is interesting that the purest commercial form in which the mineral is sold, acid grade concentrate, contains a minimum of 97 pct CaF2, and as such is of comparable purity to many reagents used in chemical laboratories. Fluorite has a marked tendency to occur in large, well-formed crystals sometimes six to ten inches on a side. It crystallizes in the isometric system, frequently forming cubic and octahedral crystals or combinations thereof. The mineral also occurs in massive and in earthy forms, and in crusts or globular aggregates with radial fibrous texture. Crystalline fluorspar exhibits a great array of colors, from colorless and water clear to yellow, blue, purple, green, rose, red, bluish and purplish black, and brown. The colors are often arranged in alternating bands parallel to cube faces. They may be altered by exposure to X-rays, heat, ultraviolet light, and pressure, and are caused by a variety of factors including the presence of trace impurities and displaced ions in the lattice. Sometimes the changes induced by X-rays can be reversed by ultraviolet radiation. The mineral has a hardness of 4, and is the model of that hardness on the Mobs scale.

Jan 1, 1960

By J. B. Austin

In considering so complex a process as the smelting of iron in the blast furnace, there is obviously no single method of calculating efficiency that gives a complete appraisal of the performance of the furnace in all its several functions; such a comprehensive view as is required to evaluate producing ability and manufacturing costs for a given furnace is obtained only by considering a group of efficiencies, each of which measures the performance of the furnace from a specific point of view. For instance, there is the rate of consumption of coke per ton of iron produced, which is probably the most frequently considered, and is certainly one of the most important of the group; there is the efficiency of recovery of iron charged; and there is the efficiency of utilization of energy, both chemical and thermal, in some respects related to the former two yet in other ways independent of either. In each of these cases, the calculation can be made on the basis of the actual input of material or energy, or it may be based upon a comparison with the minimum amount of material or energy that would be required by a "perfect" furnace; that is, an imaginary ideal furnace analogous to the perfect steam engine used in thermodynamic calculations, when this furnace is operating under optimum conditions. Moreover, the furnace itself can be considered either as an apparatus for smelting iron or, taking a somewhat less common point of view, as a gas producer yielding iron and slag as by-products. Some of these efficiencies are more useful than others, yet all are instructive; for a knowledge of them not only leads to good engineering practice from the standpoint of control but also discloses limits to possible improvement in performance and indicates the lines along which improvement is most likely to be profitable. Estimates of some of these efficiencies have appeared from time to time in the literature, but many of them are open to objection because they are based on data of uncertain accuracy or because they have been caleulated without due regard to the thermodynamic principles involved. Moreover, so far as the author is aware. no general survey of the blast furnace comparing its performance in all the aspects mentioned has been made.

Jan 1, 1938

By J. B. Austin

In considering so complex a process as the smelting of iron in the blast furnace, there is obviously no single method of calculating efficiency that gives a complete appraisal of the performance of the furnace in all its several functions; such a comprehensive view as is required to evaluate producing ability and manufacturing costs for a given furnace is obtained only by considering a group of efficiencies, each of which measures the performance of the furnace from a specific point of view. For instance, there is the rate of consumption of coke per ton of iron produced, which is probably the most frequently considered, and is certainly one of the most important of the group; there is the efficiency of recovery of iron charged; and there is the efficiency of utilization of energy, both chemical and thermal, in some respects related to the former two yet in other ways independent of either. In each of these cases, the calculation can be made on the basis of the actual input of material or energy, or it may be based upon a comparison with the minimum amount of material or energy that would be required by a "perfect" furnace; that is, an imaginary ideal furnace analogous to the perfect steam engine used in thermodynamic calculations, when this furnace is operating under optimum conditions. Moreover, the furnace itself can be considered either as an apparatus for smelting iron or, taking a somewhat less common point of view, as a gas producer yielding iron and slag as by-products. Some of these efficiencies are more useful than others, yet all are instructive; for a knowledge of them not only leads to good engineering practice from the standpoint of control but also discloses limits to possible improvement in performance and indicates the lines along which improvement is most likely to be profitable. Estimates of some of these efficiencies have appeared from time to time in the literature, but many of them are open to objection because they are based on data of uncertain accuracy or because they have been caleulated without due regard to the thermodynamic principles involved. Moreover, so far as the author is aware. no general survey of the blast furnace comparing its performance in all the aspects mentioned has been made.

