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By C. S. Smith, Chih-Chung Wang

TURNBULL and his collaborators1,2 have developed the theory of homogeneous nucleation as applied, inter alia, to solidification of liquid metals. Vonnegut³ and Turnbull4 have shown that if a liquid metal is subdivided into small droplets a vast majority of them will undercool very considerably before solidification, generally to as low as about 0.8 of the freezing temperature on the absolute scale. The nuclei effective at small degrees of supercooling in bulk metal seem to be internal or surface heterogeneities, relatively small in number. If the metal is subdivided, those droplets that happen to contain such nuclei will solidify at a temperature not greatly below the true freezing point, but only a small part of the whole volume will be affected and the majority of the drops will under-cool to the much lower temperature at which homo- geneous nucleation occurs as a result of fluctuations. It occurred to one of the authors that an appropriate subdivision to give effective freedom from random nuclei is produced during the solidification of many alloys that contain a minor amount of a phase of low melting point, and that one might then expect marked undercooling of the distributed phase. Experimental: The alloys selected for initial study were copper with minor amounts of lead and bismuth, and aluminum with tin. In all these alloys, the major component freezes at a temperature not much below that of the pure metal, and there is little further change in constitution on cooling until the lower melting point constituent freezes in an almost pure state. Cooling curves were taken using the controlled heat flow method permitting approximate specific heats to be obtained. Chromel-alumel thermocouples were used, with the standard emf tables, since extreme precision was not needed. The crucible (3/4 in. id, 5/16 in. wall) was made of B & W K-20 insulating brick. It held about 10 cc of the alloy being investigated. The cooling rate was 2.5" to 2.9°C per min under a controlled temperature difference of 20°. Approximate specific heats were computed from the inverse rate curves together with data from a blank run and from a standard run with a copper cylinder of known heat capacity. The alloys for investigation were made from high-purity metals (99.99+pct) and cast into graphite molds. The castings were machined to fit the crucible and to provide a hole for the inner thermocouple. Cooling curves were taken after heating to a temperature about 50" above the melting point of the minor, lower melting-point, constituent. Results The lead phase in an alloy of copper with 5 pct lead did not undercool more than 3" below the melting point of lead (327°C) either as cast or after annealing to produce a new dispersion of the liquid phase. A copper-zinc-lead alloy with 23.75 pct zinc and 5 pct lead undercooled more but showed no thermal effect below 319°C. A cast alloy of copper with 5 pct bismuth undercooled to 249°C (M.P. bismuth 27l °C), but once solidification started it was completed at the same temperature. This was anticipated, since the bismuth forms a nearly continuous phase between the grains of copper, and a solid crystal nucleated anywhere would rapidly* con- sume the entire network of liquid, unless the physical continuity of the liquid were broken through volume changes, inadequate fluidity, or gas evolution. Similar arguments apply in the case of copper-lead alloys, where the lead-rich liquid forms a network along grain edges, though not grain faces. In both cases there would be a few isolated particles

Jan 1, 1951

By Anna H. Connard

SUMMARY The discussion focusses on developments in the debt/equity swap market since the Marte project was negotiated in early 1988. It emphasises carrying forward the recent market trends to anticipate the breadth and scope of debt/equity conversions for mine development in the 1990s. Secondary market prices of LDC paper, conversion values and political influences in the host countries and the use of near debt and commodity-based instruments as components of mine financing in debt/equity deals will be placed in the perspective of recent trends and expectations for the future. THE MARTE PROJECT The Marte mine is a gold porphyry deposit in Chile's high Atacama, for which financing was put together at the beginning of 1988. The Marte project was financed by a combination of common equity and loans. It was unusual that the equity infusions were made under different programs. Some of the international equity was infused with fresh funds via DL 600. Other common foreign equity was provided through the conversion of Chilean bank debt under Chapter XIX. On the loan side,. export credits for the import component of machinery and equipment were sought. Local bank financing was negotiated for the remainder of ' the project's anticipated cost. The debt conversion market in Chile was at its apex in terms of interest, activity and government support when the mine financing was arranged. The price of Chilean paper in the secondary market hovered about 62 to 66 cents per U.S. dollar of face value. Meanwhile, the Chilean government was negotiating conversion redemptions significantly closer to full face value. The government differentiated between debt paper exchanged for corporate investors who had sourced that paper in the secondary market, and debt paper held by bank investors who would incur a transaction loss in the conversion. The use of a combined DL 600lChapter XIX equity financing created different yield calculation bases for the various investors. Chapter XIX prevents remittance of profits before year 5 and capital repatriation before year 11. Investors choosing this vehicle have either for a corporate policy in the target project not to declare dividends until repatriation is allowed, or they have to seek uses for the peso liquidity that would be generated through dividend declarations in the early years. However, DL 600 investors face no such waiting period on dividends, nor do they have restrictions imposed on cashing out of the investment before the 11th year. Therefore, any equity structure with components of both investment mechanisms will have inherent differences in cost basis and future income flows for the various participants. This equity imbalance is defensible if the investment motivations of the parties are analyzed: a mining investor using fresh funds looks for a hurdle return on equity calculated at conservative commodity prices, with as much flexibility to reap upside benefits as possible; a mining investor choosing to invest through a debt conversion mechanism will realize a modest short term gain on the conversion, reducing his effective cost basis, but sacrificing some return because of the waiting period on repatriation of dividends. INVESTMENT OBJECTIVES A bank investor exchanging his own paper for an equity participation in a mining project realizes a conversion loss on the transaction. He seeks a risk adjusted acceptable hurdle rate of return to recoup that loss over time. Motivation for the bank investor to take that loss may be derived partly from a strategy to diversify its existing portfolio by internal policy and externally regulated guidelines. The bank will compare yields on its loan portfolio to that country with anticipated dividend flows discounted back at a risk adjusted rate. It will analyze the project with return objectives of yield enhancement over time and with

Jan 1, 1990

By S. D. Dahlgren

ORDERED G.P. zones having the cesium chloride structure were found to exist in the bcc iron-rich grains of an Fe-Au-Cu alloy that had been supersaturated with approximately equal atomic percentages of gold and copper, and aged at 400° and 350°C. Streaks and superlattice spots in electron diffraction patterns revealed the presence of the ordered zones in the aged material. The ordered Ll2 structure is commonly found for precipitates in fcc metals (e.g., Ni3A1 in nickelL7') but it is uncommon to find precipitates in bcc metals having the cesium chloride structure. The formation of the G.P. zones caused age hardening of the grains. Samples containing 3.8 at. pct each of gold and copper (with the remainder being iron) were annealed at 95@ or 1125°C in quartz capsules and were quenched by breaking the capsules under water. X-ray diffraction patterns revealed two solid solutions in the quenched samples. One solid solution was bcc and the other was fcc. The microstructure consisted of iron-rich grains of 0.3 mm diam surrounded by a yellow gold-copper-rich grain boundary network. The Au-Cu phase diagram %hows continuous solid solubility of gold and copper with ordered phases forming below 410°C. None of the ordered Au-Cu phases have the cesium chloride structure. Both Fe-Au and Fe-Cu phase diagrams3 show extended miscibility gaps and only terminal solid-solution phases. Consequently, it is reasonably certain the iron-rich grains consisted of an a-phase terminal solid solution, and the grain boundary network consisted of a gold-copper-rich terminal solid solution. Lattice parameters of the quenched solid solutions were consistent with the suggestion that the quenched phases were terminal solutions. The lattice parameter of the bcc phase (2.879A) obtained upon quenching from 950°C was higher than that (2.866A) for pure iron. The fcc phase in this sample had a lower lattice parameter than that for a 50 at. pct Au and 50 at. pci Cu solid solution, i.e., 3.866 compared to 3.877A. The lattice parameter for the 50 pct Au and 50 pct Cu solid solution was interpolated from data for Cu-Au solid solutions.4 More gold and copper were soluble in iron at 1125°C than at 950°C as indicated by a 0.012A increase in the bcc lattice parameter for a sample quenched from 1125°C. After the alloy had been quenched from 950° and 1125°C, the bcc lattice parameters were 2.879 and 2.891A1 respectively G.P. zones having the cesium chloride structure-which formed during low-temperature aging—were detected by electron diffraction and observed with electron transmission microscopy. In Fig. 1, the asymmetrical streaks parallel to ( 100) directions indicate that platelike G.P. zones had formed parallel to (100) planes of the matrix. The direction of streak asymmetry shows that the bcc unit cell of the G.P. zones was larger than the bcc cell of the matrix. The ordered cesium chloride structure is indicated by low-intensity superlattice spots at 010 positions which are nonallowed for bcc structures. The superlattice spots are streaked; therefore they are from the G.P. zones and are not caused by rel-rod effects of a thin matrix phase. The appearance and size of the zones observed in electron transmission microscopy and the appearance of the asymmetrical streaks in the electron diffraction patterns for the Fe-Au-Cu alloy were the same as those observed for a similarly treated Fe-Au alloy.' Ordered G.P. zones were detected also for an Fe-Au-Cu sample aged only at 400°C. The production of the ordered cesium chloride structure zones by low-temperature aging of super-

