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By W. Philippoff

ALTHOUGH Gaudin1 and more recently Sutherland2 have calculated the probability of collision of a falling mineral particle with a rising bubble, there is no published information concerning the details of the mechanism of attachment of a collector-coated particle to a bubble. During the past year the writer has developed a theory for the mechanism of attachment, which has been substantiated experimentally. Funds for the investigation and for some of the equipment used have been supplied by the Mines Experiment Station of the University of Minnesota. Motion picture studies of the phenomena involved in the collision between mineral particles and bubbles, such as those of Spedden and Hannan," show that the contact can be completed within 0.3 millisec. Formulas developed for rigid bodies have hitherto been used' for the calculation of the motion of bubble and particle, but it is obvious that a bubble cannot be regarded as a rigid body. On the contrary, Spedden and Hannan's pictures show a great degree of deformation during the collision. The time of attachment was calculated as the time the particle drifted past the bubble. Time of Collision The theory presented in this paper enables calculation of the time of collision, using the concept that the bubble, or more generally, a liquid-air interface, acts as an elastic body. The elasticity, defined as the restoring force on a mechanical deformation, is caused by the surface tension and is the result of the principle of the minimum of free surface energy. It is well known that an elasticity together with a mass determines a frequency of vibration. The vibrations of jets and drops caused by the elasticity of the interface are known to comply exactly with the classical theory of capillarity.' However, the vibrations of isolated bubbles, as distinct from foams, have not been investigated previously. The following equation, presented elsewhere,' has been deduced for these frequencies: 3_____________________ fB = 9.20.vV.vn. (n-1).(n+2)/8 [I] in which fB is the frequency of a harmonic of the bubble in cycles per second, V the volume of the bubble in cc, n a number determining the order of the harmonic, and n = 2 the basic vibration. The first (basic) harmonic describes a change of the spherical bubble to an ellipsoidal bubble. The higher harmonics are more complicated, for the circumference of the bubble is divided approximately into as many parts as the order of the harmonic. As an example, Spedden and Hannan's published motion picture of a vibrating bubble corresponds to the sixth harmonic. Eq 1 shows that only the first and third harmonics are simple multiples (1 and 3), all the others being irrational fractions of the basic frequency. This means that the shape of the vibration can change with time and is in general unsym-metric in respect to the time axis. Such conditions prevail when there is a distributed elasticity or mass, as in the case of vibrating membranes or rods. The constant 9.20 is valid for water at room temperature, but a general solution involving the physical constants of the liquid has not been found. The case of the floating particle is much easier to treat than that of the bubble. It can be assumed that the elasticity is caused exclusively by the interface and that the mass is concentrated in the particle together with some adhering water. The following expression for the frequency of a system of one degree of freedom can be applied: fP = -1/2-vE/m [2] Here fp is the frequency of the particle vibration in cycles per second, E the elasticity in dynes per cm, and m the mass in grams. The classical theory of impact phenomena gives the time of collision during the striking of a spring (in this case the surface of the bubble) by a mass, as: t, = 2/f = nvm/E [3] It is now possible to develop an expression for the elasticity of a floating cylindrical particle. The force equilibrium of a cylinder floating end on at the air-liquid interface is given by the well-known equation (Poisson7 1831) P = /4 D2-pL-g-h + D.y sin a [4] which accounts for the buoyancy and the action of the surface tension where P is the force acting on the particle in dynes (weight-buoyancy), D the diameter of the cylinder in cm, PL the density of the liquid in grams per cc, g the acceleration of gravity = 981 cm per sec2, h the depression of the cylinder below the surface of the liquid in cm, y the surface tension in dynes per cm and a the supporting angles or the one required to insure equilibrium, a being smaller than the contact angle 0. Although demonstrated by Poisson, it has not

Jan 1, 1953

T. L. Joseph (University of Minnesota, Minneapolis, Minn.)—Mr. Killian is to be commended for his inquiry as to why a decrease of 15.3 pct in coke consumption was accompanied by a decrease of only 1.9 pct in the CO/CO, ratio of the top gas. Although I encouraged him in his efforts to find a more significant and meaningful carbon-gas ratio, the method, calculations, and conclusions originated entirely with the author. Whether we agree entirely with the assumptions underlying his corrected ratio, I think we can all agree that a better ratio is needed, and that he deserves credit for recognizing the need and for doing something about it. To be most useful, the CO/CO, ratio for the top gas should reflect the way in which the carbon is gasified in the furnace, particularly the degree of oxidation and the extent of heat release. The effect of CO, from the decomposition of the limestone and the effect of the reaction of CO and water vapor in the upper part of the furnace on the quality of top gas should be isolated from the effect of more basic reactions such as ore reduction and solution loss. The reduction of sufficient iron oxide to produce a ton of pig iron and the accompanying changes in the proportions of the carbon gases can be expressed on a mol basis as follows: 16.5FeA + 16.5CO - 33FeO + 16.5CO, [1] 33FeO + 33.0CO = 33Fe + 33CO. [2] The CO, from eq 1 normally escapes from the furnace because it does not react with coke at the temperature of its release. However, as much as 50 pct of the CO, from eq 2 may react with coke because it is released at temperatures above 1000°C: 16.5CO. + 16.5CO2 = 33CO [3] Thus we see that the gasification of 16.5 mols or about 200 lb of C in solution loss will regenerate as much CO as is required for the last stage of reduction. The pronounced effect of reaction 3 on the final proportions of CO and CO, in the gas stream is obvious. It also follows that reaction 3 materially alters the heat release but it cannot be entirely eliminated in Lake ore practice. A previous study indicates that 100 lb of solution loss may be necessary to maintain the reducing power of the gas. A reduction of 100 lb from the normal level of 200 lb would mean that over 1,-000,000 additional Btu are released in the process. The 100 lb of additional carbon which will be burned at the tuyeres will release 437,000 Btu and the absorption of 583,000 Btu by eq 3 would be prevented. One of the chief objectives of sized ore burdens and more uniform distribution of the gas stream is to minimize solution loss by completing reduction higher in the furnace and in turn to release the maximum amount of heat from the carbon charged. It was odd, indeed, to find that the use of sized ore and sinter in the careful tests reported by Dobscha had changed the CO/CO2 ratio very little. The author has stressed the close correlation between his corrected CO/CO, ratio and production. A correlation of fuel consumption and the CO/CO, might be more logical. Fuel consumption on the prepared ore burden decreased 15.3 pct whereas the corrected CO/CO2 ratio decreased 19.0 pct. Although this agreement between the reduction in fuel and the reduction in corrected CO/CO2 ratio is not as close as the correlation with tonnage, it indicates the corrected ratio is superior to the normal ratio which decreased less than 4 pct. Some adjustment should be made for the reaction: CO + H2O = CO2 + H2 —700Btu [41 because there is evidence to indicate that about one half of the hydrogen is formed in the upper 21 ft of

