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By W. Francis

OF THE methods that have been used for studying the chemical composition of coal, attack by reagents has not, in general, yielded much information. Most of the reagents used have been strong oxidants such as nitric acid or Schulze's solution. The use of a milder oxidizing agent, such as air at low temperatures, enables progressive changes in the character of the coal substance to be studied and thus helps toward an understanding of its constitution. British bituminous coals frequently have a banded structure. These bands (of four types) can be separated one from another and have been found to possess markedly different chemical characteristics, even when taken from contiguous portions of the same lump coal. It has been found convenient to give each of the ingredients of banded coal a distinctive name, more or less descriptive of its appearance, and the study of the chemistry of bituminous "coal" in England has resolved itself into a study of each ingredient separately. . The coal chosen for this work was taken from the Top Hard seam at East Kirkby colliery, Nottinghamshire, a detailed chemical analysis of which has been recorded by Baranov and Francis.1 The banded structure was well marked and the bands could readily be separated. The research was confined to the brilliant vitreous bands (vitrain), the dull hard bands (durain) and the "sooty partings" (fusain); for previous work had shown that the fourth type, to which the name clarain has been given, is intermediate in character, chemically, between vitrain and durain.

Jan 3, 1925

During the war period of quicksilver activity there were a number of departures from what may be termed the classical quicksilver metallurgy. Attempts were made to beneficiate low-grade ores by gravity concentration and flotation; mechanical furnaces began to replace the Scott furnace and the vertical coarse-ore furnaces, and condensers of sewer tile and redwood tanks were used in place of the older brick and stone condensing chambers. Other developments that have occurred during the current period of quicksilver activity are mainly in the nature of improvement and further refinement of those started during the war period. Each period of quicksilver activity has been accompanied by the proposal of various new processes, including wet methods for the treatment of quicksilver ores and innovations in furnaces, retorts and condenser equipment. As far as the author knows, nothing of economic significance in the way of "new processes" has been developed. There is in fact no real need for any essentially new process for the treatment of quicksilver ores; the direct furnace treatment is simple and inexpensive. Moreover, with rare exceptions, the quicksilver industry has no complex or refractory ore problems corresponding to those which are receiving more and more attention from metallurgists in other branches of the nonferrous field. Untler these conditions improvements in quicksilver metallurgy must be looked for through the adaptation of current developments in engineering and metallurgy generally to the particular needs of quicksilver practice rather than through the invention of new processes. Preliminary Treatment of Quicksilver Ores At Sulphur Bank, in the treatment of old dump material left by the early operators, wet screening is being used as a preliminary step in concentration ahead of flotation. Power shovels and trucks are used to deliver some 400 tons of ore per day to the lower terminal of a hoist, which in turn discharges the material at the top of the screening plant. Wet screening is carried on in two stages. Depending on the character of the material, 1-in. or 2-in. punched screens are used on the first trommel.

Jan 1, 1930

By A. E. Hunt, G. P. Clapp

This paper constitutes in substance a part of a more elaborate chapter, accompanied with extended tables of analyses, prepared for the book of Mr. Fred. H. Whipple on " Water-Supply." In advanee of that use of the material, however, it seemed appropriate to lay a portion of it before the Institute; and this opinion of the authors, the Council, by accepting the paper, has ratified. It may seem at first glance, nevertheless, that a paper dealing chiefly with this subject in its sanitary aspects, and only treating in a subordinate way of the one subject (boiler-scale) usually deemed to concern our professions, is somewhat out of place in our Transactions. But reflection will, we trust, correct this impression. In recent periods, and in continually increasing degree, the managers

Jan 1, 1889

By Robert W. Hunt

The American Institute of Mining and Metallurgical Engineers was the first American technical organization to consider steel-rail specifications and sections. If I am not mistaken, the first contribution on those subjects to the Proceedings of the Institute was presented by Prof. Thomas Egleston, in 1874, and was entitled "Investigations on Iron and Steel Rails made in Europe in the Year 1873.1" The next contribution was Dr. C. B. Dudley's report of his investigation for the Pennsylvania Railroad of the wear of steel rails in their tracks, in 1878, which contribution led to a very memorable discussion that extended through several meetings.2 In 1880, Mr. C. P. Sandberg3 presented an article on rail specifications and inspection and rail sections. This was followed, in 1881, by A. L. Holley,4 in his exhaustive report on the then used American rail sections. The next contribution, I believe, was made by myself5 at the Buffalo meeting, in 1888, on steel-rail specifications, which I followed,6 in 1889, by a paper on steel-rail sections. Since that time there have been numerous contributions to the Transactions of the Institute in relation to the manufacture of steel rails. The American Society of Civil Engineers officially took up the investigation of the relation of rail sections to the wear of car wheels in 1888. In the prosecution of this work, the Society appointed a special committee, whose labors extended through several years and resulted in an exhaustive report to the Society in 1893.7 Later, another committee was appointed to consider specifications for the manufacture of steel rails; the labors of this committee extended over a period of several years, a final reporta being made in 1910. It was my fortune to be the secretary of both of those committees. The American Society for Testing Materials, organized in 1899, took up the consideration of rail specifications and is still giving attention to that subject through its established procedure of investigations by committees. In 1900, the American Maintenance of. Way Association was organ-