Jan 1, 1968

By John Chipman

THE equilibrium between titanium in liquid iron and titanium oxides has been studied by Hadley and Derge.' They have shown that a minimum occurs in the oxygen content of the metal between 0.1 and 1.0 pct Ti, but its exact level was not fixed. The oxide phase in this minimum range was principally TiO, containing some iron oxide. On the other hand, for concentrations above 5 pct Ti the oxide phase was TiO and the oxygen content of the metal increased rapidly with increasing titanium content. From their observations and the free energy of Ti0 and TiOz reported by Kelley and ah,' it is possible to derive approximate values for the activity coefficients of titanium and oxygen in liquid iron-titanium alloys and the conditions for equilibrium in steel deoxidation. Neglecting possible departures from the stoichio-metric composition, the condition of equilibrium with Ti0 may be expressed as follows: TiO= Ti_ + C) log K = log NTl + log [% O] + log yTi + log fQ Here as a matter of convenience the titanium concentration is expressed in mol fraction while that of oxygen is in weight percent. The activity coefficients are yTi and fo. The value of log fo approaches zero as the concentration of titanium approaches zero, while that of log yTi approaches a limiting value of In Fig. 1 the sum of log NTi + log [% 0] is plotted for mol fractions of titanium between 0.05 and 0.50. The smooth extrapolation gives a value of —4.15 which corresponds to log K — log y:i . We therefore have the equation: According to the data of Kelley and Mah,' the free energy of formation of Ti0 at 1900°K is -82,400 cal. The free energy of solution of half a mol of oxygen in iron, taking 1 pct 0 as the standard state, is -29,300 cal. From these we write: From these equations the activity coefficient of titanium at infinite dilution in iron is found to have a value of 0.011 or log y°. = -1.96. This is only an approximate value but is certainly better than the estimated 0.05 in Basic Open Hearth Steelmaking To obtain approximate values for the activity coefficient at intermediate concentrations, it is as- sumed that log yTi(l is constant and equal to -1.96. This corresponds to a value of E;: = 3 In yTi/aNTi = 9.0 which is not unreasonable We now have the value for the activity of titanium and the percentage of oxygen in equilibrium with TiO. It is therefore a simple matter to calculate the activity coefficient of oxygen which is shown in Fig. 2. The effect of titanium is rather large, being comparable to that of vanadium, but not so large as has been reported for aluminum. The slope of the line at low concentrations corresponds to E: = aln yo/ aNTi=-0.37. At concentrations below 1 pct Ti the deoxidation constant and oxygen content for equilibrium with TiO, can be calculated from the foregoing data and the free energy of formation of TiO,, which according to Kelley and Mah is -144,600 cal at 1900°K. The free energy of solution of oxygen has been given; that of Ti to form a dilute solution with 1 pct Ti as the standard state is RT ln (0.5585 y:i/47.9) = -34,800 cal. From these data we find (for concentrations in wt pct): TiO, = Ti + 2 -0; hFTgO0= + 51,200 cal log if =-5.89 The interaction coefficients, concentrations being expressed as wt pct, are e;: = alogfTi/a[% Ti] = +0.048 and e:' = a logfo,/a[ojTi] = -0.187. The calculation gives the following results which, in view of the impurity of the oxide phase, must be regarded as approximate:

Jan 1, 1961

By J. M. Smith, G. P. Willhite, J. S. Dranoff

Heat transfer rates were measured in sandstones with flow of gases perpendicular to the direction of energy transfer. Effective thermal conductivities ker ranged from 0.7 to 1.7 Btu/(br)(ft)(°F). The contribution of the solid phase appeared to be the most important in these consolidated materials, although the thermal conductivity of the gas had some effect. The velocity of the gas through the pores of the sandstones had no influence upon ker up to values of 168 lb/(br) (sq ft) in agreement with data obtained for unconsolidated beds of glass beads. The present results indicated that gas mixing, and hence heat transfer by convection in the pores, is less for perpendicular transfer of energy than when fluid flow and energy transfer are in the same direction. HEAT TRANSFER PERPENDICULAR TO FLUID FLOW IN POROUS ROCKS Heat transfer in porous media with pore sizes in the micron range depends upon the fluid in the pores and the geometry of the solid phase. The best characterized system is a bed of solid spherical particles. Heat transfer in this system has been studied extensive1y (Ref. 8 summarizes the literature up to 1959) when the pores contain stagnant fluid. When the fluid is in motion the directions of flow and energy transfer have an effect on the heat transfer rates, as demonstrated by comparing the work of Willhite, et al l3 for perpendicular flow and that of Kunii and Smith9 for parallel flow of energy and fluid. For perpendicular flow, no increase in effective thermal conductivity ke was noted up to mass velocities G of 77 lb/(hr) (sq ft). In contrast, for parallel flow ke, increased with G in the same range of flow rates. These higher values of ke in the direction of flow also have been observed3,4,10 in beds of larger particles, 0.1- to 0.5-in. diameter. For beds of consolidated materials, such as porous rocks, data are not available for these compar- isons, although Adivarahan1 reported results for the parallel case. Hence the primary objective of this work was to measure ke values for perpendicular flow of fluid and energy in porous rocks. Of interest also was the variation in effective conductivity with fluid velocity. APPARATUS AND PROCEDURE In the experimental method, a constant heat flux was applied to the inner surface of an annular section of the porous rock. By cooling the outer wall, a temperature gradient through the annular sample was established and measured with thermocouples placed within the sample at various radial positions, and at three elevations (A,B.C). The location of the 2-in. O.D., 3.75-in. long sample in the apparatus is shown in Fig. 1. Fluid entered the bottom (1) of the 3-in. I.D. (approximate) steel shell, flowed upwards through the sample and out at the top (3). pressure taps (2,4) were used to check the permeability of the sample. The energy flowed radially from the centrally-located electric heater through the sample and was absorbed in the water-cooled jacket. The samples studied were naturally occurring sandstones from different locations with the properties given in Table 1. These materials are identical with those used by Adivarahan 1 for the parallel flow of energy and fluid. Prior to use they were refluxed with toluene to remove hydrocarbons and leached with distilled water to remove soluble salts. Each sample was visually examined and discarded if large nonhomogeneities, such as cracks or stone particles, were noted. Eight copper-constantan thermocouples were inserted in holes drilled radially into the sample with