Jan 1, 1938

By Charles A. Stickels, Edward E. Hucke

The dihedral angle, formed by the intersection of three interfaces, is often determined by measuring a sample of apparent angles of intersection seen on a random plane of polish, then comparing the exerimental distribution of angles to the distribution calculated by Harker and Parker. Statistical tests show that the latter distribution does not satisfactorily describe the population from which samples are drawn. It is concluded that the major reason for this discrepancy is the presence of a range of dihedral angles in all specimens. When reasonable care is used experimentally, random measuring error is unimportant. It is shown that measurements made on dispersed second-phase inclusions are subject to a systematic error depending on inclusion size, which can be minimized by using adequate magnification. A dihedral angle, calculated from a sample of observed angles as though a unique dihedral angle were present, is termed an "effective dihedral angle". Experience has shown that "effective dihedral angles'' are reproducible quantities, useful for characterizing samples. Methods of determining an "effective dihedral angle", establishing its reliability, and making comparisons between samples are discussed. THE authors have recently reported measurements of the dihedral angle formed by liquid-lead inclusions lying in nickel grain boundaries.' Di- hedral angles were measured by the statistical method first employed by Harker and parker2 and used subsequently by many other workers.3"8 Since a relatively high degree of accuracy was necessary in the authors' experiments, the reliability of this method of dihedral-angle measurement was examined. Briefly, this method of measuring dihedral angles is usually performed as follows. A multiphase alloy is prepared, equilibrated under conditions which allow sufficient interface mobility to establish equilibrium, quenched to room temperature, then prepared for metallographic examination. A large number of observed angles, formed by the traces of grain boundaries and/or interphase boundaries on the plane of polish, are measured at high magnification. If all orientations of interfaces in the specimen are equally probable, Harker and parker2 showed that the population of observed angles is described by a distribution function containing a single parameter, the dihedral angle, 8. certain properties of the population, e.g., the mode or median, have been calculated from this distribution function in terms of the dihedral angle.3, 9 Thus, if the mode or median of a sample is identified with the corresponding property of the population, a unique value for the dihedral angle is determined. One defect in this procedure lies in identifying the properties of a sample of observed angles with the properties of the population from which they are drawn. If one were to proceed in a more rigorous fashion, it would be necessary to find a function of sample properties which is an estimator of the dihedral angle. Then by determining the distribution function for the estimator one could set limits on the value of the dihedral angle. The most apparent obstacle to this straightforward approach is the complexity of the distribution function assumed to describe the population. In analytical form, the distribution function may be written:2, 10

Jan 1, 1964

By Bernt Ellingsaeter, Terkel Rosenqvist

IN the silicothermic reduction of magnesia, burned dolomite is treated with high grade ferrosilicon in an evacuated steel retort at temperatures between 1150° and 1200°C. The following reaction is assumed to occur MgO + CaO + 1/2 Si (Fe) - Mg(g) +- & Ca,SiO, + Fe with the equilibrium constant on the basis of thermodynamic data for the substances involved and assuming unit activity for all solid constituents, Kubaschewski and Evans' calculated the magnesium pressure as a function of temperature logp,, (mmHg) = 15.06-1.61 T- log T- 13,16O/T. Pidgeon and King," who measured the magnesium pressure by means of a flow method, found values about three times the calculated ones. This may be caused by uncertainties in the thermodynamic data, but may also be caused by the formation of other reaction products, such as Ca,SiO,, which is known to be the stable silicate in equilibrium with lime. Whatever the exact reaction may be, it is evident that as long as all other factors are maintained constant the magnesium pressure will vary with the silicon activity, viz: p,, = &,. (p,,) ", where (p,,)" is the magnesium pressure by the reduction with silicon of unit activity. In the present investigation, p,,, was therefore measured for various grades of ferrosilicon and their silicon activities were calculated. The experimental method was similar to that used by Pidgeon and King. Briquettes of burned dolomite and Fe-Si alloys were placed in a 1 in. heat resistant steel tube and were heated to 1200°C. By means of a flow of purified hydrogen, the magnesium vapor was swept into a condenser filled with steel wool. From the amounts of hydrogen used and magnesium condensed the magnesium partial pressure was calculated. First a tube of 28 pct Cr steel, and later a tube of Kanthal D (a ferrous alloy with 22.6 pct Cr, 2 pct Co, and 4.5 pct Al), was used as a heat resistant tube. The latter tube showed the best heat resistance. The dolomite used had the following composition: 43.6 pct MgO, 55.5 pct CaO, 0.2 pct K,O + NalO, 0.2 pct Fe,O,, and 0.3 pct insoluble. The ferrosilicons were prepared from 98 pct Si of technical grade (0.7 pct Al, 0.3 pct Ca, and 1 pct Fe) by melting with various amounts of electrolytic iron of high purity. The alloys thus obtained were analyzed on their iron and silicon contents, which added up to between 99 and 100 pct. The amounts of reactants were chosen so that there would always be an excess of the oxides, and the average decrease in silicon content during the experiments would be about 1 pct. Most of the reaction occurred in the part of the reaction mixture facing the gas flow. The change in the silicon concentration in the part facing the condenser was, therefore, negligible. To facilitate the reaction, about 1 pct fluorspar was added to the briquette mixture. Fluorspar does not enter the reaction, but is known to act as a