Jan 1, 1920

By B. R. Banerjee

MATERIAL used throughout this investigation was high-purity aluminum (99.998 pct). The 1/2-in. cubes were cut out of a cold-rolled slab and annealed at 550°C for 1 hr before deformation. The single crystal specimen was 1 in. in diam x 0.33 in. thick, cut from a cylindrical crystal produced by cooling at about 55°C per hr in a furnace which had a convenient gradient of about 10°C in every 4.5 in. vertical crucible length. Specific data on the ten specimens studied are summarized in table I. Three types of deformation were employed: (I) compression in a hand-operated hydraulic press; (2) impact with a 7-lb sledge hammer; and (3) rolling, using a wedge-shaped specimen' to obtain a gradient of deformations varying from 0 to 50 pct along the length of the wedge. Specimens were either deformed at room temperature, or first cooled in a freezing mixture of dry ice and ether at a temperature of —72°C and then deformed between steel blocks cooled with dry ice. The specimens deformed at the low temperature were ground and polished through 000 emery paper and wheels impregnated with alundum and alumina No. 1. During this entire procedure the specimens were dipped frequently in the freezing mixture of dry ice and ether in order to maintain constantly a frosty surface as insurance against overheating. All specimens were given a final electrolytic polish, using two different electrolytes* to insure that the surface effects observed were not char- acteristic of the polishing technique. With both electrolytes, the annealed specimens gave even surfaces with good polish. Several standard etchants were tried without success. The best results were obtained with an immersion etchant, developed in this connection, containing: hydrofluoric acid, 4 parts; nitric acid, 1 part; glycerine, 3 parts. Discussion of Results Typical strain markings have been observed within deformation bands, as shown in figs. 1, 2, and 4. By stereographic plotting of metallographic measurements, the strain markings within a deformation band in a single crystal of aluminum deformed by compression were found to be traces of (111) planes within a maximum scatter of 6". The edges of the deformation band were found to be traces of the (100) planes also within the maximum scatter of 6" (in agreement with previous workers). At 30 pct deformation, this scatter was considered quite normal because of the fragmentation and rotation of the crystal. This solution, based on the traces on one plane of observation is not unique, but as the planes were observed to be those normally and logically to be expected, further work in this regard was not felt to be necessary. The study of strain markings in a wedge-shaped specimen, rolled to obtain a gradient of deformation from 0 to 50 pct, revealed prominent strain markings at 25 pct reduction in thickness (fig.5). Faint and weak strain markings were visually observable up to a minimum reduction in thickness of about 12 pct. Since strain markings have been observed in other face-centered cubic metals after much smaller deformations;1, 2 and since the rate of recovery in aluminum is high, it is believed that, at lower deformations, self-recovery removes the localized strains at the slip interfaces, thus removing the source of the etching effects that give rise to strain markings. At high magnifications, strain markings sometimes seem to appear as very thin, light-banded re-gions bounded by a pair of dark edges. This so-