By Lucien F. Trueb

The microstructure of explosion-bonded pairs of similar and dissimilar metals has been investigated by electron microscopy. A review of the specific problems encountered and the methods used for obtaining surface replicas and thin-film transmission specimens of the bond interface is given. The bond area is mainly characterized by continuous and practically diffusionless metallurgical bonding. The very large shear stresses induced along the collision front of the plates being joined causes extreme grain elongation and a symmetrical pattern of subgrains in the bonding direction. The bond zone is also characterized by a very high density of dislocations and pressure-induced twins. Localized heating occurring during the cladding process can result in partial re-crystallization or the formation of thin layers of molten material. The force of precisely controlled explosions causing a high-velocity impact between metal plates has been used for several years to achieve metallurgical bonding between an extremely wide variety of metals. This method essentially consists of accelerating a plate to high velocity toward a stationary plate by a detonating explosive. Since the restrictions to bonding are not those encountered with conventional nethods, it becomes possible to bond pairs of metals having widely different mechanical properties that are immiscible or form brittle intermetallic compounds. Many applications of such composite metals are found in the field of corrosion protection as well as numerous other fields; for example, explosion bonding is being applied for fabricating the materials used by the United States Mint in the new sandwich-type coins. The primary condition for establishing a metallurgical bond is that absolutely clean metal surfaces be brought together. Any metal exposed to the atmosphere is covered with oxides, adsorbed gases, and other contaminants; even a very forceful impact of two such surfaces is not sufficient for bonding. Cowan and Holtz-man,"' who reviewed the dynamics of colliding plates in detail, showed that in order to achieve a good bond the explosion conditions must be chosen in such a way that the plate collision velocity is less than the sonic velocity, in which case no oblique shock waves are attached to the collision front. A pressure wave is then generated ahead of the collision line, and the material forming the colliding surface of each of the plates flows forward and is ejected in the form of a spray, the so-called jet. The dynamic elastic limit of the metals must be exceeded so that there is sufficient plastic deformation. At the point where the jet formed by the junction of the inner surface layers of both plates separates from the combined plates, the material experi- ences a very high shearing strain and the pressure can reach several hundred kilobars. This process strongly influences the microstructure of the bond zone as will be seen later. Behind the collision front, uncontami-nated layers of internal material are brought together under high pressure and are thus metallurgically bonded. I) STRUCTURE OF EXPLOSION BONDS The different types of explosion bonds that can be obtained depend on the explosion conditions, and have been investigated by Cowan and Holtzman,1'2 Holtzman,3 Klein; Bahrani and crossland,' and Buck and Horn-bogen. The preferred kind for practical applications is the so-called wavy bond, typical examples of which are given in Fig. 1 showing light micrographs of various metal-to-metal interfaces. In forming this type-- of bond the collision energy is mainly expended in jetting, the formation of waves, and localized melting. Beyond the crest of the waves, eddy-shaped areas are observed in which the two metals are mixed in a complex pattern of streaks. Cowan and Holtzmanl first proposed that this wavy pattern is analogous to periodic eddy shedding in the flow of a viscous fluid around an obstacle (Von Karman's eddy street). The mass of metal ahead of the stagnation point, which is associated with the jet and has forward momentum, plays the role of an obstacle and the eddies created in the flow of solid metal around the stagnation point are preserved in the final clad specimen. This idea has been reviewed more recently by Klein4 and the variables involved in the wave formation have been discussed in some detail by Bahrani and crosslands and Buck and Hornbogen.6 Several studies of the structure of explosion bonds by light metallography have already been published.1-6 Aside from the waviness and the eddies which were mentioned above, the most striking characteristic of the area in the vicinity of the bond interface is a very considerable longitudinal grain deformation which appears to be strongest at the metal-to-metal boundary and dies out as one moves away from it. Large twins are often observed within the deformed grains, and molten areas are found in the center of the eddy-shaped structures situated beyond the crest of the waves. The large hydrostatic pressures and shear stresses occurring at the interface modify the mechanical and chemical properties of the bond zone. Increases in hardness in this area have been reported by various authors.396 The defects along the interface can also cause a local increase of the chemical reactivity and thus might be expected to boost the etching rate. However, the effects of this preferential etching cannot be observed by light microscopy due to its inherently limited resolution power. The same limitation precludes the observation of morphological features directly along the bond interface as well as the interface itself. Furthermore, no information can be gained by light-

Jan 1, 1969

By R. J. Brison, O. F. Tangel

The development of a new method of mineral separation was sponsored by the International Salt Company, which requested Battelle Institute to investigate means for improving the quality and appearance of rock salt from the Company's Detroit mine. Although developed specifically for removing impurities from rock salt, the general method may be applicable to other separation problems. The principal impurities in rock salt from the Detroit mine are dolomite and anhydrite which represent 2 to 5 pct of the weight of the mined salt. In the size range from 1/4 to M in. (the range of primary interest in this project) the impurities are only partially liberated from the halite in normal production. Further size reduction to improve the liberation of impurities is not practicable in view of the market requirements for the coarse grades of rock salt. Laboratory separations in heavy liquids showed that, to improve the quality and appearance of the rock salt substantially, it would be necessary to remove not only free gangue particles but also a large proportion of the locked-in particles. Because rock salt is an inexpensive commodity, a low-cost process was required. Gravity methods were, of course, considered. The heavy-liquid separations indicated that a split at an effective specific gravity of 2.2 to 2.3 would be required. (The specific gravity of pure halite is 2.16.) Heavy-media separation was investigated but had the disadvantages that it was necessary both to operate with saturated brine and to dry the cleaned salt, and that the cleaned salt was darkened by the magnetite medium. Air tabling was tried but did not give the desired separation. It soon became apparent that established methods would not provide a satisfactory solution and work was undertaken on the development of a new process to solve the problem. PROCESS DEVELOPMENT Preliminary Experiments: At the start of the investigation, an analysis of the problem indicated that the diathermacy of rock salt—that is, its ability to transmit radiant heat—might form the basis for an efficient separation process. Under this theory, the impurities might be selectively heated by radiant heat. The particles could then be fed over a belt coated with a heat-sensitive substance so that the warm impure particles would adhere preferentially to the coating. After the initial experiments, made by heating the rock salt with an infrared lamp and separating the product on small sheets of resin-coated rubber, proved encouraging, a small continuous separation unit was set up. This comprised 1) a simple heating unit consisting of a vibrating feeder covered with aluminum foil and an infrared lamp mounted above the feeder and 2) a separation belt 6 in. wide and 36 in. long. A sketch of the device is shown in Fig. 1. Results with this apparatus confirmed the fact that a good separation was possible. It was apparent, however, that a considerable amount of experimental work would be needed to develop the scheme to a practical and economical process. The Process: Basically, the process consists of two main steps: 1) selective heating by radiation and 2) separation of the heated particles on a heat-sensitive surface. Because neither of these steps had previously been utilized commercially in mineral processing, it was necessary to do basic research on both aspects. Factors studied in the investigation included type of heat source, design of heating unit, design of separation belt, selection of heat-sensitive coating, removal of heated particles from the belt, contact between particles and coating, and maintenance of the heat-sensitive surface. Part of the experimental work was carried out on a small-scale unit consisting of the 36x6 in. belt and auxiliary apparatus, and part on a larger unit. For simplicity, discussion of work on both of these units is grouped together. SELECTIVE HEATING Radiant-Heat Source: The essential requirements for a radiant-heat source were 1) that the radiant heat be in a wave length range which is effectively absorbed by the impurities but not absorbed appreciably by the rock salt and 2) that it be dependable, practical, and economical. Selection of a heat source of suitable wave length range was one of the first considerations. It is well known that pure halite is highly transparent to radiant energy in wave lengths from 0.3 to 13 microns. However, the available data on infrared transmission by dolomite and anhydrite, particularly in the range below two microns, were not complete enough to serve as a reliable basis for selection of a heat source. Although it may have been possible to obtain sufficient data on infrared transmission and absorption to enable one to select the best heat source, a more direct procedure was used. This consisted simply of exposing the crude rock salt to each of several types of radiant-heat source on the small continuous separation device. The heat sources investigated, approximate source temperature used, and calculated wave length of maximum radiation are tabulated in Table I. Of the two types of tungsten-filament lamps investigated, both the short wave length photoflood lamps and the longer wave length infrared lamps were satisfactory from the standpoint of selectivity

Jan 1, 1961

By L. T. Larson, M. L. Picklesimer

The relationship between the apparent angle of rotation of monochromatic plane polarized light and the tilt of the basal pole from the surface normal has been experimentally determined for zirconium over the wavelength range of 500 to 655 mp. This relationship allows the determination of the spatial orientation of the basal pole of an individual grain in a polycvystal-ling zivrconium specimen to within ±3 deg by three simple tneasurements with a polarized-light metallurgical microscope. The method of measurement is discussed in detail. THE optical anisotropy of materials having noncubic crystal structures has long been used to reveal features by polarized-light microscopy. Petrographers have used measurements of certain optical properties to identify and classify transparent or translucent minerals. More recent work (i.e., Cameron1) has extended such measurements to opaque minerals in reflected light. Few attempts have been made to make similar measurements on noncubic metals. Couling and pearsall2 have reported that a sensitive tint plate can be used in a polarized-light metallurgical microscope to determine the position of the basal-plane trace in a grain of polycrystalline magnesium. Reed-Hill3 has reported that the same technique can be used for zirconium. We have found that the precision of measurement can be increased to about ±0.5 deg by using a Nakamura plate4,5 to determine the exact extinction position after the sensitive tint plate has been used to locate approximately the basal-plane trace. This report describes a method for measurement of another optical property, the apparent angle of rotation. This measurement permits determination of the angle between the basal pole of a grain of a hcp metal and the normal to the surface of the specimen. When the two measurements are combined, the orientation of the basal pole in space can be determined from three simple measurements on a single surface. One to two hundred such determinations will permit plotting of a basal-pole figure for the polycrystalline material with reasonable accuracy. When normally incident, monochromatic, plane-polarized light is reflected from the surface of an optically anisotropic material, the light may be converted to elliptically polarized light, the plane of vibration may be rotated, or both may occur. The el- lipticity, the angle of rotation, and the reflectivity can be related to the indices of refraction and the absorption coefficients of the material.6,7 Ellipticity values can be determined with an elliptical compensator, but not with the ease and precision desirable for the present purposes. Measurement of the angle of rotation requires only the determination of the angle from the crossed position (90 deg to the polarizer) that the analyzer must be rotated to obtain extinction when the trace of the optical axis in the surface is at 45 deg to the vibration direction of the polarizer. The angle of rotation of the analyzer is approximately 6/5 that of the true angle of rotation of the light as reflected from the specimen because there is a small amount of additional rotation produced during the passage of the reflected light through the mirror of the microscope. Since we are presently interested only in determining the tilt of the basal pole, the angle of rotation of the analyzer (the apparent angle of rotation of the light, i.e., uncorrected) can be used. Precision of the measurement can be increased substantially by the use of a Nakamura plate4,5 in determining the extinction position. In an optically uniaxial material (hcp or tetragonal crystal structure) the angle of rotation depends only on the optical properties of the material and the orientation of the optical axis of the grain relative to the plane of incidence of the plane-polarized light.7,8 Thus, in a metal such as zirconium, the apparent angle of rotation at the 45-deg position in any given wavelength of light is a direct measure of the tilt of the basal pole from the normal to the surface. If the optical properties vary with wavelength, the apparent angle of rotation for any given tilt of the basal pole will vary. None of the required information exists in the literature for zirconium nor for any other non-cubic metal. MEASUREMENTS ON SINGLE-CRYSTAL ZIRCONIUM A single-crystal sphere of zirconium 9/16 in. in diam was spark-cut from a single-crystal rod grown from iodide bar by an electron-beam zone-melting process.9 The damaged surface was removed by chemical polishing in a 45/45/10 mixture (by vol) of water, concentrated HNO3, and HF (48 pct) and then electropolishing at 50 v in a bath1' of methyl alcohol and perchloric acid (95/5 by vol) at -70-C. The single-crystal sphere was mounted in a five-axis goniometer stage having a removable eucentric X-ray diffraction goniometer head for the two inner orientation axes. The basal pole of the single-crysta sphere was aligned parallel to a third axis of the goniometer stage by using the sensitive tint method to determine the basal-plane trace at several rotational positions of the sphere. The alignment was then checked by removing the sphere and eucentric gonio-