Jan 1, 1957

By J. L. Jernegan

In the summer and fall of 1875, the author was present during a short smelting campaign at the Hall Valley works, and having had occasion to make a number of chemical analyses of the ores, fuel, and fluxes, deems that the results of the same, and also an account of the smelting operations, may be found of interest to members of the Institute. The mines and reduction works of the Hall Valley Silver—Lead Mining and Smelting Company (limited) are situated at Hall Valley, Park County, Colorado. The smelting works are located about half way from the mouth to the head of the above-named valley, and the mines high up on the mountains, near its head. The three principal mines of the company are the Whale, Leftwick, and Coldspring. They are all on different veins, running parallel to one another, with a general trend from southwest and northeast. The

By H. B. Pulsifer

THE unprecedented high price of zinc ore prevailing through the early months of 1915 caused great activity in the Joplin district of Missouri. The Media mill is conspicuous as one of the first of the new "big mills" of the district. The mill was built over a mine previously worked but abandoned in 1912 because of the leanness of the ore and the large quantity of water encountered. The ore prices prevailing-$100 a ton in June, 1915, as against $50 in 1912-favored the new undertaking. The mill was designed for good recovery so that it might operate in times of depression. In design and equipment, the mill is exclusively local in conception and construction. Former Exploitation The tract of land is a part of the large Guinn holdings; 70 acres are comprised in this particular lot, which is situated just a mile north of the center of Webb City on the Alba line of the Southwest Missouri Electric Railway. The ore lies 242 ft. below the' surface at the top of the knoll which is surrounded by the well-known properties: Black Cat, Ground Floor, Florence, Hurry-Up, Electrical and Mercantile. Since the abandonment, in 1913, of the Yellow Dog. a bit farther to the north, the Black Cat, Ground Floor and Florence workings had been flooded. However, as there was no cut through from this side into the area it was proposed to exploit, it was thought that moderate pumping facilities would take care of the water.

Jan 5, 1917

By C. E. Violet, R. J. Borg, E. M. Howard

The miscibility gap in the Au-Ni system has been determined by Mossbauer spectroscopy, with used as a probe. The phase boundaries were determined from the compositional dependence of both the isomer shift and Curie temperature. X-ray diffraction measurements were also used to confirm the Mossbauer results. 1 HE purpose of this research is to demonstrate the application of Mbssbauer spectroscopy to the determination of phase boundaries and to redetermine the miscibility gap by an independent and novel technique. The techniques evolved in this study are readily applicable to other polyphase systems and are generally as quick and accurate as the more conventional methods, e.g., metallography, X-ray diffraction, thermal analysis, and so forth. To be sure, not all polyphase systems will lend themselves favorably to Mijssbauer investigations, but this is a problem met in the use of conventional methods as well. The Mbssbauer spectrum responds to a different set of physical parameters, and consequently provides an entirely independent method of analysis. It is especially useful if the system has either a ferromagnetic or an antiferromagnetic transition. The Au-Ni system was selected because alloys containing more than -60 at. pct Ni become magnetically ordered at low temperatures; also the miscibility gap is quite well established (see Ref. 7 for a compilation of pertinent references, also Fig. 11, and thus provides a reliable test of this novel procedure. As Fe is the most commonly used Mijssbauer isotope, there exists a wealth of information concerning its behavior in iron-containing alloys and compounds. However, as yet there have been relatively few experiments using it as a probe to investigate nonferrous systems. By choosing a nonferrous alloy system, we are able to demonstrate that its use is not restricted to systems containing iron as one of the major constituents. Wertheim and ~ernick' have used the same method to investigate Cu-Ni, and demonstrated that one can obtain a systematic variation in the isomer shift and magnetic hyperfine field. However, we believe this to be the first time these techniques have been used to establish phase boundaries. Two hyperfine interactions were measured and used to determine the phase boundaries, viz., the magnetic hyperfine splitting and the isomer shift which in this alloy system are both strong functions of composition. Calibration curves were established based upon single-phase solid solutions obtained by quenching from temperatures well above the maximum of the miscibility gap, see Fig. 1. Solid solutions containing 25, 50, 65, 75, 85, 92, and 96 pct Ni as well as pure nickel were used in the calibration procedure. Fig. 2 shows the Curie temperature, TC, and the isomer shift, v,, as determined from the Mbssbauer spectra, and variation in lattice parameter as determined by X-ray diffraction, as functions of composition. The compositions of the two-phase systems quenched from temperatures within the miscibility gap are obtained by comparing their respective values of TC and v0 with the calibration data. I) EXPERIMENTAL Mbssbauer sources were made by fusing the component metals in a tungsten arc melter, which has a water-cooled copper hearth. Both nickel and gold were 99.999 pct pure, and the melting was done in an atmosphere of purified argon. The alloys were rolled, diced,