Jan 1, 1951

By G. W. P. Rengstorff

In an effort to find an oxidation-resistant alloy of molybdenum, binary and ternary alloys containing aluminum, chromium, cobalt, iron, nickel, silicon, titanium, tungsten, vanadium, and zirconium were screened. Fourteen other alloying additions were also tested. Many of the alloys were more oxidation-resistant than molybdenum, but none were entirely satisfactory. MOLYBDENUM oxidizes extremely rapidly above 1450°F in air. At 1800°F, a loss of metal at the rate of 0.1 in. in 4 hr is typical. The high speed of this oxidation may be judged by comparison with the oxidation rate of 0.1 in. per year (0.00005 in. in 4 hr), sometimes taken as the maximum permissible oxidation rate at 1800°F for a satisfactory Fe-Cr-Ni alloy. Great strides have been made in the development of coatings and cladding to protect molybdenum from oxidizing atmospheres. These developments in surface protection will undoubtedly make it possible to take advantage of the excellent hot strength of molybdellum and its alloys in many new applications. Still, even the best coating can protect molybdenum only as long as the surface layer is unbroken. Research was undertaken to determine whether an alloy of molybdenum could be found which would resist oxidation. Such an alloy would not deteriorate suddenly when the protective surface layer was destroyed in a small area. In seeking an alloy of molybdenum to resist oxidation, the physical properties of molybdenum could not be sacrificed entirely. The development of an alloy with the desired resistance to oxidation was not achieved. The information obtained on the effect of a large number of elements on the oxidation of molybdenum is, however, of value in the development of coatings. Indeed, many of the alloys tested for oxidation resistance were already known to have poor mechanical properties but were tested to aid in the development of coatings. Oxidation of Molybdenum The rapid oxidation of molybdenum is usually attributed to the volatility of Moo,,. Gulbransen and Wysong have shown that molybdenum oxidizes very slowly up to 850°F, the temperature at which the oxide film begins to evaporate. Melting as well as evaporation of molybdenum oxides promotes the oxidation of molybdenum. MoO melts at 1465°F. MOO, the oxide which is believed to form at the metal-oxide interface, combines with MoO, to form a eutectic having a melting point of 1432°F.' The liquid oxide, even if nonvolatile, could cause poor resistance to oxidation by allowing easy transport of molybdenum and oxygen ions through the oxide. Actually, a sudden increase in the rate of oxidation of molybdenum at 1460°F has been observed to coincide with the appearance of a liquid phase. The formation of a volatile oxide is not unique with molybdenum. The problem is also encountered with vanadium, tungsten, and some of the Pt-Pd group of metals. Vanadium not only forms the volatile V2O3 but, like molybdenum, forms a liquid oxide coating. Few attempts have been made, however, to prevent the rapid oxidation of these metals by alloying. Oxidation of Molybdenum Alloys At the beginning of this work, very little was known of the oxidation resistance of molybdenum alloys. It was known that molybdenum disilicide (with 37 pct Si) has extremely good oxidation resistance,' but this compound is so brittle that it has few uses. It is an effective protective coating for molybdenum when allowance can be made for its brittleness. Chromium was known to retard the oxidation of molybdenum,' but at least 50 pct Cr was necessary to have an appreciable effect. Other, unpublished, reports show that a few other alloys have been given preliminary tests, but the results have not been promising." Choice of Alloys to be Investigated An alloying element might be expected to protect molybdenum in either of two ways: Its oxide might combine with molybdenum oxide to form a stable, nonvolatile complex oxide (a molybdate); or the oxide of the alloying element might form in preference to molybdenum oxide, developing an impervious layer which would prevent the formation of a volatile molybdenum oxide. The knowledge available about the formation of molybdates was meager. Therefore, the initial study was made on alloys of molybdenum with elements having especially stable oxides. On this basis, binary and ternary alloys containing the following six elements were investigated: aluminum, chromium, titanium, zirconium, silicon, and vanadium. Nickel was also added as an alloying element. Although it does not form a more stable oxide than molybdenum, it does impart some oxidation resistance to copper and iron. Its inclusion in the study was fortunate because its alloys proved to be the most promising of those first tested. Apparently nickel formed a stable molybdate. Because nickel was effective in reducing the oxidation rate of molybdenum, the elements iron, cobalt, and tungsten were added to the list. The ten alloying elements mentioned form ten binary and 45 ternary alloying systems with molybdenum. A series of alloys was tested in each of these systems. In addition, at least one test was made on the effect of each of the following alloying elements:

Jan 1, 1957

By C.P. Proctor, J. T. Crawford, J.A. Younkins

Coal-cleaning plants using the launder process generally wash the fine coal (minus ? or minus 5/16-in.) separately in a plant consisting of washing launders or troughs placed one below another and sometimes supplemented by additional washing equipment such as tables and jigs. The coal and its associated impurities enter the feed end of the top launder, with a current of push water. As the material moves along the impurities, being heavier than coal, settle toward the bottom of the launder and are drawn off, with some coal, through "free discharge" boxes to the launder below. These boxes were given their name because their discharge falls freely; that is, it does not discharge into a water seal. Thus the impurities are progressively concentrated in the lower launders until box products are sufficiently free of coal to be discharged to refuse. The overflows of the upper launders go to clean coal while the overflow of the lowest launder, and perhaps that of the one immediately above, is usually recirculated to the plant feed. Thus the bulk of the clean coal is removed rapidly and the impurities are concentrated more slowly. The chief purpose of this paper is to present the cleaning data of such a plant under different operating conditions. OpeRating Equipment The washing units considered here are part of a complete plant cleaning minus 4-in. coal. The primary cleaned product is a high-quality gas and metallurgical coal and another portion of the output may be shipped as a steam coal. The units consist of two parallel Rheolaveur free-discharge units each containing five launders, together with three 7 by 14-ft. Plato tables. The launders are designated by the letters A-B-C-D-E (Fig. I), launder A being the top and longest; E being the bottom and shortest. Launder details are given in Table 1. The launders are equipped with a series of free-discharge Rheolaveur boxes, which are integral parts of the launder (Figs. 2 and 3). Each box with-