Jan 1, 1953

By L. A. Walker

DURING the past twelve years the underground shaft of the United States mine at Bingham has been sunk an additional 2000 ft. with stations and pockets cut every 200 ft. without interrupting the mining of 600 tons of ore per day and the advancing of 1500 ft. of development per month. Following is a brief description of the way the joint work is conducted. The vertical underground shaft is a three-compartment shaft with outside dimensions of 6 ft. 4 in. by 15 ft. 6 in., and inside dimensions for each compartment of 4 ft. 2 in. by 4 ft. 8 in. The manway compartment of the main shaft is used as the hoisting compartment in sinking operations; it is partially lined with 2 by 12-in, lagging and a bucket is used without guides or crosshead. Preparatory work includes the placing of a bulkhead in the manway compartment, 60 ft. above the lowest station or level, the installation of a hoist, a head sheave, a fleet sheave, a-signal system, air and water lines, and a trap door for handling waste.

Jan 1, 1937

By H. E. Brauer

PART I INTRODUCTION Among the zinc base alloys used for casting in metal moulds, particularly die casting, those alloys containing aluminum usually together with copper, are probably the most widely used. The reason lies in their desirable mechanical properties and the fluidity and absence of hot shortness which facilitate casting. Objection to the use of these alloys may bee raised on account of the rather frequent instances of failure of a type variously described as disintegration, exfoliation and intercrystalline corrosion. In all cases which have come to our knowledge where the conditions of service were known, failure has occurred upon exposure to moisture and heat varying from a hot moist atmosphere to high pressure steam. Moreover, the alloys described in all such cases contain impurities or alloying metals which the present authors have found to have enormous accelerating effects on intercrystalline oxidation in zinc-aluminum alloys. Thus Williams1 experimented with an alloy containing a large percentage of tin exposed in Cuba. Bauer2 reports failure of a boiler plug containing over 1 per cent. of impurities, doubtless lead for the most part, and Rawdon's3 examinations were made on an alloy containing 0.4 per cent. lead also exposed to the Tropics. No thorough investigation of the nature and cause of this type of failure has been made heretofore, so far as the authors are aware, although Rawdon correctly classified it as internal oxidation. We have, therefore, carried out this investigation in order to determine the exact nature of this phenomenon and the effect of other metals present as impurities or intentional additions in accelerating or-retarding it. In the appendix we include a considerable amount of data which may be valuable in selecting an alloy combining good physical properties with high resistance to oxidation.

Jan 8, 1922

By Ivor Jenkins

PROCESSES employing controlled atmospheres in the heat-treatment of metals and alloys are now well established on an industrial scale, and the general principles involved and the advantages to be gained in the use of the technique have received considerable publicity over a period of years. During this time the greatest emphasis has been on the establishment of the process in industry, the main effort being devoted to development work on various types of atmospheres, their useful fields of application and the design of suitable heat-treatment furnaces in which they are to be used. The various types of controlled atmospheres are fairly well standardized, but there still remains a considerable field for the investigation of related problems, in connection with both the gas-generating equipment and the surface chemistry of the heat-treatment of metals, especially in complex controlled atmospheres. This paper describes certain investigations of this nature that were carried out in England up to 1939. The development of processes employing controlled atmospheres has been associated to a very large extent with the heat-treatment of steels, both because of the major importance of steel in industry and the many diverse and difficult problems of surface chemistry involved when steels of such a wide range of composition are heated in the presence of active gases Controlled atmospheres such as dissociated and burnt ammonia or charcoal gas are used in the heat-treatment of low-carbon and high-carbon steels, but from certain points of view a suitable atmosphere generated by the partial combustion of city gas is to be preferred. Both the ammonia derivatives are comparatively expensive, and even if the burnt ammonia is regenerated, thereby reducing operating costs, the capital expenditure of the gas plant may make it prohibitive for the smaller type of furnace installation. Charcoal-gas generators are not without their operating difficulties: especially those associated with the quality of the charcoal, clinker formation and the removal of carbon dust from the generated gas. City gas has the advantage of being comparatively cheap and "on tap" in most if not all industrial centers. The use of raw city gas as a protective atmosphere in the heat-treatment of steels has been described,1 but it presents certain difficulties because of its complex composition and its explosive nature when mixed with air. These factors, together with the tendency toward sooting at elevated temperatures, arising mainly from the hydrocarbon gases present, all militate against its use as a protective atmosphere in industrial furnaces. The following analysis, based on the analyses of city gas in different localities in Great Britain, indicates the wide limits existing