Jan 1, 1969

By AIME AIME

UNTIL recently, practically all geophysical prospecting in Australia was conducted by government departments, either by the Aerial, Geological and Geophysical Survey of Northern Australia or the New South Wales Department of Mines. At present, in addition, the Shell company is carrying out an extensive geophysical campaign in South West Queensland. The Northern Australia Survey has now been in operation for over six years, its work being carried out principally in the northern and central parts of Australia over an area of about a million square miles. At present this Survey is being brought to a conclusion but it appears certain that the geophysical section will be transferred to a Commonwealth Government department on a permanent basis. At present the officers of the Geophysical Section are preparing or have issued some 150 reports on their field work and also a special technical report on the geophysical practice of the Survey.

Jan 1, 1942

By A. J. Ardell, O. D. Sherby

The elevated-temperature steady-state creep behavior of polycrystalline a Zr was studied in vacuo under constant tensile stress. The experiments were conducted from 660° to 845°C over the stress range 870 to 5400 psi. The steady-state creep rate, is, of a Zr was found to be related to the applied stress, a, and temperature, T, by the equation where C is a constant. Two interpretations of the data are considered, each requiring different values of the parameters ß, Q, and . It is shown that this formula can be derived using Gilman's phenomeno logical equation relating dislocation velocity to the shear stress for the case where dislocation mobility is limited by the nucleation of kink motion. From the fundamental dependence of strain rate on dislocation velocity and the density of mobile dislocations, the factor exp(ßo) can be related to the stress dependence of the dislocation density, and Q to the energy of kink formation. The two interpretations considered are as follows: Case I—the parameters are adjusted so that the equation above describes the data over the entire range of stress and temperature, implying that creep is controlled exclusively by dislocation glide; Case IIthe parameters are adjusted to allow for the possibility that creep is diffusion-controlled at high stresses but glide-controlled at low stresses. For both cases the values of the parameters are within the spread permitted by the data. Factors favorable to the observation of the unusual stress -dependence of i, for a Zr are discussed and it is shown that the anomalously rapid rates of self-diffusion and the low modulus on the principal glide system are primarily responsible for the anomalous creep behavior. Metal-lograflhic observations are presented and discussed with reference to the overall creep behavior. PREVIOUS investigations of the creep behavior of a Zr have been conducted from room temperature to about 500C The results of these investigations are primarily of engineering significance because of the variety of conditions under which they were carried out, and the low testing temperatures employed. Little information is available concerning the fundamental nature of the elevated-temperature creep behavior of a Zr. This investigation of the creep behavior of a Zr above half the melting temperature (the melting temperature, T,, of a Zr is estimated to be about 1860"K was initiated because there are two significant anomalies of the physical properties of a Zr: a) the rate of self-diffusion in polycrystalline a Zr is anomalously rapid: b) both Young's modulus for polycrystalline a Zr and the shear modylus as-sociated with the prismatic slip system { 1010)( 1120) (the principal slip system in a Zr 7) have anomalously large temperature variations The importance of these quantities to the understanding of creep behavior has been demonstrated, and it was hoped that this investigation would provide a critical test of the predictions based upon the analysis of creep data for other pure metals. However, as the investigation progressed it became increasingly clear that the unusual creep behavior of a Zr could not be analyzed in a conventional manner. 1) EXPERIMENTAL EQUIPMENT AND PROCEDURES Two grades of zirconium, designated A and B, were used in this investigation. The analyses, as supplied by the vendors, are presented in Table I. Material A, with a nominal purity of 99.84 pct, was supplied by the Wah Chang Corp. in the form of cold-rolled sheet from which specimens were machined without further fabrication. Material B, with a nominal purity of 99.95 pct, was purchased from the Nuclear Materials and Equipment Corp. in the form of iodide crystal bar.