Jan 1, 1967

By L. Leibowitz, M. G. Chasanov, L. W. Mishler

A drop calorimeter system is described for use in measuring enthalpies to 3600°K. Data are presented for tungsten between 2800" and 3600°K. The enthalpy of tungsten in cal per mole between 2000° and 3600°K can be represented by the equation HºT- Hº298 = - 1.7622 X 103 + 5.7772T + 8.9861 where T is in degrees Kelvin. A tabulation of com -puted values is presented for heat capacity, entropy, and free energy function. A drop calorimeter has been constructed to carry out enthalpy measurements at temperatures to 3600°K. Samples are heated by induction1 and dropped into a commercial adiabatic calorimeter, modified for this purpose. The experimental temperature is limited by the melting point of container materials and compatibility of the container and its contents. Several high-temperature drop calorimeters have been described in the literature1-5 but none has been used at temperatures as high as those in the present work; our measurements of the enthalpy of tungsten range from 2800" to 3600°K. DESCRIPTION OF EQUIPMENT An overall schematic view of the equipment is shown in Fig. 1. Power for the induction coil is supplied by a 25-kw 250 kHz Ther-Monic generator coupled to an iron core RF transformer. The Sample capsule is suspended in the work coil by 10-mil diam tungsten wires which are wrapped around a horizontal 5-mil diam tungsten wire. The horizontal suspension wire is clamped between two massive copper electrodes which are fixed in an x-y motion device that allows adjustment of the position of the heated capsule from outside the vacuum chamber. The copper electrodes are connected by flexible copper straps to a 1250-joule (5 kv, 100 pfarad) condenser bank. When it is desired to release the capsule, the condensers are discharged through the horizontal suspension wire causing it to vaporize rapidly. Very reliable and precise release of the capsule is achieved in this manner. Experiments have shown that no heat correction is required for this discharge energy. As part of the temperature measuring system, two prism holders have been incorporated in the apparatus. The upper prism holder is in the main vacuum chamber itself, whereas the lower one is in a side arm attached to the drop tube below the gate valve. The upper prism is mounted on a rotary vacuum feed-through, and may be moved under a protective shield when not in use. This prevents deposition of vapors on the prism surfaces when temperature measurements are not being made. Similarly, the lower prism is mounted on a push-pull vacuum feed-through, and when not in use may be pulled into its side tube. The prism mountings are fitted with guides and stops so that they may be moved precisely into the desired position. The aim throughout is to minimize the time the prisms are exposed to vapors from the hot samples. At the high temperatures reported in this paper, only the lower prism was used. The upper prism holder in these cases was fitted with an additional radiation shield. By using a prism and viewport, the lower surface of the samples can be observed by an optical pyrometer. The measurements discussed in this paper were obtained with a Leeds and Northrup 8622-C-S series manual pyrometer which is estimated to be accurate to 0.5 pct. Pyrometer calibrations and prism and window corrections were carried out in the conventional manner6 using tungsten strip lamps calibrated by the National Physical Laboratory, Teddington, England. Prism corrections were rechecked after each use. All work to date has been done in vacuum, and no measurable change has been observed in the prism correction below -2300°K for the upper prism and below -2800°K for the lower one. The total time of exposure of the prisms is about 50 sec per run. At high temperature, the final temperature reading is corrected by using the final A value for the prism; see Ref. 6 for details of this procedure. The calorimeter is a modified Parr Instrument Co. (Moline, lll.), Series 1230 adiabatic calorimeter with automatic jacket control. Other authors5 have used a similar calorimeter with good results. The calorimeter jacket cover and calorimeter cover are attached to the drop tube which contains a radiation shield. This shield is a gold-plated copper disc which can be operated manually from outside the calorimeter. The receiver is attached below the radiation shield and is lined with tungsten. In a typical experiment, the calorimeter and its jacket water temperatures were adjusted to 0.000°K temperature difference. The sample was allowed to equilibrate in the furnace at the desired temperature for about 20 min. The initial calorimeter temperature was then recorded, the sample dropped, and appropriate shutters closed. After about 3 min, the drop tube and receiver were filled with helium to 60 torr. The final calorimeter temperature was recorded after it had remained constant over a 5-min period. The equilibration time in the calorimeter was about 25 min. Thermistor probes are used to operate a hot and cold water supply system to maintain the jacket temperature equal to the calorimeter temperature. For actual measurements of the calorimeter temperatures, a quartz thermometer was used (Hewlett Packard Dymec Thermometer, Model #2801A). This thermome-