Jan 1, 1947

By John L. Lamont, Walter Crafts

SECONDARY hardening in tempering has long been recognized as a typical characteristic of steels containing large amounts of carbide-forming alloys. These steels, when quenched and tempered, tend to soften somewhat after tempering at low temperatures, and to reharden at intermediate tempering temperatures before finally softening to low hardness. This behavior in tempering has been studied by many investigators, chiefly with respect to the secondary hardening of high-speed steels. The initial softening has usually been ascribed to decomposition of martensite and growth of iron carbide particles. The secondary hardening has been explained by formation of fresh martensite from residual austenite, formation of very fine alloy carbide particles and by precipitation hardening of metallic compounds in the ferritic matrix. However, factors derived for the calculation of tempered hardness in low-alloy steels1 indicated only a tendency toward retarded softening rather than a discontinuous rehardening. A study was, therefore, made to determine whether fresh martensite from residual austenite and precipitation hardening are essential to rehardening and the degree to which tempered martensite could be rehardened by precipitation of alloy carbides. The mechanism of carbide rehardening was also investigated to determine the nature of the process. The causes of secondary hardening in high-speed steel have received serious consideration for about thirty years. Among the earlier workers Bain and Jeffries2 in 1923 recognized residual austenite as a significant factor, but in addition, emphasized the effect of the formation of alloy carbide particles of "critical" size. They conceived that freshly quenched martensite forms low-alloy iron carbide at low tempering temperatures; with further tempering the iron carbide is then modified by alloying elements that can diffuse most readily at intermediate temperatures (850°F); and that the iron carbides grow in size by coalescence so that the steel tends to lose hardness. At higher tempering temperatures carbide stability rather than alloy availability becomes the controlling influence and in high-speed steel "iron-tungsten carbide is the most stable one and forms to the elimination of the earlier formed carbides. . . . The iron-tungsten carbide particles reach approximately the size for critical dispersion after a short reheat at 1100°F." This concept, the formation of alloy carbide nuclei, redissolving of the iron carbide, and diffusion of carbon to the alloy carbide, was restated for vanadium steel in 1932 by Houdremont, Bennek, and Schrader.3 Subsequent studies have confirmed that iron carbide changes to alloy carbide at 1000 to 1100°F, but the mechanism of the process has received little consideration .

Jan 1, 1948

By J. E. Fox Jr., J. L. Lummus, J. P. Gallus

Fresh water or brine drilling fluids may be kept free of suspended drilled solids by the addition of a water soluble acrylamide-carboxylic acid copolymer at the flowline. Addition of from .01 to 0.2 lblbbl of the polymer solution to drilling fluids containing less than 5 per cent clay solids by weight causes the solids to flocculate and settle rapidly to the bottom of the pits. Solutions of the polymer injected at the pump suction reduce the loss of water to permeable formations without impairing the permeability to oil. The use of drill-itlg fluids clarified with the polymer has resulted in increased drilling rates, extended bit life, and lower drilling fluid costs. INTRODUCTION Field experience and the results of a number of investigations have established that the accumulation of solids in drilling fluid reduces drilling rate.'-' Drilling with water makes possible higher drilling rates than can be achieved with mud but in many areas drilling with water may not be feasible because of the possibility of encountering high formation pressures or by-dratable formations. To combat these conditions, the drilling fluid must possess certain physical properties such as viscosity, density, fluid loss, etc., which require the presence of solids. The current trend in drilling fluid treatment is to maintain as low a percentage of solids as is possible without harmfully affecting the mud properties needed for drilling. Mechanical separating devices such as wet cyclones and decanting-type centrifuges are proving to be an economical means of controlling the percentage of solids and thereby maintaining low solids muds. Also: special muds have been developed for the purpose of retarding the hydration of drilled solids so that they may be more easily removed by shale shakers or settling pits. In some areas, such as West Texas, the characteristics of some formations will permit drilling with water. However, because of the dispersion of drilled solids, it is usually not possible to maintain clear water even with the aid of mechanical separators, or by utilizing large settling pits. For this reason the commonly used term "water drilling" is a misnomer since the water usually contains some solids. Because of the improved drilling rates and other benefits which might be effected, a laboratory and field study was made of the use of flocculating agents for maintaining clear water for drilling. PROCEDURE Laboratory—Solids Settling Two techniques were employed to determine the effectiveness of flocculating agents in settling solids from drilling mud. First, the rate of fall of solids was measured in graduated beakers containing mud treated with various flocculating agents. Natural gum, oil-in-water emulsions prepared with ethoxylated nonyl phenols and diesel oil. and a powdered synthetic acrylamide-carboxylic acid copolymer* (hereinafter referred to as "polymer") were tested as flocculating agents in both fresh water and salt saturated muds containing 4 per cent solids. The polymer was not added in the powder form directly to the muds but was first dissolved in water in a concentration of 3.5 lb/bbl. The polymer solution was then added directly to the mud. The concentration of the flocculating agents, including the polymer, was varied. High rates of fall of the solids indicated high flocculating efficiency. A second technique consisted of measuring the time in minutes required to obtain clear water at the pump suction after addition of the various flocculating agents at the flowline. These tests were made using a model mud circulating system having a total volume of approximately 10 gal. The natural fresh water and brine muds used contained 4 per cent solids. A sketch of the circulating system appears in Fig. 1. The circulating rate