Jan 1, 1940

By C. P. Proctor, J. A. Younkins, J. T. Crawford

Coal-cleaning plants using the launder process generally wash the fine coal (minus ? or minus 5/16-in.) separately in a plant consisting of washing launders or troughs placed one below another and sometimes supplemented by additional washing equipment such as tables and jigs. The coal and its associated impurities enter the feed end of the top launder, with a current of push water. As the material moves along the impurities, being heavier than coal, settle toward the bottom of the launder and are drawn off, with some coal, through "free discharge" boxes to the launder below. These boxes were given their name because their discharge falls freely; that is, it does not discharge into a water seal. Thus the impurities are progressively concentrated in the lower launders until box products are sufficiently free of coal to be discharged to refuse. The overflows of the upper launders go to clean coal while the overflow of the lowest launder, and perhaps that of the one immediately above, is usually recirculated to the plant feed. Thus the bulk of the clean coal is removed rapidly and the impurities are concentrated more slowly. The chief purpose of this paper is to present the cleaning data of such a plant under different operating conditions. OpeRating Equipment The washing units considered here are part of a complete plant cleaning minus 4-in. coal. The primary cleaned product is a high-quality gas and metallurgical coal and another portion of the output may be shipped as a steam coal. The units consist of two parallel Rheolaveur free-discharge units each containing five launders, together with three 7 by 14-ft. Plato tables. The launders are designated by the letters A-B-C-D-E (Fig. I), launder A being the top and longest; E being the bottom and shortest. Launder details are given in Table 1. The launders are equipped with a series of free-discharge Rheolaveur boxes, which are integral parts of the launder (Figs. 2 and 3). Each box with-

Jan 1, 1940

By Eric J. Jette

In thermodynamic studies of gas mixtures and liquid solutions, the respective problems have been greatly simplified by the use of two general limiting laws; Dalton's law of partial pressures and Raoult's law. It is generally recognized that these two laws have a common physical and chemical basis which may be stated as follows: The law may be expected to be strictly valid only for systems in which the different molecular species are so nearly the same in their physical and chemical properties that a molecule is unable to recognize whether its neighbor is one of its own kind or not. Positive and negative deviations from both laws are frequently encountered. The occurrence of negative deviations in both gases and liquids is ascribed to attractive forces which, in the more extreme cases, may be so large in magnitude and so highly specific in character as to lead to the formation of definite chemical compounds. Positive deviations in gases develop only at higher pressures where the intermolecular distances are so decreased that factors such as molecular size and shape, which ultimately become concerned with the repulsive forces, come into play. In liquid mixtures, positive deviations are generally considered as due to differences in the symmetrical (nonpolar) fields of force which surround the various molecular species and which are supposed to give rise to a tendency for each species to associate with its own kind and thus to "squeeze out" the other variety. Fundamentally this also involves the existence of repulsive forces between unlike molecules. If the fields of force are unsymmetrical (polar) a tendency towards compound formation results. Stated in more exact terms, strict adherence to the law means that the "activity" (or any adequate measure of this quantity) of a component in a mixture is a linear function of the molecular (or atomic) fraction of that component between the mol fraction limits 0 and 1. A positive deviation means that the activity is greater than corresponds to the law; a negative deviation that the activity is less. The deviations from Raoult's law have been fully discussed by many writers1

Jan 1, 1934

By E. H. Lancaster, M. E. Mitchell

A MUD-conditioning program found to be very effective for drilling and completion operations on routine field wells requiring relatively short drilling time involves a moderate alkaline-tannate-bentonite treatment resulting in an ultimate filtration rate of 10.0 cc or less (API test). Mud weight schedules are planned from pressure information on completed wells in producing reservoirs and drill-stem test data obtained on other zones not being produced at present. In general, terminal mud viscosities average 45 sec (Marsh). This value has been found to be sufficient to remove cuttings from the well bore on the average well, with the slush pumps in general use on the rigs. On field wells requiring drilling times in excess of approximately 30 days, an alkaline-tannate-lime-bentonite treatment has been effective in maintaining desirable viscosities and filtration rates with a substantial reduction in chemical costs. This system has shown particular advantage on heavily weighted muds and those with abnormal flow-line temperatures. For the most part, the chemical treatment utilized in wildcat drilling follows closely the program used on field wells, depending on depth and duration of drilling operations. Wildcat mud programs are planned from information available from various geologic and operational sources, taking into consideration the possibility of encountering mud problems of a special nature in the wildcat area. Careful planning of wildcat mud pro- grams has proved to have definite value in avoiding most serious mud problems. An analysis and recommended treatment are presented on several special. mud problems which have been encountered in the area in the past. Those problems discussed are lost circulation, blowouts, sloughing shale, excessive chloride contamination, sulphate contamination, and prevention and correction of cement contamination. Introduction Drilling-mud control in the Southwest Texas area, in general, does not involve the multiplicity of problems encountered in other coastal areas. For instance, it is rare that a mixture of problems such as lost circulation, abnormal pressure, severe sloughing shale, and others, occurs on one well within close enough limits in vertical depth not to be taken care of by a sensible casing program, together with a relatively clear-cut mud program. There are conditions such as the fairly widespread occurrence of abnormal pressure in the lower Frio and Vicksburg zones, and the tendency for sloughing shale in the Jackson section which make for rather expensive mud control. However, the availability of fairly accurate geologic and operational information makes possible a reasonable degree of standardization on mud treatment over a relatively large area. It may be said that, over most of this area where drilling is currently in progress, the natural mud made is very poor in quality, but responds readily to moderate chemical treatment to yield very good wall-building characteristics. AS far as field development drilling is concerned, the mud engineer's principal job, once the routine treatment best