Jan 1, 1970

By P. A. Laxen, H. R. Spedden, A. M. Gaudin

WHEN a mineral particle is fractured, bonds between the atoms are broken. The unsatisfied forces that appear at the newly formed surface1 are considered to be responsible for the adsorption of ions at the mineral surface. A knowledge of the mechanism and extent of ion sorption from solution onto a mineral surface is of interest in the development of the theory of flotation.2,3 Study of the adsorption of sodium from an aqueous solution on quartz offers a simple approach to this complicated problem. The availability of a radioisotope as a tracer element meant that accurate data could be obtained.4,5 Three main factors which appeared likely to affect the adsorption of sodium are: 1-concentration of sodium in the solution, 2-concentration of other cations in the solution, and 3-anions present in the solution. Hydrogen and hydroxyl ions are always present in an aqueous solution. By controlling the pH, the concentration of these two ions was kept constant. The variation in the amount of sodium adsorbed with variation in sodium concentration was then determined under conditions standardized in regard to hydrogen ion. The effect of concentration of hydrogen ions and of other cations was also measured. A few experiments were made to get a preliminary idea on the effect of anions. The active isotope of sodium was available as sodium nitrate. Standard sodium nitrate solutions were used throughout these experiments except when the effects of other anions were studied. It was found that sodium adsorption increased with sodium-ion concentration, but less rapidly than in proportion to it. Increasing hydrogen-ion concentration, or conversely decreasing hydroxylion, brings about a comparatively slight decrease in sodium-ion adsorption. Increasing the concentration of cations other than hydrogen or sodium decreases somewhat the adsorption of sodium ion. It would appear as if the kind of anion is a secondary factor in guiding the amount of sodium ion that is adsorbed. Materials and Methods Quartz The quartz was prepared as in previous work in the Robert H. Richards Mineral Engineering Laboratory4 except for the refinement of using de-ionized distilled water for the final washing of the sized quartz, prior to drying5 To minimize the laborious preparation of quartz, experiments were made to determine whether the sodium-covered quartz could be washed free of sodium and re-used. The experiments were successful as indicated by lack of Na' activity on the repurified material and by its characteristic sodium adsorption. Table I gives the spectrographic analyses of the quartz used. The quartz ranged from 16 to 40 microns in size, averaging about 23 microns (microscope measurement), and had a surface of 1850 sq cm per g (lot I), 2210 (lot II) and 2000 (lot III) as determined by the Bloecher method.6 Radioactive Sodium Method of Beta Counting for Adsorbed Sodium: Na22, the radioisotope of sodium, possesses convenient properties.7 It has a half-life of 3 years, thus requiring no allowance for decay during an experiment. On decay it emits a 0.575 mev ß radiation and a 1.30 mev ? radiation. The decay scheme is illustrated in the following equation: [Y Nam S. - 'Net 3 years] The ß radiation is sufficiently strong to penetrate an end-window type of Geiger-Mueller counting tube. This, in turn, makes it possible to use external counting, a great advantage in technique. Furthermore, it permits the assaying of solids arranged in infinite thickness, while assaying evaporated liquors on standardized planchets. The equipment used was standard and similar to that employed by Chang8 The original active material was 1 ml of solution containing 1 millicurie of Na22 as nitrate. This active solution was diluted to 1000 ml. Five milliliters of this diluted active solution was found to give a quartz sample a sufficiently high activity for accurate evaluation of the sodium partition in the adsorption measurements. Also, 1 ml of final solution gave a sufficiently high count for precision on the liquor analyses. The sodium concentration of the diluted active solution was 1.2 mg per liter, so that 6 mg of sodium for 60 ml of test solution and 12 g of quartz was the minimum amount used. The active solution was stored in a Saftepak bottle. Procedure for Adsorption Tests: The method consisted of agitating 12 g of quartz with 60 ml of solution of known sodium concentration for enough time to establish equilibrium between the solution and the quartz surface. The quartz was separated as completely as possible from the solution by filtering and centrifuging. The activity on the quartz and in the equilibrium solution was measured and the partition of the sodium was calculated from the resulting data. The detailed procedure for the adsorption test is set forth in a thesis by Laxen5 In brief, it included the following steps: 1-Ascertainment of linearity between concentration of Na22 and activity measured. 2-Evaluation of factor to translate activity on solid of infinite thickness in terms of activity on an evaporated active film of minute thickness, on the various shelves of the counter shield. 3-Taking precautions to avoid evaporation of water during centrifuging.

Jan 1, 1952

By B. W. Roberts, V. A. Phillips

A copper alloy containing- 25.5 at, pct Zn and 19.0 at. pct Ni, which was previously found to show an anoma1old.s hardening effect on quenching- from 600 "C and aging- at 400oc, has now been examined by neutron diffraction. No evidence of long-range order was found. The aged sample showed diffuse scattering- consistent with clustering. The anomalous hardening effect is now attributed to lattice strains caused by clustering rather than (long-range) order hardening. SOLID-solution Cu-Ni-Zn alloys (the commercial 'nickel silvers") have been reported to show anomalies in: change of resistivity on cold working,1-6 temperature coefficient of resistance,2-12 resistivity at low temperatures,13,14 parameter (vs temperature),2"4 calorimetric data,2,4 specific heat,15,16 dilation,2-4 and elastic modulus.17 The structure responsible for the anomalies is produced by annealing typically near 400°C and is rather loosely referred to as the ('K-Zustands" (K state), a term coined by Thomas1' who apparently meant simply that the arrangement of atoms on the sites deviated from that expected statistically. Thomas proposed that the K state occurred in a variety of (solid-solution) alloys such as Cu-Ni-Zn, Ni-Cr, Ni-A1, Ni-Cu, Fe-A1, and Fe-Si and is recognized because its formation is strongly temperature-dependent and results in an increase in electrical resistance which can then be decreased by cold working. Later workers on ('nickel silver" have interpreted the K state variously as short-range order, long-range order. or a combination. The present work was prompted by the discovery by Phillips and Jones19 of a substantial hardening effect when an 18 pct "nickel silver" alloy which is fairly close to the Cu2NiZn composition, was reheated in the range 150" to 450 C after previously quenching from 600°C or, alternatively. was slow-cooled from 600°C or above. The phenomenon was attributed to (long-range) order hardening. Due to the similarity in the atomic scattering factors of copper. nickel, and zinc atoms, the ''nickel silvers" are unfavorable for X-ray diffraction studies aimed at detecting ordering. Nevertheless Bialas et a1.,20 using a powder sample containing 47.96 wt pct Cu, 24.03 wt pct Ni, and 27.98 wt pct Zn, slow-cooled from 400" to 200°C taking 500 hr, observed weak super lattice lines. Further unpublished work" using an anomalous dispersion X-ray technique indicates that zinc atoms are regularly ordered at the corner points of the lattice cell, while the nickel and copper atoms are statistically distributed on the remaining sites. Köster 17 also observed X-ray superlattice lines, for example, in an alloy containing 43.5 wt pct Cu, 28.6 wt pct Ni, and 27.9 wt pct Zn superimposed on the basic fcc cell with a = 3.62 kX. He proposed a Cu3Au-type superlattice with the Ll2 structure in which the A sites were statistically occupied by copper and nickel atoms and the B sites by zinc. He adds that substitution must be possible so that zinc atoms partly occupy A sites. Below about 35 pct Cu, Koster had some evidence for a CuAu-type superlattice with the Llo tetragonal fcc structure with a = 3.82 kX, c/a = 0.88 which could be preserved by quenching. This is suggested17722 to correspond to CuNiZn. While the present work was in progress Hirabaya-shi et a1.23 made an independent comprehensive neutron-diffraction study of a single crystal containing 50.05 at. pct Cu, 26.57 at. pct Ni, 0.25 at. pct Mn, 0.13 at. pct Fe, balance zinc. The presence of manganese and iron is surprising since the crystal was supposedly grown from high-purity metals. The homogenized crystal showed evidence of long-range ordering after an anneal of 5 months at about 300°C. Three possible crystal models were proposed. A curious feature of their results23 is that they could not find any neutron-diffraction evidence of ordering in a powdered polycrystalline near-stoichiometric Cu2NiZn alloy. There appears to be some essential difference between a near-stoichiometric Cu2NiZn alloy and one somewhat further off stoichiometry as used by the present authors. Thus Sato14 was able to reproduce the low-temperature resistivity anomaly reported by one of the authors13 on the present alloy if he used a similar composition, but found the normal behavior of the residual resistivity in a near-stoichiometric alloy. satol2 found that the resistivity of a cold-drawn slightly off-stoichiometric alloy increased to a maximum on isothermally annealing at 300°C and then decreased ("over-aged"). Since he could not explain this on the basis of ordering phenomenon, he proposed that zinc atoms were segregating to stacking faults (Suzuki effect) and found etching bands on the surface by replication which were attributed to the widening of faults. Sato suggested14 that the hardening effect observed by Phillips and Jones19 is partly due to the Suzuki effect. EXPERIMENTAL The starting material was 1/4-in.-diam hard-drawn rod of a commercial 18 pct "nickel silver" alloy identical with that used in a previous study by Phillips

Jan 1, 1967

By H. D. Outmans

In steady vertical flow, the interface of an immiscible liquid-liquid displacement is horizontal for any flow rate below the critical. In nonvertical flow, however, the shape of the interface in the steady state does depend on the flow rate, and the purpose of this paper is to calculate the unsteady interfaces during the transition of one steady state of flow to another. A knowledge of these transient interfaces is of considerable importance in reservoir engineering where the calculation of breakthrough recovery depends on the instant the interface reaches the producing wells and on the shape of the interface at that time. Although the emphasis is put on transient interlaces, which eventually approach stable equilibrium, it is shown that if the displacement exceeds a critical rate no equilibrium is possible. The interface is then unstable and viscous fingers are formed during the displacement. The critical rate and the shape of the transient and equilibrium interfaces are affected by the effective interfacial tension; but since this effective interfacial tension appears in the calculations only in combination with the inverse square of the thickness of the medium, its effect in the reservoir would appear to be negligible compared to its significance in model experiments. INTRODUCTION Stability criteria and the early growth of interfacial disturbances in a plane parallel to the boundaries of a dipping formation in which oil is displaced by an incompressible fluid were described in a previous paper.l This type of instability is significant in thin reservoirs. However, if the reservoir has appreciable thickness, then interfacial stability in vertical planes, normal to the upper and lower boundaries, also becomes important (the displacement is supposed to be parallel to these vertical planes). The difference between the two stability problems is that, in the first case, the intersections of the interface with planes parallel to the boundaries are normal to the direction of the displacement; in the second case, the intersections, this time with vertical planes, are not normal to the displacement. Instead, they are tilted at an angle which depends on the displacement rate. The tilt of steady interfaces was calculated by Dietz2 who also determined the critical rate of displacement for stability in the vertical plane by assuming that this rate would coincide with an interfacial tilt equal to the dip of the formation. The critical rate thus calculated is the same as has been found for thin reservoirs (see Eq. 1.1 of Ref. 1 and of the present paper). Dietz's calculation of the stable tilt was verified by laboratory experiments and the agreement was found to be fairly good.3 It is doubtful, however, that stable tilts actually exist in the reservoir because a change in production rate is not followed by an instantaneous adjustment of the interface to the new rate but, rather, by a transition period during which the interface changes from one equilibrium tilt to the other. The principal objective of this paper has been to describe these transient interfaces without putting any restrictions on the flow conditions or the shape of the interface, as had been done previously. The second objective was to compute the critical velocity, taking into account capillary effects, and the third was to evaluate, at least qualitatively, the shape of the front at rates above the critical, again without making the simplifying assumptions introduced by previous investigators.2,3 In the following sections two examples are given of the calculation of interfacial motion. The first describes this motion for an initially horizontal interface in a dipping layer, and the second for a vertical interface in a horizontal layer. The mathematical formulation of the problem is nonlinear in the boundary conditions, and this prohibits its solution in closed form. Instead, the solution is obtained in the form of higher-order approximations. 1 Before proceeding to a description of the mathematical model, however, we define two quantities