By Allan T. Gwathmey, J. Bruce Wagner, Kenneth R. Lawless

Between 250°and 550°C in oxygen pressures of 10 to 760 mm Hg, the relative oxide thicknesses formed per unit time on the (100), (111), (110), and (320), decreased in this order. The predominant oxide orientation was (001)Fe3O4 and [110] Fe304 A small amount of a-Fe2O3 which exhibited a fiber pattern was observed in all oxides except those formed at 250°c in low oxygen pressures. IN order to understand the properties and behavior of thin films, particularly their role in oxidation reactions, there is needed more experimental information on their structure, composition, and kinetics of formation on clean surfaces of known geometry. The present study was undertaken to obtain such information for thin oxide films formed on single crystals of a body centered cubic metal, iron. Crystals in the form of spheres were used in order to expose all possible crystal planes to the reactant gases simultaneously. Using this procedure the relative rates of oxidation of all planes could be estimated, and those exhibiting, maximum or minimum oxidation rates could be selected for a more intensive study of composition and expitaxy. Since the three types of information were obtained from the same experiment using a single crystal substrate, any differences between rate, composition, and expitaxy on the several planes may be attributed to the influence of the substrate structure. EXPERIMENTAL The starting material for this study was Armco iron rods, 6 in. long and 3/8 or 1/2 in. in diam. The analysis was reported to be 99.8 pct Fe, with major impurities listed as carbon 0.018 pct, manganese 0.027 pct, phosphorous 0.005 pct, sulfur 0.029 pct, silicon 0.005 pct, and copper 0.11 pct. These rods were cleaned with ether and heated in an atmosphere of moist hydrogen at 950°C for three days. The purpose of this treatment was to decarburize the iron and to provide a consistent, uniform grain size for the growth of single crystals. Crystals in the form of rods, up to 1/2 in. in diam and 2 in. long, were prepared by a method similar to that reported by Leidheiser and Buck.2 Spherical crystals, 3/8 and 1/2 in. in diam and having a handle about 1/4 in. in diam by 112 in. long, were machined from the single-crystal rods. After machining, each crystal was etched in aqueous nitric acid to remove the cold-worked metal at the surface. Before each experiment, the crystal was polished mechanically with metallographic papers through number 4/0, and electropolished in a perchloric acid-acetic anhydride mixture by the method of Jacquet and Rocquet.3 The crystal was washed in running distilled water for at least 5 min. The excess water was blotted with a soft paper tissue, and the crystal was placed in an all-glass reaction vessel (See Fig. 1). The crystal was heated at 550°C in hydrogen for at least 8 hr prior to the oxidation in order to reduce any surface oxides and to help relieve any stresses in the metal. For the structure and composition studies, flat faces were cut parallel to (loo), (111), and (110) planes on the iron crystal spheres. The orientation of these faces was checked by a back-reflection X-ray diffraction technique. The faces were within 2 deg of the desired orientation. The flat faces were treated as described above except that prior to electropolishing they were given an additional polish on metallographic felt saturated with twenty-minute levigated alumina. After the crystal was heated in hydrogen for at least 8 hr, the temperature was adjusted to the desired value, and the hydrogen was evacuated. Commercial oxygen which had been purified by successively passing through tubes containing magnesium perchlorate, Ascarite and magnesium perchlorate was admitted to the desired pressure as measured by a mercury manometer. A resistance-wound furnace surrounded the oxidation chamber, and a temperature controller maintained the temperature within ±3°C. The furnace was provided with a small window for observing the crystal. The changes in thickness of the oxide films were followed by observing the interference colors. The oxidation was allowed to proceed until the desired oxide thickness was attained on a given crystal plane. The experiment was terminated by evacuating the oxidation

Jan 1, 1962

By F. J. Fayers, R. L. Perrine

For many years the problem of increasing ultimate recovery of oil from a reservoir has been a subject of interest to the oil industry. At present, a standard secondary recovery technique is to flood the reservoir with water once natural forces of the system are depleted. The permeability characteristics of the rock, together with interfacial forces which exist between the two fluids and the porous material. allow only part of the oil in the rock formation to be recovered by the water-flooding process. Laboratory experiments have shown that when detergents are added to the flooding water, the flow properties of oil in a porous rock arc improved. This improvement results in greater oil recovery. Even though higher recoveries are obtained using detergents, the extra cost associated with the method may make it economically unsatisfactory. To establish economic feasibility requires experimental laboratory measurement of fluid and rock properties together with a calculational procedure to predict field results. Pilot tests in the field may also be required. This paper presents a mathematical procedure for predicting detergent flood behavior. A number of reasonable simplifying assumptions are made to obtain a tractable system of equations. The resulting method may be regarded as a generalization of Buckley-Lev-crett' theory to solve simultaneously for water saturation and detergent concentration profiles. Consequently this type of calculation can be used in much the same manner as Buckley-Leverett theory is used to evaluate a water flood. The mathematical method employed is the so-called method of characteristics for solving hyperbolic partial differential equations. This application of the method is instructive because several other problems in reservoir analysis may be analyzed in a similar manner. FLUID FLOW EQUATIONS The flow behavior of oil and water without detergent through porous reservoir rock is usually expressed by Darcy's law and a continuity equation for each phase. If gravitational forces are neglected, vrg = kr (s)µr v p rg.........(1) vrg = kr (s)µr v p rg.........(1) ? pa va = F ?/?t (sd) where v is the volumetric flux, k represents permeability, S is saturation, and P the pressure. Fluid viscosity is denoted by 11, p is the density, 4 is porosity, and I the time. The subscripts w and o refer to water and oil. The capillary forces in the system lead to a difference in pressure between phases. This may be expressed by the relation: Pm -P0 =Pc(S).........(5) The capillary pressure? P,, is determined experimentally as a function of saturation. DETERGENT BALANCE EQUATION Addition of detergent to the water phase affects the flow properties of the system. Capillary pressure and relative permeability become functions of detergent concentration, c, as well as fluid saturation. That is: P--P (S,c) and k,,,.- - -- k,,,. At low oil saturation values, the presence of detergent reduces capillary pressure and reduces the relative permeability ratio. Detergents are surface-active and adsorb on rock surfaces. The quantity adsorbed, a, will depend on the concentration c of detergent solution and may also depend on the saturation; thus, a = a(S,c). In this analysis we have assumed that the detergents used are water soluble but not oil soluble, and their movement is therefore restricted to the water phase. The dispersion of detergent in water is neglected by comparison with transfer by flow within the system. Detergent movement is determined by the water flux and adsorption: ? cv m = -F ?/?t (cs + a) We will assume that the quantity of detergent in solution is too small to significantly change water density or viscosity. When the permeability and capillary pres-