Jan 1, 1949

By James T. Waber, Allen C. Larson, Karl Gschneidner, Margaret Y. Prince

The original graphical method proposed by Darken and Gurry for predicting which elements are soluble in a given element was slightly modified and was used to predict terminal solubilities in 1455 known binary combinations. it was found that the modified Darken and Gurry method had a reliability of 61.7 pct in predicting extensive solid solubility (greater than 5 at. pct) and of 84.8pct in predicting limited solid solubility (less than 5 at. pct), an over-all reliability percentage of 76.6. Using the same experimental data, it was found that using only the simple Hume-Rothery size-effect criterion was 50.1 pct reliable in predicting extensive solid solubility, only slightly better than a purely random choice. and 90.3 pct reliable for predicting limited solid solubility, an over-all reliability percentage of 67.6. THE first rational rules for determining a priori whether two metals are not freely soluble in the solid state were announced by Hume-Rothery and coworkers.1,2 These well-known rules have been accorded a special place in metallurgical literature. Since the "electronegative" and "relative valence effect" rules of Hume-Rothery were only qualitative in nature it was difficult to use them in a quantitative analysis. The next major step was made by Darken and gurry3 and apparently went unexplored for a number of years. They prepared graphs illustrating the influence of both electronegativity and size difference on the solubility of elements in silver, magnesium, and aluminum, and they drew elliptical figures, whose maximum width was ±15 pct of the solvent radius and the maximum height was ±0.4 electronegativity units. The purpose of the present paper is to assess and compare the effectiveness of using the simple size-factor and the Darken-Gurry criteria to predict which elements will be soluble and insoluble in a given solute. In 1957, waber4 prepared Darken-Gurry plots for determining the solutes that were likely to be soluble in 6 and plutonium and introduced an inner ellipse as an aid to determining which elements should be soluble to a considerable extent. As illustrated in Fig. 1, the major axis of the outer ellipse corresponded to ±0.4 electronegativity units (OD) while the minor axis corresponded to ±15 pct of the radius of the solvent phase (OB). This simultaneous "action" of the two Hume-Rothery criteria was used to indicate which elements would have little or no solubility in the host lattice, namely those elements whose points lay outside this ellipse. An inner ellipse, "centered" over the same point of the solvent was drawn with ±0.2 electronegativity units (OC) and ±8 pct (OA) as the major and minor axes. Solutes with points lying within the inner ellipse were expected to be capable of forming extensive solid solutions with the host element. Use of this method of applying the earlier Hume-Rothery criteria was moderately successful for plutonium. For 6-phase plutonium, only one element out of the eight predicted to be extensively soluble was known to be almost insoluble, and of the sixteen elements predicted to have more restricted solubility, five were known to be essentially insoluble. The success of discerning solubility in the E phase by this method was comparable. One prediction made on the basis of this analysis was that the heavier rare earth metals, such as holmium, erbium, and thulium, should be soluble in the 6 phase, whereas the lighter rare earth elements, such as lanthanum or

Jan 1, 1963

By W. W. Wirth

RESEARCH looking toward the reduction of the cost of roof support by substitution of longer-life materials for wooden timber is fully justified by the fact that roof support is an important element of all production costs. Permanent or semipermanent roof support will reduce the expense of timber-maintenance crews during steady operations, but even more markedly during idle periods. The management, therefore, is faced with the important problem of timber renewals, which in times of regular operation are frequently obscured by more urgent problems of production. Increased use of timber in the Anthracite Region of Pennsylvania is caused mainly by increased percentage of coal obtained from robbing areas, which requires more timber for safety than develop-ment work, and maintenance of long haulageways through crushed ground despite the fact that less coal is transported over them. The timber reserve in the immediate vicinity of the mines has been depleted to such an extent that it is necessary to secure 70 per cent of the timber requirements from distant sources. Originally, mine timbering in this region was done by largely utilizing round props or legs with round collars. The whole cross section of the tree from which timber was cut was utilized by forming the joints between the legs and the collars with saw and adze, using plank or round saplings for lagging behind the legs and over the collars to prevent material falling between them. The Mine Inspectors' report of 1898 records an important digression from the use of round timber, when two tunnels at the Babylon colliery, near Pittston, Pa., were timbered with 12 by 12-in. square timber sets with mud sills, through quicksand for distances of 425 and 160 ft., respectively. The timbers were lagged with 3-in. plank to control sand.