Jan 1, 1968

By James P. Kimball

Sulphur is always present in mineral coal of every variety. In the oxidized state it may exist as sulphuric acid in combination with a base. In the unoxidized state it exists in combination with iron as bisulphide of iron. It is also supposed by some chemists to exist in unknown combinations with the organic elements of the coal. This supposition requires the demonstration as a fact that certain coals yield more sulphur than what may exist in a free state, or what belongs to recognized combinations, not only with the accompanying iron but with other inorganic bases abundantly occurring in coals, but which unfortunately are very rarely estimated. This practically as well as theoretically important question it is at present impossible to decide, simply for want of available thorough ultimate coal analyses including the ash. Such analyses, at the best imperfect, are luborious and intricate, and therefore seldom made, the much simpler proximate analyses, so-called, being resorted to by most chemists for technical purposes, and commonly substituted for more scientific work even in the laboratories of government surveys. And it is unfortunate enough that few ultimate analyses are extended to the composition of the ash, much less to its relation to the original constitution of the coal. Sulphur chiefly occurs in most coals in the form of yellow pyrites (pyrite) and white pyrites (marcasite), both minerals, characterized by differences in crystalline form and in physical properties as well as in color, but having the same chemical composition (FeS2). No coal is entirely free from one or both of these dimorphous forms of bisulphide of iron. It may be disseminated through the mass so as to be invisible, in plates or scales between the laminæ of the coal, or in conspicuous segregations or nodules, sometimes of considerable dimensions. Coals greatly differ as to the proportion of sulphur which they contain. They also differ as to the relative proportion in which its several forms of combination occur. Such qualitative and qnantitative disparities arc scarcely, if at all, more marked in separate coal seams of a uniform type than in different parts of one and the same coal seam, whether it be considered locally as constituted of several

Jan 1, 1880

By James P. Dr. Kimball

SULPHUR is always present in mineral coal of every variety. In the oxidized state it may exist as sulphuric acid in combination with a base. In the unoxidized state it exists in combination with iron as bisulphide of iron. It is also supposed by some chemists to exist in unknown combinations with the organic elements of the coal. This supposition requires the demonstration as a fact that certain coals yield more sulphur than what may exist in a free state, or what belongs to recognized combinations, not only with the accompanying iron but with other inorganic bases abundantly occurring in coals, but which unfortunately are very rarely estimated. This practically as well as theoretically important question it is at present impossible to decide, simply for want of available thorough ultimate coal analyses including the ash. Such analyses, at the best imperfect, are laborious and intricate, and therefore seldom made, the much simpler proximate analyses, so-called, being resorted to by most chemists for technical purposes, and commonly substituted for more scientific work even in the laboratories of government surveys. And it is unfortunate enough that few ultimate analyses are extended to the composition of the ash, much less to its relation to the original constitution of the coal. Sulphur chiefly occurs in most coals in the form of yellow pyrites (pyrite) and white pyrites (marcasite), both minerals, characterized by differences in crystalline form and in physical properties as well as in color, but having the same chemical composition (FeS2). No coal is entirely free from one or both of these dimorphous forms of bisulphide of iron. It may be disseminated through the mass so as to be invisible, in plates or scales between the laminæ of the coal, or in conspicuous segregations or nodules, sometimes of considerable dimensions. Coals greatly differ as to the proportion of sulphur which they contain. They also differ as to the relative proportion in which its several forms of combination occur. Such qualitative and quantitative disparities are scarcely, if at all, more marked in separate coal seams of a uniform type than in different parts of one and the same coal seam, whether it be considered locally as constituted of several

Jan 1, 1880

By Charles T. Baroch, Charles J. Baroch

In 20 years of commercial development, nuclear reactors have demonstrated that they are a safe, dependable, and economical source of power. Operating experience with commercial power reactors has firmly established nuclear power as a practicable source of energy. For both boiling-water (BWR) and pressurized-water (PWR) reactors, performances to date have generally met design predictions. Furthermore, it has become possible to analyze and understand the nuclear, chemical, and physical behavior of this class of reactors. The United Kingdom has had similar success with gas-cooled reactors. The Experimental Boiling Water Reactor (EBWR), the first United States experimental power reactor, began operation in 1956. It proved to be capable of supplying 4500 kw (kilowatts) of power. This reactor was followed in 1957 by the Pressurized Water Reactor at Shippingport, Pa. It was the nation's first full-scale central-station nuclear power plant and the first in the world designed exclusively for the production of civilian electric power. The Shippingport reactor was originally designed to produce 60 megawatts (MW) of electricity, and it was increased to 100 MW in 1964. In 12 years of operation, this reactor generated over 4.5-million MW-hr of electricity in spite of many shutdowns for experimental alterations. By 1969, a total of 15 central-station nuclear power reactors were operable in the United States with an aggregate electrical capacity of over 4200 MW. Early in 1964, Jersey Central Power & Light Co. announced plans for constructing a 515-MW nuclear plant at Oyster Creek, N.J., to be built without government financial assistance. The company stated that a nuclear plant had been selected competitively with fossil fuel. Their economic analysis stated that the plant would generate electricity at less than 4 mills per kw-hr, competitive with coal at 200 per million Btu (British thermal units). Coal cost in 1964 for that region averaged 26.00 per million Btu. The Jersey Central report created wide interest in public-utility circles; nevertheless, no other nuclear plants were announced in 1964. However, in 1965, six nuclear plants were announced by utilities, followed by 26 in 1966, 29 in 1967, and 10 in 1968. By Sept. 30, 1969, 97 reactors were operable, being built, or planned. The cost of these, all committed by electric utilities, was estimated at about $12 billion. When constructed, they will have an electrical capacity of 72,000 MW. The unprecedented surge in power reactors that started in 1965 tapered in 1968, and only seven reactors were announced in