By Gerald Sherman

MINE fires are always dangerous and are frequently accompanied by loss of life during the period of confusion which is apt to follow their discovery. In metal mines, fires may result from the accidental ignition of some combustible material, or they may be of spontaneous origin resulting from the rapid decomposition of sulphide. They occur frequently enough to demonstrate the need of some special equipment and a general plan for controlling them, in addition to measures for their prevention. Nearly all the large copper mines have had fires, and the methods of fighting them have been well described in recent papers, notably-by C. L. Berrien,1 R.. E. Tally,2 and others in discussion. The Copper Queen mine has many shafts, which are connected by underground workings. The deeper parts are ventilated by fans, but in the shallower portions natural ventilation through numerous connecting raises or shafts is sufficient. There have been several fires in the past few years, of which all are extinguished but one, and that is under control. These notes cover particularly the preparations that are being made-to check a new fire, partially or temporarily, and to facilitate the escape of workmen in the interval before a definite plan of fighting it can be established. A fire may occur in a shaft or station, or in some working father away. In case of fire in an upcast shaft, the gas would escape to the surface and the immediate result would probably not be dangerous to workmen, as they could escape by other shafts. In a downcast shaft, however, the gas would be distributed very rapidly throughout a large portion of the mine, and men might easily be trapped and asphyxiated. A fire in mine workings, drift, raise, or stope, would be dangerous in a degree, but the draft there is likely to be less strong than in a shaft and probably a smaller area would be invaded by the fire gases.

Jan 1, 1918

By John C. Branner

No precise geographic limits can be given for the zinc- and lead-region of North Arkansas. In general terms it lies N. of the Boston mountains and W. of the St. Louis, Iron Mountain and Southern railway; but the prospecting and the development of the ore-deposits have not gone far enough to outline more than vaguely the areas over which workable deposits are to be expected. The tardiness of the development of the region is due in part to its topography, as a hilly and partly mountainous country, through which there have been no railways until recently. There is no longer any doubt, however, about the existence in that region of large bodies of zinc-ores. I. General Geology. The general geology of the region is, in the main, quite simple, but that of the ore-deposits is less so. The zinc-regions of North Arkansas lie about the southern flanks of the Ozark dome. The rocks are approximately horizontal, but have a gentle southward dip away from the axis of this dome. Figs. 1, 2 and 3 show the broad features of the to-. pography and geologic structure. South of the zinc-region, the sandstones and shales of the lower Coal-Measures form the north-facing escarpment of the Boston mountains. Beneath the Coal-Measure rocks are the limestones and cherts of the Lower Carboniferous; and these rest upon Silurian and Ordovician beds. The uppermost beds (Coal-Measures) have been cut into by erosion along the mountain-slopes so that their edges or outcrops have a meandering or dendritic form. The same thing happens with the Lower Carboniferous beds; but these, haying been more or less protected by the overlying Coal-Measured, have broader bases, and cover a much larger area. In places,

Jan 1, 1902

The early records of coal in Kentucky by Walker and Gist have already been mentioned. Thomas Hutchins was aware of it in 1778, or perhaps several years earlier, as in writing of the Buffaloe, now Green, River, he said, "several persons who have ascended this River, say, that Salt Springs, Coal, Lime and Free Stone etc. are to be found in a variety of places."1 The next record found is an entry to Ellis and Marshall, of 878 acres on Coal Bank Creek, in the, then Fayette County on July 14, 1784.2 The settlement might have been made, or the name given, some time before. Hermeline, in 1783, mentioned iron ore and coal on the Green River,' although he had not been west of the Susquehanna River; his knowledge of coal might have come from Hutchins, although the latter made no mention of iron in that locality. In November 1790, coal was mined on Sturgeon's Creek in Lee County and floated in three barges down the Kentucky River to Cleveland's Ferry, where it was hauled to Lexington. The results were not equal to the expectations, and it was 1793 before the experiment was. repeated 4 In 1791, the estate of Samuel Wharton advertised for sale 31,000 acres "in the county of Jefferson, on the North Side of the Green or Buffaloe river, in the State of Virginia."5 In November 1795 three patents were issued for land in the then Lee County, aggregating 130,000 acres. These patents cover much of Harlan County. The descriptions of these surveys mention passing stone coal. on Rough Branch of Martin's Fork, a "great deal of stone coal" on Blacksnake Branch of Pucketts Creek, and "a quantity of stone coal" probably on Crummies Creek.6 Jedediah Morse, in The American Gazetteer, 1798, said that in Kentucky "in many places there are appearances of potter's clay, and coal in abundance." It is possible that shipments may have been made from near

Jan 1, 1942

By W. B. Boggs, J. N. Anderson

Originally, the copper produced at the Noranda smelter was shipped in the form of blister bars to the Laurel Hill refinery of the Nichols Copper CO, New York. In 1930 a refinery was built at Montreal East to refine Noranda copper and copper from the Hudson Bay Mining & Smelting Co., at Flin Flon, Manitoba. After investigation of the probable costs of making anodes at Noranda and at Montreal, it was decided to make them at Noranda rather than to continue to make blister bars there. Fuel is a major item of expense in making anodes, and since less fuel would be required in making them from molten copper than from blister bars, a lower anode-furnace cost could be expected at Noranda than at Montreal. Further, the expense connected -with making blister bars at Noranda would be eliminated. The cost of treating anode and wire-bar furnace slags is a serious item in a refinery, and it was found that the cheapest method would be to ship such slags back to Noranda. With the anode furnace at Noranda, much less anode-furnace slag would be made at the refinery. Against these savings effected by making anodes at Noranda must be set the high operating cost of an anode furnace at Montreal, using only tank-room scrap and the Flin Flon copper. This furnace would be handling a comparatively small tonnage and would have a high cost per ton. The usual equipment for making anodes from liquid copper consists of either a stationary reverberatory furnace or a tilting Tacoma-type furnace together with an anode wheel of the Clark or Walker type. The reverberatory type of furnace has been developed from the furnace used in the old Welsh process of smelting and refining copper, while the tilting furnace is a development of the holding furnace, which is essentially a Peirce-Smith converter without tuyeres and provided with burners. Refining as carried out in either of these furnaces is a batch process; that is, several converter charges are accumulated and then refined and cast. Colonel H. H. Stout recently developed in Arizona a so-called