Jan 1, 1940

By R. O. Williams

A study utilizing neutron diffraction, electrical resistance, and chemical extraction has been carried out to clarify the chromium-rich part of the miscibility gap previously proposed for this system. This gap appears to be more symmetrical than previously supposed and is very flat. This flatness is believed to be the result of a cooperative phenomenon perhaps of magnetic origin; in particular, it is believed that the chromium-rich phase is antiferromagnetic. The presence of antiferromagnetism is believed to result in an additional strengthening mechanism very sinzilar to that for ordered precipitates. Likewise, it is proposed that the quenched alloys which are known to be ferromagnetic have antiferromagnetic regions which accounts for the maximum in hardness around 75 pct Cr. It is also believed that the existence of antiferromagnetism in other alloys of transition elements might explain some of their anomolous characteristics. THE iron-chromium phase diagram at low temper atures has recently been constructed as shown in Fig. 1(a)1 based upon that work and the work of Fisher, et al2 This system exhibits a number of extraordinary features but perhaps the most striking is the odd shape of the miscibility gap (in the

Jan 1, 1959

By C. H. Cheng, C. E. Birchenall

The fundamental problem in the thermodynamics of solid solutions is the determinatiorl or calculation of the activities of the components as a function of temperature and composition. Since the theory of metals is not suficiently developed to allow a priori calculation of these quantities, they must be obtained from experiment. C. Wagner1 has reviewed the literature of this subject for the period before 1940. Although several important and extensive studies have been made in the meantime, the number of systems to which any sort of quantitative information can be assigned is vanish-ingly small. These data have become of great potential importance in studies of the structure of solid solutions2 and intermetallic compounds, the nature of the diffusion process,3,4 and perhaps even the mechanism of mechanical deformation.5 For these reasons, it. seems very worthwhile to extend the experimental data in this field. Although there is little use in duplicating Wagner's review, attention should be directed to the most recently reported investigations. A brief enumeration of the methods of measurement previously employed also should be valuable. The most direct method is the determination of the partial pressure of the components in the vapor phase in equilibrium with the solution. Both equilibrium and kinetic methods have been tried in metal systems, but almost exclusively on liquid phases. Only in the ease of carbon in iron alloys and in the copper-zinc system have extensive measure- ments been made which include solid phases. When one of the components is an element, such as nitrogen or carbon, which forms compounds which are very volatile and stable at normal temperatures and pressures (CH4, Co2, CO NH3), it is frequently possible to equilibrate mixtures containing these (such as CH4-H2, CO2-CO, NH3-H2) independently with the elernents (C, X) and with the metal (Fe, Ni, etc.). Such measurernents have been made for carbon in iron, iron-silicon, and iron-manganese alloys by Smith6 and in iron and iron-nickel alloys by Toensing.7 Differences between carbon activity values at the same temperature and carbon content when carboil is introduced from CH4-H2 rnixtures or CO-CO. mixtures indicate that the effects of hydrogen and oxygen in the system are not negligible, and one can only hope that the true value lies somewhere between these sets of results, probably nearer the CH4-H2 data since hydrogen is less soluble in iron than oxygen. This is essentially an equilibrium method, although flowing gas is employed. A kirletic method has been employed which consists of sweeping an inert gas (generally hydrogen) over the alloy at a series of rates, condensing the metal vapor out,, and analyzing it. The metal content can be extrapolated to zero flow rate (equilibrium). Wejnarth's8 work on Cd-Mg and Zn-Mg is a good example of this frequently used method. A variant of this consists of equilibrating a known volume of inert gas with the alloy, sweeping it out quickly, and analyzing for metal. In common with the above method, it has the disadvantage that the "inert" gas is generally somewhat soluble in the alloy. Moreover, the former continuously displaces the system from equilihrium and may give low values if solid diffusion is involved. The dew point method applied by Hargreaves9 to the alpha and beta brasses and by Schneider and Stolll0 to A1-Zn avoids the introduction of another component to the system, but is useful only in systems in which one component is much more volatile than the other. The alloy sealed in one end of an evacuated silica tube is heated to the desired temperature. The temperature of the other end is lowered until droplets of the volatile component condense. When the temperature is raised slightly, the droplets will evaporate. By careful adjustment of temperature, the range between evaporation and condensation can be narrowed appreciably. An independent determination of the vapor pressure of the . pure volatile component is necessary to give the partial pressure over the alloy. This is the method employed here to determine the vapor pressures of zinc and cadmium over their silver alloys up to 34 pct in cadmium and 76 pct in zinc. The former involves only the a solid solution, but the latter covers the a, ß, y, and e fields. In recent determinations, Herbenar, Siebert, and Duffenbarkl1 used the