By Harold A. Krueger

FACILITIES and mining operations of the National Lead Co., St. Louis Smelting and Refining Division, near Fredericktown, Mo., are situated in a famous mining area. Copper, lead, nickel, and cobalt have been mined here for more than 100 years, work having been started on a high sulphide copper outcrop in 1847. Lamotte sandstone is characterized by differential compaction on a rigorously eroded pre-Cambrian surface. The Bonneterre formation was therefore a good host for minerals not generally found in mineable quantities in these midwestern areas. Unusually complex minerals, however, make beneficiation difficult, and because of irregular ore thicknesses and elevations many engineers and operators have not attempted to mine the property. Others have tried who failed. This paper deals with economic, efficient, and competitive methods of mining these highly irregular orebodies, as compared to the open-stope, room-and-pillar methods normally used for horizontal-bedded lead deposits. For the purpose of this study it should be understood that the ore is found in two distinctly different types of occurrences, one to be designated as basin ore and the other as contact ore. Mining of basin ore is complicated by many faults, fractures, cross faults, and breaks. Contact ore is complex because it is found on flanks or slopes of pre-Cambrian knobs or highs. The dip of the mining floor for the latter type varies between 18" and 45". Occurrences of both types of ore are complicated by water courses or solution channels which carry unconsolidated shale, lime, sand, and dolomite. This material is also found between the bedding planes of the members of the Bonneterre formation. The water found where there are fractures, faults, and channels makes it very fluid and tacky, see Fig. 1, particularly after it has been blasted and handled by loading and hauling machines. Much of the ore can be wadded and thrown without dispersing. During early operations by the Buckeye Copper Co. in 1861 and the North American Lead Co. from 1900 to 1910, conventional narrow-gage railroad and side dump mine cars were used with hand shoveling. The complications of mining the contact ore, the only type attempted at this time, can be appreciated when it is realized that operators were obliged to use mules for haulage. Haulageways constructed on these slopes were of necessity similar to wagon trails or goat trails up the side of a mountain. In other words, it was merely a matter of going from side to side of the strike length of the slope, gaining a little in elevation on each shuttle trip. Production totaled only one to two tons per manshift. A few years later, about 1913, the property was purchased by combined Canadian interests known as the Missouri Cobalt Co., and the use of trolley locomotives was initiated. Between 1900 and 1928 a land agent using churn and diamond drilling methods prospected scattered sections of the area. In 1928 the first property was purchased by the present company, then operating as the St. Louis Smelting and Refining Co. Check drilling and prospecting was carried out by the company at various times between 1928 and 1939 to correlate the erratic mineralization. Much information about both types of orebodies was accumulated, but it was still questionable as to whether money should be invested to work these occurrences. In anticipation of high lead and copper prices, about the time World War II started, it was decided to develop and bring into production some of this ore. In 1942 No. 1 shaft was put down on the largest basin-type orebody and in 1943 No. 2 shaft was put down on contact-type ore. Operations were expanded when No. 3 shaft was completed in 1943, and progressed further in 1948, when National Lead Co. dewatered and opened No. 5 and 6 mines, old workings of the North American Lead Co. and the Missouri Cobalt Co. Because of the differential compaction of Lamotte sandstone over the pre-Cambrian porphyry, in some instances mineable thicknesses of basin-type ore occurred 20 to 30 ft above the sand. This is the exception rather than the rule, since most of the mineralization starts at the sand and is variable in thickness. The ore was attacked, therefore, by development drifts and crosscuts at the lowest possible elevation, where the ore immediately overlying the Lamotte sandstone could be drained and made accessible for mining. It was planned to connect to the drifts and crosscuts with raises to mine ore deposited 20 to 30 ft higher. The higher orebodies were thus mined as slusher levels. Slusher hoists were used to drag the ore into the raises, which were made into hoppers. The ore was then loaded into 32x32-in. ore cans, hauled to the shaft by battery locomotives, and hoisted by the conventional Tri-State method. The rate of efficiency was 5 to 6 tons per manshift underground. The contact-type ore was attacked in a similar way, except that the orebodies were not nearly so wide, so that they were more flexible for slusher loading into cans. This advantage was offset, however, by haulage complexities, since the railroad was constructed on steep slopes. Through experience and ingenuity, many improvements were made in mining both types of ores. The two levels, so-called, in the basin-type ore-bodies were connected as previously planned, more efficient locomotives replaced the older ones, and a

Jan 1, 1954

By J. Sibakin, R. D. Hindson

In order to devise a practicable soaking pit schedule for use at The Steel Co. of Canada Ltd.'s Hamilton Works, soaking pit heating temperatures, sooking times, pit capacity, and safe maximum mill drafts were correlated with fluctuations in the current or load of the bloom mill driving motor. Other variables such as total delays in the pit, rolling schedules, mill delays, and track times were also investigated. IN order to show an easily applied and accurate means of establishing soaking pit heating temperatures, soaking times, pit capacity, and safe maximum mill drafts, these various factors are correlated herein with fluctuations in the current or load of the bloom mill driving motor. Rolling practices have a considerable influence on the production capacity of a blooming mill. The maximum values of the torque, in particular, are of importance, since even instantaneous current peaks lead to the tripping of the motor by the overload relay and result in loss of mill time. The establishment of safe maximum drafts and accelerations for ingots of different sizes and of a soaking pit practice which would ensure a consistent and satisfactory plasticity of the metal is of considerable importance for increasing the efficiency of both the blooming mill and the soaking pits. The Bloom Mill Dept. of the Hamilton Works, The Steel Co. of Canada Ltd., is equipped with one 44 in. mill driven by a 7000 hp motor with the setting of the overload relay at 22.0 ka. The speed of rotation of the motor is regulated after the Ward-Leonard system. There are three basic speeds of 9.5, 28, and 47 rpm and a further possibility of increasing the speed by weakening the field. This last possibility is hardly ever used during practical operations. The rolling program of the blooming mill is varied, both in the size of the ingots to be handled and in the steel grades. The total tonnage handled by the mill is about 2,000,000 ingot tons per year. At the time of the investigation, the Bloom Mill Dept. was equipped with 22 soaking pits (6 regenerative, 14 bottom-fired, and 2 one-way top-fired pits) with a total bottom area of 2770 sq ft. The pits are fired with a blast furnace-coke oven gas mixture having a calorific value of 155 Btu per cu ft. The foregoing figures show that the production program was such as to impose the necessity of a most efficient usage of the available equipment. For this purpose, the operations of the 44 in. mill and of the soaking pits were investigated, and the results of the investigation were used as a basis for a revised soaking pit schedule and drafting practice. The plasticity of an ingot of a certain chemical composition when being rolled is determined mainly by the following factors: I—the ingot size, both thickness and width; 2—the length of the gas soak; and 3—the surface temperature. The first two factors determine the uniformity of the temperature distribution over the cross-section of an ingot. The third factor introduces the level of the heating of an ingot. The torque produced by an ingot being rolled is determined by the area of the metal displaced, its plasticity, and acceleration values. On the other hand, with shunt motors the torque is determined by the current. This can be assumed to be correct with only a small degree of error for compound motors with a relatively small effect of the series windings as long as the velocity is not regulated by weakening the field. Since the spread is relatively unimportant when compared to the width of an ingot and since it is also reduced several times during rolling by edging passes, the draft alone and not the area of the metal displaced may be taken into consideration with ingots of a similar size. It is therefore possible to determine the main features of the heating and drafting of an ingot by measuring the current and acceleration of the mill motor. After the acceleration has been taken into account, the amount of current will be an indication of how the motor responds to a heating and/or drafting practice and these practices can be adjusted in order to get the desired result. As peak currents are more likely when heavier ingots are rolled, the rolling of plate and slab ingots was investigated. Conditions prevailing when smaller ingots are rolled can be deduced from the results obtained on heavier ingots. All measurements were made when plain carbon grades under 0.15 pct C were rolled. The motor current, the voltage across the armature, and the rpm were recorded simultaneously on synchronized charts, Fig. 1, which moved with the speed of 6 in. per min. Each draft was recorded by a special observer. The rpm curve made it possible to establish the acceleration at any given moment. For purposes of correlation, the maximum current during a pass and the corresponding acceleration were used. The charts made it possible to establish the position of the roller's lever at any given moment as well as the total time of a pass. The slab ingots were divided into three groups (28x35, 28x45, and 27Mx53 in. ingots) and each group was investigated separately. Since they account for most of the current peaks, only flat passes were used for purposes of correlation, a total of 1373 having been investigated.