Jan 1, 1934

By J. J. B. Rutherford

IT is now well known that troublesome intercrystalline corrosion may occur in austenitic stainless steels following exposure of the metal to a temperature within the range 1000° to 1500° F. (540° to 815° C.). The present paper describes a satisfactory method of estimating the extent of such corrosion, based on the measurement of the electrical resistance of a specimen before and after attack. This new method enabled us to study quantitatively the effect of several factors upon intergranular corrosion in the 18 Cr, 8 Ni type of alloy. The results show that susceptibility to this attack increases with increasing carbon content and grain size and appears to pass through a maximum for certain combinations of temperature of sensitization and period during which the alloy was maintained at that temperature; and are in complete accord with our interpretation of the mechanism of this phenomenon. The method is probably applicable to other metals or alloys subject to intercrystalline attack, such as the aluminum alloys of the duralumin type. The methods hitherto in use for estimating the degree of intergranular attack fall into three types: (1) microscopic examination,1 (2) macroscopic examination of fractures, and (3) determination of the time required for complete failure or disintegration .2 None of these lends itself very well to a measurement of the extent of corrosion. The first two are qualitative in nature and the third provides an arbitrary value largely dependent on individual judgment, since failure is a progressive phenomenon and not a sudden event. Our experience is that weight-loss determinations, although valuable in some types of corrosion investigations, bear no simple relation to intercrystalline corrosion in this type of alloy, as is to be expected since the phenomenon probably involves only the thinnest films between adjacent metallic grains.

Jan 1, 1932

By Emil Gathmann

Through wide experience at numerous mills in the United States I have found that there is a decided difference of opinion among the producers of steel as to what constitutes commercially sound steel. Some metallurgists insist upon having, for certain grades of steel, a so-called "open steel," i.e., one which contains numerous blowholes of varying sizes, and consequently but little volume of true pipe, although a central intermittent shrinkage cavity often extends well down into the ingot. Such blowholes and pipe are expected to weld up during rolling or forging, because their surfaces are not oxidized. Even if this be admitted, included slag particles and a high degree of segregation are bound to be present in the product of such ingots. Blowholes are the result of an oxidized heat, and all heats, unless made or finished in the electric furnace, are oxidized more or less. Subsequent deoxidation, or rather degasification, either in the ladle or in the mold, or in both, is necessary to reduce or prevent blowholes. As is well known, a greater yield of billets or sheets is secured from the ingot by allowing the formation of blowholes, but this is undoubtedly obtained at the expense of the quality of the product. Decided segregation of carbon, phosphorus, and sulphur, as well as small included slag particles, undoubtedly exists throughout the greater portion of all so-called open steel, and cannot be removed by cropping. The first requisite for sound, homogeneous steel ingots and blooms is therefore, in my opinion, so to treat the steel in the furnace, ladle, and mold that "piping" steel is produced. The line of demarcation between harmful and so-called "harmless" blowholes is practically impossible to define. Is it not, therefore, the better and safer practice to use means for the elimination of blowholes and correspondingly reduce the segregation and allow the formation of a well-defined shrinkage cavity or pipe at the upper end of the ingot? With the relatively cheap deoxidizers available at the present time, e.g., ferro-silicon, aluminum and titanium, there is no commercial reason why all steel should not be thoroughly degasified. A degasified steel being provided, the method of freezing or solidifying the liquid steel into an ingot, and the subsequent working into blooms and thence into various products, is of great importance in reducing the crop or scrap portion of the steel, due to segregation and pipe. How to ac-

Jan 1, 1916

By R. W. Smith, K. H. Lee

Bond type simulated closed-circuit grindability tests and batch grindability tests were run on six pure minerals plus a limestone and a taconite ore. The simulated closed-circuit tests were made at five different meshes of grind. The minerals tested varied widely in hardness and breakage pattern. For all simulated closed-circuit tests both Bond and Holmes work indices were calculated and compared. The Bond grindability testlm6 has been widely and quite successfully used for predictions of such items as ball mill power requirements and as an aid in plant comminution equipment selection. The test is interesting in that although run as a series of batch tests it is over-all a simulated closed-circuit test with a circulating load of 250%. The simulated closed-circuit feature is probably the primary reason for the notable success of the test. Perhaps the major criticism that can be brought against the test is that it is time consuming, since it normally takes a trained technician about an eight-hour shift to perform it.4 For many purposes this is an acceptable time requirement. However, if a grindability test is to be used for mill control purposes it should be performed in as short a time interval as possible, preferably under an hour. Sometimes in industry strictly batch tumbling mill tests are run and an attempt is made to correlate such batch tests with plant mill operation. Then an attempt is made to adjust operating tumbling mills based on data from the tests. The tests, however, frequently do not correlate well with operating data. The purpose of the present work was to explore some of the similarities and differences between a simulated closed-circui.t grindability test and a batch type test. Six different minerals plus a limestone and a taconite ore were tested in the experimentation. These materials varied widely in hardness, breakage characteristics, etc. Standard dry Bond grindability tests were mn on all materials at 48, 65, 100, 150 and 200 meshes of grind. Feed material was prepared by stage cmshing to -6 mesh. Initial feed volume was 700 cc. Care was taken to maintain the standard constant weight (about 20125 gm) and number of balls (283) during all the tests. Rotational speed was 70 rpm. Table I lists the materials studied along with pertinent data regarding the materials and Bond grindabilities obtained. In addition, dry batch tests were performed on all materials. These tests were made in the same mill as was used for the Bond tests. An identical ball charge and an identical feed volume were used. After rotating the mill for a predetermined number of revolutions at the same rotational speed as for the Bond test, the material was removed and separated from the ball charge. A screen analysis was performed on this product. Knowing the original size distribution of the feed and the size distribution of the product, it was possible to calculate the grindability or grams of a particular mesh produced per revolution of the mill. After the screen analysis of the product, the various fractions were recombined and placed back in the mill for further grinding. After grinding for additional revolutions of the mill the procedure was repeated. Thus, it was possible to obtain grindabilities for each material at a number of meshes of grind and for various revolutions of the mill. Grind-abilities obtained from batch tests are shown in Table 11. COMPARISON OF BOND AND BATCH GRINDABILITIES Figs. 1A through 1D show relationships between batch and Bond grindabilities. Figs. lA, lB, 1C and 1D show respectively graphs indicating the relationships for batch tests run for 100, 300, 500 and 700 revolutions of the mill. For a particular material on each graph, points are shown for 200, 150, 100, 65, and 48 meshes of grind except for several missing coarse meshes of grind for galena which did not fall conveniently on the figures. For each material and graph the point nearest the origin is for 200 mesh, the next for 150 mesh, the next for 100 mesh, etc. Considering Fig. lA, it is interesting to note that all relationships shown are essentially straight lines. There are, however, considerable differences