Jan 1, 1976

By O. N. Cole, R. E. Davis, T. D. Brotherton

Pvfoperties of rubidium and cesium are compared with those of other alkali metals. Methods for the preparation of rubidium and cesium metal are reviewed briefly, ad hazards and safety precautions required in handling rubidium and cesium metal are described. SimPle methods for handling laboratory quantities of elemental rubidium ad cesium under oil and under argon are illustrated. CESIUM and rubidium were both discovered by Bunsen and Kirchoff in the years 1860 and 1861. Cesium was discovered while Bunsen and Kirchoff were making a spectrographic study of spring water from Durkheim, Germany. It was the first element discovered by this technique. The element was given the Latin name "caesius" for sky blue because of the color it imparted to flames. Elemental cesium was first prepared by Setterberg in 1881 through electrolysis of a molten mixture of cesium and barium cyanides.' In 1861, Bunsen and Mirchoff discovered rubidium while making a spectrographic study of the alkali content of lepidolite ore from Saxony. Two prominent dark red lines appeared in the spectrum and so the element was named "rubidius" or dark red. In 1861 Bunsen and Kirchoff first prepared elemental rubidium through the electrolysis of molten rubidium chl~ride.~ The alkali metals are very similar in their chemical and physical properties. They are the most active metals, and all exhibit a single oxidation state of one. They are so reactive that they are never found in nature in the elemental state. The reactivity of he metals increases with atomic number. Rubidiurn and cesium ignite spontaneously in air and react explosively with water. This extreme reactivity makes necessary special equipment and techniques for the safe preparation and use of the metals. The cation: of Group IA can be separated from the metallic cations of other groups with relative ease, but the separation of the individual alkali cations is much more difficult because of their close chemical similarity. This close chemical and physical similarity of alkali metals can be inferred from the atomic radii, oxidation numbers, and ioni-zation potentials shown in Table I. A difficult but the most practical physical method of separating the elemental alkali metals from one another is by distillation. Only lithium has a boiling point sufficiently far-removed from the boiling points of the other alkali metals to make this method of separation feasible without elaborate and expensive equipment. This method is not used, however, for lithium because it possesses sufficient chemical dissimilarity from the other alkalies for it to be separated relatively easily as lithium hydroxide monohydrate or as lithium carbonate. Francium, the last member of the group, has no known stable isotopes. The naturally occurring

Jan 1, 1962

By R. E. Wade

The Butte, Anaconda & Pacific electrification is of peculiar interest, in an incidental way, to the entire mining fraternity, and especially the engineering branch, not only in this great Northwest country but throughout the entire Western mining country, which is rich in minerals and water power. It is probably fair to say that the prime object of mining and smelting engineering is to reduce the cost of production, and in the case in hand the relative location of mines and smelter brings the cost of transportation of ore to the front. While some might assign this item to the railway people, it is inseparably a part and parcel of the general scheme of the production of metal from the ore. In considering the electrification of the B., A. & P. railway the mining and smelting engineer, above all, wants to know what saving will be effected by the change in motive power. Unfortunately the new power has been in use during a very limited period and on the Smelter Hill section of the road only, and no reliable data, from actual service conditions, can be obtained until the entire electrified section has been in service for a reasonable length of time. Any remarks on this subject at the present time, therefore, must of necessity be general in nature and more or less descriptive. The railway, electrical and mining worlds and the country in general are indebted to the B., A. & P. railway for the pioneer work it is now doing, as it undoubtedly marks the beginning of the electrification, within the comparatively near future, of all transcontinental roads between the Missouri river and the Pacific coast. Together with this goes the development of an untold wealth in water power and all natural resources within the same territory. For the first time in the history of electric railway work, in this country, direct current at a potential of 2,400 volts is being used. With this potential there is a great saving in transmission of energy to the locomotives and there are only two substations, one at either end and 26 miles apart, for supplying the power for the movement of trains of heavy tonnage over the main line and for switching movements at terminal and intermediate yards, and comparatively little feeder copper is required.