Jan 1, 1956

By Whitman E. Brown, Louis J. Erck

L. A. ROE*—This paper is one of great value to the iron ore industry. The Humphreys spiral is a relatively new tool and gives promise of being quite useful in solving certain problems of iron ore beneficiation. Spirals have been tested on a martite ore at the Benson mine of Jones and Laughlin Steel Corp. in northern New York State. Our New York ore is considerably different, physically and mineralogically, than the one mentioned in this paper, and contains only 25 pct iron. This ore can be processed on spirals to give a concentrate containing 62 pct iron with an 85 pct recovery. On our particular ore we found operating difficulties when the spiral feed was coarser than 14 mesh. These were chiefly due to excessive "build-up" of locked middlings in the spiral circuit. In extreme cases these middling particles would accumulate to such an extent that the plant had to be shut down and the spiral surge tanks cleaned out. It is interesting to note that there exists a close relationship between the results of tabling a given iron ore and concentration of this same ore on Humphreys spirals. The size range of the ore must, of course, be within those limits acceptable to spiral concentration. Comparative tests on several of our mar-tite ores showed tabling results to be the same as spiral results. The authors make no mention of the use of a tailing stream splitter (now available from the spiral manufacturer) which is a useful tool in studying iron losses in the tailings stream. 011 our particular martite ore we found a considerable accumulation of fine-sized iron ore particles in the outside portion of the tailings stream. This fraction may be amenable to further treatment. E. H. ROSE*—The authors have concluded an interesting piece of work and this paper is an excellent factual account of a rapid and somewhat unusual transi-;ion in practice in the plant described. Perhaps it was modesty on their part which caused them so casually to limit to one sentence the fact that "several other methods of concentration on the fine ores representative of the Hill Trumbull group . . . failed to produce consistently an acceptable grade and recovery of finished product." The fact is that they were confronted by a difficult mineral-dressing problem and they are to be congratulated on their courage and persistence in staying with it until a satisfactory solution was evolved. A visitor to the plant might have been mildly astonished, as I was, to see one type of concentrator handling that part of the load early in the 1947 season, its experimental replacement by another a little later, and then in 1948 to see that both types had simply disappeared and their place taken by the spirals which were operating as placidly as though they had been there all the time. In working out economic methods of beneficiating Alabama red ore, most of which development is still ahead of us, it is likely that we also will pass through a period of successive disappointments, for we too have a problem where it is next to impossible either to "guess 'end right in the first place," or, because full-scale operating cost is such an important factor, to lay the ultimate answer on the line in advance by means of laboratory experimentation. Iron ore being what it is instead of what it used to be, it is encouraging to have the example the authors have given us today that a tough nut that will not crack on the first blow or the second is apt to do so on the third or fourth.

Jan 1, 1950

By W. Crafts, J. L. Lamont

Electrolytic extraction of carbides from quenched and tempered steel and their examination under the electron microscope were found to be helpful in understanding the mechanism of secondary hardening in alloy steels1 and the same technique has been applied to isothermally transformed steels. A preliminary survey of the utility of the method has indicated that it has promising possibilities for investigating the characteristics of pearlite and bainite. The examination of a few carbon and chromium steels has suggested that pearlite is formed with carbides of two varieties representing the lamellar and nonlamellar forms and that bainite appears to form with a structure analogous to, but significantly different from, martensite. Procedure The method used for examining the carbides was similar to that described previously.1 The chromium steels used in the investigation were made from an Armco iron base in an induction furnace and were not treated with grain-refining deoxidizers. The composition of the steels is given in Table 1. Three-inch square ingots were forged and rolled to 1/8-in. thick sheet for use in the isothermal studies. After rolling, the sheets were sandblasted to remove the rolling scale. Specimens approximately 3/4-in. wide and l1/2-in. long were prepared from the 1/8-in. sheet. They were heated in a salt "bath at 2100°F (1150°C) for 1/2 hour, transferred to other salt baths at 1300°F (704°C), 1000°F (538°C), 800°F (426°C), or 600°F (315°C), held for various periods up to 100 hr and finally quenched in water. After quenching, the specimens were cut in half, one half being submitted to microscopic examination and the other half being used for the electrolytic extraction. The isothermally transformed specimens were submitted to examination under the light microscope to determine the degree of transformation and type of structure and were photographed at 2000 X. Carbide residues were obtained by electrolyzing in 10 pet hydrochloric acid and collecting the residue in glycerine to minimize attack by the acid. As pointed out in the earlier paper, the carbides are attacked to some degree during electrolysis. This attack is relatively minor on the coarser carbides but may be quite severe on the fine bainitic carbides. The residues were washed free of the glycerine with water and alcohol. The alcohol was removed by repeated washings of amyl acetate, and the amyl acetate suspensions were transferred to stoppered vials. Debye-Sherrer X ray diffraction patterns of the residues were prepared using a chromium target. A selection based on the microstructure and X ray data was then made of samples considered most illustrative of the progress of transformation. Electrolytically extracted residues from these samples were submitted to examination by W. D. Forgeng and A. C. Jenkins on the electron microscope at the Research Laboratories of The Linde Air Products Co. and electron micrographs were made at X 5000 and enlarged to 25,000 X. The micrographs obtained with both the light and the electron microscopes are mounted side by side in the accompanying figures. Although no effort was made to establish the T-T-T diagram for the chromium steels, the times for holding in the salt bath were adjusted with the intention of making the samples represent different stages in the transformation at temperatures of 600, 800, 1000, and 1300°F. The degrees of transformation and results of X ray examination are shown in Tables 2—4. The carbide designations refer to orthorhombic or trigonal carbide types and are not meant to imply that the compositions are exactly as indicated. X ray Diffraction Data The occurrence of Fe3C and Cr7C3 in these steels was found to be consistent with published data on comparable chromium steels. Steels A and B with relatively low ratios of carbon to chromium contained Cr7C3 in the pearlitic structures and FeuC in the