Jan 1, 1969

By Dwight K. Smith, Greg Carter

Studies have been conducted on The properties of many deep well cementing compositions to determine their Strength behavior over curing periods to 180 days at elevated tem-peratures and 3,000 psi pressure. This pressure results in essentially the .vat, compressive strength as that obtained with much higher pressures in ac-cordance with the findings of an API subcommittee ' These different compositions include API C1asses A, E, and F cements containig additives such as retarders, berrtorlite, heavy weight materials and pozzolans. All compositions except mixtures of Poz-zolrrrts and hydrated lime show from mild to severe degrees of strength lass over a temperature rang from -730 to 320" F after setting. Pozzolatl-time compositions actually gain in strength with time at these high temperatures. Other chemical find physical properties evaluated to observe their inter-relation.ship with Strength loss show very little correlation except in per-meability. As retrogression in strength increases, the permeability of set cement increases. X-ray difraction patterns on the set products indicate the formation of certain compounds having little or no strength value in those cementing compositions where strength loss was more severe. INTRODUCTION As a result of the growing trend toward deep well completions, a study has been made on the properties of the various cementing slurries presently in use at elevated temperatures and pressure. The strength of these compositions is of prime importance in selecting the most suitable material for use at high temperatures, to determine WOC time and the proper time to perforate with a minimum of shattering. Of primary interest in this investigation was the strength behavior of various compositions currently in use, and the effect of additives on cement after long periods of curing under severe conditions. Earlier investigators have pointed out that the strength of some cements will increase with increasing curing temperature to about 220 to 340" F, but at higher temperatures a loss in strength occurs at extended time intervals. Studies by the API Mid-Continent District Study Committee on Oil Well Cements' outlined a testing procedure whereby field conditions of temperature and pressure could be simulated in the laboratory.' It was observed that retarded cements undergo changes at elevated temperatures and some lose as much as 50 per cent of their early strength when cured at high temperatures. The scope of these tests was limited to curing periods of 1 to 28 days; additives were not covered in this study. Saunders and Walker' found that the use of additives influenced the strength behavior of cements at high temperatures, but studies were conducted only to a seven-day curing period. Ludwig and Pence' conducted an investigation of two types of cements under elevated pressures and temperatures in an effort to explain the causes of this loss in strength phenomenon. It was observed that with retrogression in strength there were other physical and chemical changes which took place as the cement aged. Today there are a number of cementing compositions available for use at well depths below 10,000 ft. Since all these earlier investigations were limited in curing time as well as the number and type of compositions studied, it was believed that a more extensive study should be conducted on the properties of cements at elevated temperatures, and this work should include those compositions actually in general field use at this time.

By C. M. Schwartz, A. E. Austin, W. B. Wilson

High-temperature X-ray diffraction studies were conducted with Th-U alloys with up to 10 wt pet U. The solid solubility of uranium in thorium as a function of temperature was determined by the method of lattice parameters. Thorium will dissolve up to 2.5 wt pet U at 950°, 4.5 wt pet U at 1150°, and 7.5 wt pet U at 1250°C. Determinations were made of the temperature of the transition of thorium and of the effect of uranium upon the transition. The a to ß transition for thorium was observed to occur at 1330' ±20°C. Mean coefficients of expansion were calculated for thorium and two alloys, and for ThO2 in contact with the thorium, using X-ray lattice-parameter data. Values obtained at 950° C for thorium and Tho2 were 12.1 and 9.40 X 10-6 per OC, respectively. Impurities obtained during the X-ray exposure were identified by diffraction and were essentially Tho2 and ThC, with two additional unknown phases being detected. The effect of the impurities upon the results is discussed. DIRECT investigation (i.e., high-temperature X-ray diffraction studies) of the phase diagram of thorium-rich uranium alloys has been shown to be necessary since recent work1 - has disclosed the presence of an allotropic transformation near 1400°C in pure thorium with the room temperature face-centered-cubic phase transforming to a body-cen-tered-cubic structure at the elevated temperature. The effect upon the transition of the addition of uranium to thorium and of the solubility of uranium in thorium at high temperatures remained unknown, yet was of interest in understanding fabrication procedures and elevated temperature use. The present work was undertaken to provide information in this area by determining the transition temperature, the effect of uranium on the transition temperature, and the solubility of uranium in thorium as a function of temperature. Experimental Work The high-temperature diffraction data were obtained using a camera especially designed for the purpose3 and capable of reaching temperatures in excess of 2000°C at pressures as low as 1 x 10." mm Hg. Temperature regulation was provided by regulating the power input to ±0.1 pet variation, and by regulating the water flow through the camera jacket to provide a constant thermal load. The X-ray sample was a rod nominally 80 mil diam, which was further turned down to 20 mil and then etched to 18 mil over 1/2 in. of one end. This was placed in the sample holder and mounted on the camera so that the smaller part was surrounded by a cylindrical tantalum-sheet radiation-type heating element. Diffraction from the sample was recorded on film after passing through a slot in the heating element and radiation-baffle shield and through beryllium vacuum windows. The X-ray film mounting was of the Straumanis type4 with a camera diameter of 114.59 mm. Since previous work of Chiotti' indicated that impurities considerably alter the transition temperature, chemical analysis of the arc melted iodide crystal-bar thorium samples was obtained prior to testing. The analysis disclosed the material to contain as low as 0.001 ±0,0002 wt pet H and 0.007 ±0.001 wt pet 0. Carbon was 0.003 wt pet and nitrogen less than 0.002 wt pet. This material was sealed in mild steel in an inert atmosphere and subsequently hot rolled to 3/8-in. diam rods at a temperature of 732°C. Following removal of the jacket, the material was pickled and cold swaged to 1/8-in. rods, from which the diffraction samples were prepared. The alloys were similarly prepared, with the uranium being added during arc melting. The uranium analyses of the alloys prepared appear in Table I. The experimental procedure for diffraction examination of the three samples of high-purity thorium differed from those of the Th-U alloys. The original practice, later modified, consisted of pumping down the camera with the diffusion pump on and then admitting liquid nitrogen to the cold trap of the system. This was modified for the Th-U alloys by maintaining liquid nitrogen in the cold trap at all times before and while the diffusion pump was heated. This minor change produced a reduction in the amount of carbon pickup by the sample during exposure to the diffusion-pump vapors. The sample was brought to the desired test temperature and exposed for 21/2 hr at pressures which were usually 2 x 10-6 mm Hg, or lower. Exposures were made at