Jan 1, 1914

By Keith Leonard Sutherland

AEROFLOAT 25 is a complex mixture of free cresylic acid with aryl substituted dithiophosphoric acids, sulphides, disulphides, etc. Its complete composition has not been published by the makers or patentees. It is prepared1 by the reaction between phosphorus pentasulphide and carefully selected cresylic acid. We have been informed that this acid contains no phenol and very little cresol, and that it is rich in the higher alkyl phenols, particularly the xylenols. The reaction between a phenol ROH and phosphorus pentasulphide may produce compounds of the following type:2 [ ] Except for the simplest type, the thiophenols (ii), the boiling points of these compounds lie above 300" C. The amounts of the thianthren compounds formed from the five xylenols (if all these are present) will vary according to the position of the substituents. In an attempt to ascertain something of the nature of the reagent, fractional distillation under atmospheric pressure was undertaken. At the outset, hydrogen sulphide was freely evolved, and-particularly below 200°, C.-the fractions had the strong odor characteristic of the

Jan 1, 1939

By Oswald J. Heinrich

THE origin of spontaneous combustion in collieries is, of course, chiefly due to bad system in laying out the pits, unclean workings, insufficient ventilation, and neglect in damming off works after they are exhausted of the main coal. This is particularly indispensable in the Richmond field, because it is difficult and dangerous here, on account of the inferior roof, to remove the last vestiges of coal ; and we are compelled also to retain all the slates and bands, as far as possible, in the pit, to help fill up, although such material is liable to fire. This, however, can be prevented to a great extent, as mentioned below. I am satisfied that the only system of working this thick coal is by cross-cutting (Querbau, ouvrage & travers) or working in benches, as practiced in France (Creusot, Rive de Gier, St. Etienne), in Silesia (Kiinigsgrube), which I have used as far as it is practicable in an old pit, almost torn to pieces by former workings. Modifications may, of course, be needed, even in the same pit, on account of irregularities in the seam. I am also satisfied for economical reasons (on account of the heavy cost for timbering) that pits here ought to be worked upwards, even if it requires a longer period of time to win the coal, and a greater outlay of capital to commence with. The various saddle-shaped " troubles " making natural minor basins in the main basin aid in the execution of this plan. A pit worked once ought to be worked out clean, given up, and dammed off forever. If sections of proper height are assumed, according to the required amount of production for a certain period of time, they ought to be worked out and filled in as much as possible, dammed off, and ultimately allowed to fill up with water, in order to protect the upper works in future from fire in the gob below. This I consider indispensable, because we may not be able profitably to fill in all the ground. To do so we have to use the waste of the mine, although it is liable to fire in time. In using this stuff, it ought to be surrounded by walls of rock not liable to take fire, laid firmly in clay, the gob being in the middle, and firmly covered and packed with clay on top. In

By A. Satter, J. M. Campbell

Reported herein are the results of a careful and detailed study of the non-ideal behavior of pure gases and their mixtures. Included are: (1) new data on five ternary systems composed of methane, ethane and H2 S; (2) a simple compressibility factor correlation that is inherently superior to present correlations, particularly for gases containing H2S and CO2; and(3) a detailed study of combination rules and the effect of system composition on the choice thereof. This study makes use of the rather large mass of data already available in the literature. A complete re-examination of the data and ideas presented in the last 25 years was considered desirable as a prelude to our basic concern — the effect of diluents on gas behavior. A consideration of both the macroscopic and microscopic properties of gases provides a better insight which, in turn, gives a firmer basis for improved correlation techniques. Such a study has shown that expressing the compressibility factor Z as a function of acentric factor w, as well as reduced temperature and pressure, yields a correlation that is broader in scope. The study of various combination rules has shown that better results are obtained by "tailoring" the rule used to the system composition. To do so improves the basic reality of results by overcoming some of the anomalies often found when using Kay's rule alone. Tentative recommendations are made regarding the most reliable combination rule for use with a given class of gas. The data presented are useful for estimating the direction and magnitude of the expected deviation when using a given rule. Although more work is needed, particularly around the critical region and with CO2 mixtures, the advantage of the classification scheme proposed is apparent. INTRODUCTION When one attempts to write a PVT equation to fit the data for actual gases, greater precision is obtained by the use of a multiple number of empirical constants. This has lead to multiple-constant equations such as Benedict-Webb-Rubin, Beattie-Bridgman, Keyes, etc., which are capable of yielding very precise results for pure gases in a range for which data to get the constants are available. As a matter of practicality, though, the use of such equations for gas mixtures is limited. Because of the infinite number of gas analyses available, any attempt to compile the constants needed requires a prohibitive amount of experimental data. This could be overcome by the use of a combination rule, but there is no real advantage in doing so because the end result offers no practical impovement over the Z factor correlation. The most widely used method of predicting the volumetric properties of pure gases is based upon the "theorem of corresponding states". According to this theorem, "all pure substances have corresponding molal volume at corresponding temperature and pressure if the reference point of correspondence is the critical point". Generalized compressibility charts for gases were prepared first by Cope and associates1 in 1931 and later by Brown and co-workers2 in 1932. However, the most commonly used charts are those of Dodge,3 Nelson and Obert,4 Hougen and atsson: and Standing and Katz.6 The work of Katz and co-workers has provided us with basic data for the hydrocarbons most widely used today. Their original chart6 was compared with a relatively large amount of multi-component data for gases consisting almost entirely of normal paraffin hydrocarbons. A deviation of only + 1.2 per cent was obtained.39 In the 20 years following publication of this work it has been found that the behavior of most mixtures of paraffin hydrocarbons could be predicted by this correlation within at least 5 per cent. Where difficulty has been encountered it has largely involved one or more of the following circumstances: pressures above 4,000 psig, mixtures containing large amounts of heavy ends and/or aromatics, systems in the critical region and mixtures containing polar compounds and/or CO2. The abnormal error sometimes found with such gases, not too unexpected for this method, is