Jan 1, 1950

By R. K. Datta

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

Jan 1, 1968

By A. C. Fieldner, W. A. Selvig

Ash in coal has always becri regarded as an undesirable substance, as the heat content of a coal dccreases in direct proportion to its ash contcnt. It represents so much inert materid that has to be transported, handled when the coal is burned, and finally disposed of. W. R. Roberts, in an address bcfore the Engineers' Society of Western Pennsylvania, Pittsburgh, on Sept. 29, 1925, said that on an annual output of five hundred rnillion tons of coal, a reduction of 3 per cent. of ash means fifteen million tons of refusc and a decrcase of $30,000,000 in freight charges. Ash also often prevents effieient utilization of the coal through the formation of clinker causcd by the mcltirig of the ash constituents when subjected to heat. The mineral constituents of coal may be of such nature as to make the coal unsuited for speeifie uses as for instance, high-sulfur coal for making metallurgical coke. While the usual proximate analysis of coal gives the amount of ash, it gives no information as to the nature and coniposition of the ash nor of the minera1 constituents from which the ash is produced. For the efficient washing of coal to remove ash-forining constituents it is desirable to know the composition and distribution of the ash-fonning constituents. Obviously such information is also desirable for the most efficient utilization of coal. Nature and Composition of Coal Ash Coal ash may be defined as the inorganic residue remailning after cornplete ignitior of coal. It is dcrived from the mineral constituents of thc coal. The ash-forming constituents may be roughly classified as inherent impurities and extraneous impurities. The former are mixed intimately with the coal substance, and arc derived either from the original coal-forming material or from external sources such as sedimentation and preeipitation while the vegetal coal-forming plant remains accumulated. The latter are present in the coal bed as partings, bands or nodules of pyrite! slate, shale, calcit,e, bone, etc. These are formed either during the laying down of the coal bed, or subsequently. Flag-

Jan 1, 1927

By L. W. Kesler

Kansas produced 41,966,773 bbl. of oil in the year 1927, thereby taking fourth place among the oil-producing states of the Union. The daily average production decreased from 121,609 bbl. in January to 110,244 bbl. in December. Due to excessive flush production and the resulting decline in the price of crude during the year, operations, both in proved and outlying districts, were reduced materially from those of 1926. There were 2338 completions in 1926, but only a total of 1333 in 1927. Regardless of this decrease in the total number of completions, Kansas made a slight gain in total production for the year, producing 620,262 bbl. more than in 1926. This is accounted for, in part, by the comparative long life of the settled production from the Bartlesville sand areas to the east of the Nemaha granite ridge, and by prolific production in eastern Summer County from horizons new in their importance in the state, productive here at two localities along the axis of the granite ridge (Table 1 and Figs. 1, 2 and 3.) For convenience in further consideration, the state is divided into Eastern and "Western" Kansas. Special emphasis will be placed on those areas in the state of which but little is generally known, and which have not been given detailed consideration in previous publications.