Jan 1, 1959

By E. A. Farrell

A comprehensive survey is made of the status of the asbestos industry as it relates to marketing the product. Included are descriptions of the various types of asbestos and the grading and classification systems used. The uses of asbestos, distribution practices, and types of ore bodies are all related to marketing. World production, the producers and their capacities and world consumption for 1966-67 are summarized and statistical data are included. Asbestos is a general term describing a family of fibrous minerals of the serpentine and amphibole mineral groups. Asbestos has a long history going back to the time of the Egyptians, when it was used as a lamp wick. The commercial mining of asbestos started in Canada, Russia, and Africa in the 1800's, and the first asbestos products were made in Italy and Russia. The five main types of asbestos are: chrysotile, accounting for 95% of the total mined, amosite, crocido-lite, anthophyllite, and tremolite. Canada, Russia, and Africa are the major producers of asbestos. The commercial utility of asbestos was at first based on the heat resistance of the fibrous mineral in the form of packing, at the start of the industrial revolution. Its current utility is based more on its ability to reinforce binders such as portland cement, rubber, and plastics. Its inertness to the chemical nature of most binders is unique. Most important is its ability to maintain its reinforcing utility when the product is exposed to weather and soil conditions as in asbestos cement boards and pipe, and heat, pressure, and chemical exposure as in brake linings and gaskets and packings. The mineral asbestos is also unique because its fibrous form permits it to be spun and woven to cloth or formed into paper. Many asbestos applications are critical to national defense and at the present time, there are no satisfactory substitutes. Grading and Classification Canadian chrysotile asbestos fiber is graded and priced by length since basically the longer the fiber the higher the utility. The Canadian asbestos industry does not, however, classify the fiber by direct length measurement, but by a dry screening test. The method is called the Quebec Standard Screen (QS) test. One pound of fiber is mechanically shaken in four vertically stacked sieve boxes. The relative proportions remaining on the sieves defines the grade. The longer the fiber, the larger is the amount that stays on the top coarse screens and the less on the lower, finer mesh screens. Other tests can be used to further define the length distribution of fiber such as the wet screen Bauer McNett and the Suter Webb Comb (3 group only). The Canadian grading system divides the milled fibers into 5 main groups: group 3, 4, 5, 6, and 7, with 3 group being the longest, and 7 the shortest. Each group is further divided to subgrades, identified in each group by the letters A to Z, with "A" the longest and "Z" the shortest. See Appendix 1 for the Canadian QS classification system. The Russians also use the QS test on chrysotile. The Africans classify their chrysotile into grades similar to Canadian. The African crocidolite and amosite, however, are classified into actual length groups such as l to 2 in. and 2 to 3 in. Amosite and crocidolite are generally longer than chrysotile but also more brittle. Milled asbestos is not composed of staple length fibers like fiber glass or cotton, but of a mixture or blend of fibers ranging from long to short. Milled asbestos has a fiber length distribution similar to the particle size distribution of a powder. For example, the longest group 3 chrysotile grades have a high percentage of the longest fibers (1/2 to 3/4 in.) and low percentage of short fibers (0.003 in.). The figures in Table 1 give the approximate length distribution of the longest, middle, and shortest groups. A second and further method of classifying fiber is the degree to which the fiber bundles are separated to form a larger number of smaller diameter bundles. This property is normally described as the degree of fiberization, openness or surface area. Air permeability tests are used to measure surface area. Asbestos pro-

Jan 1, 1971

By W. B. Price

AT the New York meeting of the American Institute of Mining-and Metallurgical Engineers held in February, 1926, W. H. Bassett and J. C. Bradley presented a paper entitled "Exudations on Copper Castings."§ The purpose of the present paper, as the title suggests, is to call attention to somewhat similar phenomena which the authors have encountered in brass and bronze. From a study of the examples given, a more-or-less speculative theory of "inverse segregation" is advanced. PROTUBERANCES ON ADMIRALTY BRASS In the rolling mill of the Scovill Manufacturing Co., there have been found quite commonly bars of certain alloys which had a sort of shaggy roughness on the surface due to slight metallic protuberances. No special attention was paid to these until some bars were found on which these protuberances were heavy enough at the bottom of the bars to produce a blistered appearance. A sample of the protuberances was milled off the surface of the bar illustrated (Fig.. 1a) and upon analysis was found to contain 66.66 percent. copper, 4.02 per cent. tin and .03 . per cent. lead, whereas the average composition of the bar was 70.21 per cent. copper, 1.21 per cent. tin, and .01 per cent. lead. A sample of the shaggy-rough protuberances at the -very top of a bar was also analyzed and was found to contain 2.45 per cent. tin, indicating that it was probably of the same origin as the blistered areas. These results were not entirely unexpected for previous analyses of this alloy had -revealed that the surface was richer in tin than the rest of the bar. This, of course, is contrary to what we would expect from a consideration of the equilibrium diagram and has been called "inverse segregation."

Jan 10, 1926