By H. M. Otte, A. L. Esquivel

A new leasl-squares method is Presented for determining lattice parameters of hexagonal or tetragonul structures. The method is adapted for use on electronic computers and involves a reiterative procedure. The correction factor employed raries linearly with the lattice parameter, a (determined from the Brag, angle). In contrast, Cohen's method and recent modifications of it use a correction factor that varies incersely as the squure of the lattice paramneter, a. While the recent modifications attempt to improve the precision of the extrapolated lattice parameter, a, (or-cu). by stressing the importance of the weighting factor. the present approach emphasizes the need for choosing the correct extrapolation function. A comparison between the present method (the Linear method) and Cohen's method indicates that the Linear method may be more appropriale in certain cases. through a priori no critertion appears to he available for making a chorce between the methods. The size of hexagonal and tetragonal crystal lattices is determined by two parameters, a, and c,. Although in principle the two lattice parameters can be determined independently from reflections for which h - k = 0 and 1 = 0, respectively, in practice this may be inconvenient (because of the angular positions at which these reflections may occur) or not easily possible (because of low intensity). Furthermore, if a high precision or accuracy is required, the limited number of reflections of this type available, particularly in the high-angle region, is not sufficient for the necessary corrections (mainly due to absorption) to be determined with accuracy. Several methods1-7,11-13 have been proposed employing all reflections, to obtain the optimum values, a. and co, either by a trial and error procedure or a least-squares fit. Of the latter method, cohen's5 is the best known one since it provides explicit expressions for the optimum a. and c,. However, Cohen's method is only strictly valid if an extrapolation function is used that varies linearly with l/a2 or lie2 (see Section 3), a requirement that does not appear to be generally appreciated. On the other hand, all the better known and more widely used A recent trial and error method was proposed by Massalski and King8,7 who computed extensive auxiliary tables of axial ratios vs the functions A = [(4/3)(h2 + hk +k2) + l2+(a/c)2] and C = A(c/a)2 used in computing a and c values from the observed Bragg angles. These values of a and c were then plotted against a function which permitted linear extrapolation. As a criteria; for the "optimum" values, Massalski and King rely upon a visual fitting of the line through points representing reflections of low 1-index points to compute the extrapolated value of ao and high 1-index reflections to obtain CO. The successive computations and graphical plotting required to reach the "optimum" value are quite lengthy and tedious even on a desk calculator and no quantitative assurance is obtained of having in fact selected the optimum value.* If the method of Massalski and King is used on an electronic computer, then their published tables become redundant and a least-squares fit becomes a natural selection for the choice of optimum values. Such an approach will be called the Linear method. For work now in progress on the effect of certain physical variables on the lattice parameters of hexagonal crystals, it has become essential to determine the confidence limits of small changes in the lattice parameters. Since extrapolation functions that varied linearly with a and c actually also appeared to vary linearly with l/a2 or l/c2 when tested against published as well as our data, a comparison of Cohen's method and the Linear method was considered desirable (Sections 3 and 4). For the latter method an electronic computer was required since a reiterative procedure to obtain the optimum ao and co values had to be employed. The purpose of this paper is to describe the principles of the Linear method, illustrate its application, and compare it with Cohen's method. 1) THE LINEAR METHOD The standard practice in obtaining the lattice parameters in the Debye-Scherrer method is to

Jan 1, 1965