Jan 1, 1928

By R. B. Burt, James A. Barr, I. S. Tillotson

THE pumping of solids in water suspension is an important part of many metallurgical and mining operations. In most cases, it is still in the rule of thumb category for which no universal formula has been developed, and much research is needed. Because of the limited and incomplete data available, this article may be classed as an experience paper, which is presented with the hope that some contribution will be made toward the development of the so-called universal formula. This formula, if and when developed, may be evolved from several factors, many of which are not now available for general application. The designing engineer is interested in obtaining accurate forecasts on: 1-the minimum velocities needed to prevent choke-ups in the pipeline, which in turn dictates pipe sizes, 2-power required for pumping, 3-pump selection. The basic factors for a given problem will include: 1-weight per unit of time of solids to be handled, 2-specific gravity of solids, for calculation of volume, friction and power, 3-screen analysis of solids with the colloidal acting, i.e., the slime fraction, a very important factor, 4-shape of particle or some means of determining a friction constant, 5-effects of percentage of solids, 6-development of a viscosity factor to be used in the overall calculations, 7-calculation of the lower limits of pipeline velocities permissible, 8-calculation of total head, pump horsepower, and 9-setting up of pump specifications. In certain limited cases horsepower and total heads and minimum velocities may be computed and a suitable pump selected from basic data, but in many cases, as in mining of Florida pebble, phosphate, experience rather than a hydraulic formula still should be used as a basis of selection. Pumping Florida Pebble Matrix Pumping at the Noralyn mine of International Minerals and Chemical Corp. will be used as an example. Other areas will vary as to the characteristics of the matrix, especially the slime content. A typical screen analysis of this matrix is: +14 mesh, pebble size,* 2.1 pct; -14 +35 mesh, 11.4 pct; -35 +150 mesh, 60.5 pct; -150 mesh, 25.0; total, 100 pct; moisture in bank, 20.0 pct; weight per cu ft in bank, 120 lb. The -150 mesh fraction may increase to as much as 35 pct in adjacent areas. When thoroughly elutriated, the matrix has a relatively slow settling rate, which is an important factor in permitting lower pipeline velocities without choke-ups. Exact data is not available to evaluate settling rates. For a factor of 100 a suspension of clean building sand in water is suggested. When pumping long distances, a quick settling matrix allows the coarser solids to settle out along the bottom of the pipeline, causing drag, turbulence, and increased friction. With a slow settling matrix as at Noralyn, turbulence acts to keep the solids in suspension at a lower friction head, regardless of the pumping distance. When the pebble, content of the matrix, i.e., the +14 mesh fraction, is in excess of 10 pct of the total solids, trouble may be expected from settling out even in normal pumping distances. To prevent choke-ups and maintain tonnage, an additional pump must be added in the long runs, where one pump would otherwise be satisfactory. A typical pulp handled is: total volume, 7800 gpm; water, 4500; solids pumped per hr, 4200 lb; sp gr pulp, 1.4; percent solids in pulp, 46.; pipe size, 16-in. ID; pulp velocity, 12.85 fps; probable critical velocity, 10 fps, as below this minimum -velocity choke-ups would be numerous. In calculating friction heads the Armco handbook is used where a roughness factor based on 15-year-old pipe is set up. Because the pipe used in pumping matrix is, smooth and- polished because of the scouring, action of the phosphate and its silica content, the head losses in the Armco table for water are practically the same as in pumping the Noralyn matrix through smooth pipe, plus the fact that conditions vary widely over short periods, making accurate determinations difficult to obtain. New pumps and pump, changes are being tested continuously and a wealth of data built up. This has resulted in a substantial improvement and lower relative costs in pumping matrix. The Florida phosphate industry is constantly seeking to offset higher wage and material costs with improved technique. Until a few years ago a 12-in. discharge pump was commonly used, with heads as low as 80 ft. Sizes have gradually increased and heads more than doubled. For example, the following pump was placed under test at the Noralyn mine: make, Georgia Iron Works; size, suction 16 in., discharge 14 in.; impeller, 39-in. diam; motor, 600 hp, slip ring; full load speed, 514 rpm. The results were increased head, higher capacity than the older design, with fewer pumps in the line from mine to washer.

Jan 1, 1952

By T. M. Berry

FOR the past several years it has been growing practice to install circular shafts at deep mining operations. Several factors have brought this about. Throughout eastern and midwestern coal fields circular shafts have been conventional for many years. Where large bodies of coal are mined, a production shaft may have a life of 20 to 30 years. Quantity production is essential; therefore the shaft must have a large cross-sectional area for larger skips and cages. Mechanical mining has become a necessity if a company is to stay in business today. Continuous mining machines and cutting, loading, and hauling equipment must be taken in and out of the mines. If the access shaft is not large enough there will be expensive dismantling and assembling. This has become a problem at many operations, particularly in the western sections where ore was originally mucked by hand into small cars and hoisted by a skip through a narrow rectangular shaft having small compartments. Mechanical loaders must be dismantled to wheelbarrow size to go into these mines.

Jan 7, 1957

By Victor L. Stevens

The Oso tunnel is one of three tunnels located on the San Juan-Chama Project in south-central Colorado. The purpose of the tunnel is to carry water from the upper San Juan watershed through the Continental Divide into the Rio Grande watershed. The Oso tunnel contract was awarded by the U.S. Bureau of Reclamation to a joint venture of Boyles Brothers Drilling Co., Gibbons & Reed Co., and Cimco in February 1966. The Oso tunnel is 26,660 ft long and has a rock section of 10 ft, 2 in. with a lined diameter of 8 ft circular. The main portion of the rock formation was in the Lewis shale. This formation is quite consistent in hardness and texture with exception of localized limestone concretions and sandy siltstone inclusions. The job was bid on the basis of using a James S. Robbins mole of the P221 series. The decision for using a mole was predicated on the geology and the experience of the same joint venture on the adjoining Azotea tunnel where a mole was successfully used. The Robbins P221 series mole is capable of cutting from 9 ft, 11 in. to a 10 ft, 7 in. diam without any major change. It is 40 ft long and weighs 60 tons. The cutting head has 22 disk-type cutters and one center pilot (standard 9 7/8 -in.) tricone bit. The head is powered by four 75 hp electric motors. Gripper pads at about the midway point on each side of the machine are pushed into the tunnel ribs and thrust-cylinders in front of each gripper apply pressure to the face as the head rotates. The regripping cycle is 3 ft and then the grippers are retracted and advanced. Each cutter on the perimeter of the head is followed by a bucket which scoops up the cut material, almost in the same manner as a water wheel, and dumps it into a conveyor situated along the top of the mole. The muck from the mole conveyor is dumped into a gantry-type conveyor. The gantry conveyor is 350 ft long and is pulled

Jan 1, 1970