Jan 1, 1950

By C. T. Butler, W. W. Kay, R. D. Boddorff, R. L Ash

DRILLING and blasting in anthracite open-pit mines is a continuous problem to contractors and explosive engineers because of the diverse conditions caused by the nature of the geological formations, the extensive mining of the portions of coal beds near the surface, and the proximity of many strip pits to populated areas. Pennsylvania anthracite occurs in four separate long and narrow fields totaling only 480 sq miles. The coal measures are rock strata and coal beds that are considerably folded and faulted. The crests of the anticlines are eroded extensively. The beds outcrop on the mountain sides and dip under the valleys. At first only the upper portions of the syn-clines could be stripped. Now stripping to increasingly greater depths is economically possible, as is indicated by the fact that the proportion of freshly mined anthracite produced by strip mining has increased from 3.7 pct of the total tonnage in 1930 to 29.6 pct in 1950. Much of the rock overlying the deeper beds now being stripped is so extensively broken that considerable difficulty is experienced in drilling satisfactory blast holes and in using explosives in such manner as to insure a uniformly broken material easily removed by the excavating machinery. Such breaking of rock strata has occurred because the bed now being stripped has been mined extensively in former years by underground methods, and tops of gangways and chambers have subsequently failed. Draglines are used to uncover coal where the overburden can be moved with little or no re-handling. These machines range in size from those having a 2 cu yd capacity bucket on a 60-ft boom to those handling a 25 cu yd bucket on a 200-ft boom. Draglines are also used to strip to the bottom of the coal basins if the depth and the distance between the crops are not too great. For this type of operation blast holes are drilled full depth to the bed. These holes are commonly 30 to 90 ft deep; however, in exceptional cases, holes may be as shallow as 12 ft or as deep as 130 ft. Drilling is normally done for blasts of 12,000 to 60,000 cu yd of overburden, 30,000 cu yd being considered an average blast if vibration is not the controlling factor. Where the stripping of wide basins or the exposure of a moderately pitching vein makes the use of draglines impractical, dipper front shovels equipped with 4 to 6 cu yd buckets load into trucks. Overburden is removed in benches of 25 to 30 ft with blast holes drilled 4 or 5 ft deeper than the planned floor of the bench. For shovels under 5 cu yd bucket capacity the volume blasted varies from 8000 to 12,000 cu yd, whereas a volume of 30,000 to 50,000 cu yd of overburden is frequently blasted at one time for the larger shovels where vibration is not an important factor. During the past decade the churn drill, generally the Model 42-T Bucyrus-Erie blast hole drill equipped for drilling 9-in. diam holes, has become the most common blast hole drilling machine. Electricity powers half the churn drills in use and is preferred on the large strippings where electric shovels are operated and the working area is concentrated. On these operations the cost of additional electricity for the drills is less than the cost of fuel to operate diesel units because of the existing large demand load of the excavating equipment. Moreover, electric motors start more easily in cold weather and generally are less expensive to maintain. Diesel driven units are employed where a higher degree of mobility is required. The average drilling speed is 8 ft per hr, although in softer rocks a rate of 15 ft per hr is attained. Where rock is hard and strata is badly broken, drill speeds may be less than 2 ft per hr. Low drilling production results under these circumstances when loose material falling from the upper portion of the drill holes causes drill stems to be jammed. Rock formations vary so greatly in the region that a 9-in. diam churn drill bit may become dull after drilling only 2 ft or may drill satisfactorily for 56 ft; however, an average of 35 ft is usual in sandstone of medium hardness. Dull bits are hoisted to flat bed trucks by the sand line of the drill and are usually sharpened in the contractor's bit shop adjacent to the job. Care is generally taken to cover the thread end of the bit with a cap. To facilitate handling of bits around the drill, a heavy thread protector having an eye top is becoming more popular than the flat-top rubber or metal cap furnished with new bits. The 9-in. diam blast holes for a 25 to 30 ft bench are normally on 18x18 ft to 20x20 ft spacings, depending on the character of the overburden, although in broken ground 15x18 ft centers may be used to obtain better breakage and a more even bottom for the bench. The patterns of holes for shots

Jan 1, 1953

By R. D. Boddorff, R. L. Ash, C. T. Butler, W. W. Kay

DRILLING and blasting in anthracite open-pit mines is a continuous problem to contractors and explosive engineers because of the diverse conditions caused by the nature of the geological formations, the extensive mining of the portions of coal beds near the surface, and the proximity of many strip pits to populated areas. Pennsylvania anthracite occurs in four separate long and narrow fields totaling only 480 sq miles. The coal measures are rock strata and coal beds that are considerably folded and faulted. The crests of the anticlines are eroded extensively. The beds outcrop on the mountain sides and dip under the valleys. At first only the upper portions of the syn-clines could be stripped. Now stripping to increasingly greater depths is economically possible, as is indicated by the fact that the proportion of freshly mined anthracite produced by strip mining has increased from 3.7 pct of the total tonnage in 1930 to 29.6 pct in 1950. Much of the rock overlying the deeper beds now being stripped is so extensively broken that considerable difficulty is experienced in drilling satisfactory blast holes and in using explosives in such manner as to insure a uniformly broken material easily removed by the excavating machinery. Such breaking of rock strata has occurred because the bed now being stripped has been mined extensively in former years by underground methods, and tops of gangways and chambers have subsequently failed. Draglines are used to uncover coal where the overburden can be moved with little or no re-handling. These machines range in size from those having a 2 cu yd capacity bucket on a 60-ft boom to those handling a 25 cu yd bucket on a 200-ft boom. Draglines are also used to strip to the bottom of the coal basins if the depth and the distance between the crops are not too great. For this type of operation blast holes are drilled full depth to the bed. These holes are commonly 30 to 90 ft deep; however, in exceptional cases, holes may be as shallow as 12 ft or as deep as 130 ft. Drilling is normally done for blasts of 12,000 to 60,000 cu yd of overburden, 30,000 cu yd being considered an average blast if vibration is not the controlling factor. Where the stripping of wide basins or the exposure of a moderately pitching vein makes the use of draglines impractical, dipper front shovels equipped with 4 to 6 cu yd buckets load into trucks. Overburden is removed in benches of 25 to 30 ft with blast holes drilled 4 or 5 ft deeper than the planned floor of the bench. For shovels under 5 cu yd bucket capacity the volume blasted varies from 8000 to 12,000 cu yd, whereas a volume of 30,000 to 50,000 cu yd of overburden is frequently blasted at one time for the larger shovels where vibration is not an important factor. During the past decade the churn drill, generally the Model 42-T Bucyrus-Erie blast hole drill equipped for drilling 9-in. diam holes, has become the most common blast hole drilling machine. Electricity powers half the churn drills in use and is preferred on the large strippings where electric shovels are operated and the working area is concentrated. On these operations the cost of additional electricity for the drills is less than the cost of fuel to operate diesel units because of the existing large demand load of the excavating equipment. Moreover, electric motors start more easily in cold weather and generally are less expensive to maintain. Diesel driven units are employed where a higher degree of mobility is required. The average drilling speed is 8 ft per hr, although in softer rocks a rate of 15 ft per hr is attained. Where rock is hard and strata is badly broken, drill speeds may be less than 2 ft per hr. Low drilling production results under these circumstances when loose material falling from the upper portion of the drill holes causes drill stems to be jammed. Rock formations vary so greatly in the region that a 9-in. diam churn drill bit may become dull after drilling only 2 ft or may drill satisfactorily for 56 ft; however, an average of 35 ft is usual in sandstone of medium hardness. Dull bits are hoisted to flat bed trucks by the sand line of the drill and are usually sharpened in the contractor's bit shop adjacent to the job. Care is generally taken to cover the thread end of the bit with a cap. To facilitate handling of bits around the drill, a heavy thread protector having an eye top is becoming more popular than the flat-top rubber or metal cap furnished with new bits. The 9-in. diam blast holes for a 25 to 30 ft bench are normally on 18x18 ft to 20x20 ft spacings, depending on the character of the overburden, although in broken ground 15x18 ft centers may be used to obtain better breakage and a more even bottom for the bench. The patterns of holes for shots

Jan 1, 1953

By Carroll F. Hardy

The day by day loss of industrial plants to gas and oil is chiefly by default. The coal industry is not selling its superior economy, safety, and other advantages to its customers. THE position of the coal industry has been affected by a wide variety of developments in the production and use of energy. The tempo of development and change has been increasing and the end is not in sight. Legislation is currently being proposed for commercial use of atomic power, and the employment of atomic energy in significant quantity will probably occur about the same time as the decline in production of petroleum and natural gas. But these developments are in the future and have little immediate effect on utilization and marketing of coal. While no one should try to suppress or retard the development of a new and economical source of energy, both the coal and private utility industry should be allowed to question how the nuclear power is to be used, who is to use it, and who is going to pay for it. The taxpayers have a monopoly on fissionable material and the knowledge to employ it. Any commercial use must stem from this source. It is not hard to visualize either taxpayer-subsidized private utility atomic power plants on one hand and super TVA's on the other. In view of the gains of gas and oil in the home heating field, it is interesting to compare the 1940 and 1950 census reports on the kind of fuel used for heating in occupied dwelling units. Table I shows that whereas coal provided 77 pct of the fuel for central heating (furnaces and boilers) in 1940, it was down to 45.4 pct in 1950. However, only about 1 1½ million units were lost in this 10-year period. In the non-central heating category, which principally includes stoves, the percentage declined from 39.2 to 25.6, but the units declined about 2½ million in number. The big increase was in heating units designed to burn gas and oil. Use of wood for central heating declined about one-third. Data on amount of fuels used for residential heating are not available, but information is on hand for residential and comnlercial space heating, see Table 11. Commercial space heating includes office buildings, churches, schools. and similar structures. The annual use of bituminous coal in these two categories declined about 1 million tons in the 10-year period. Other forms of solid fuel showed greater losses, except wood, which remained the same. Domestic stokers reached their high point in 1948 with about 1,200,000 in use. At the end of 1951 there were approximately 1,116,790 stokers in use. Conversions to gas and oil have been from hand-fired heating plants in the ratio of about 7 to 1 compared to stokers. In other words, for every one stoker which has been converted to gas or oil, seven hand-fired units have been converted to gas or oil. A bare recital of these data would indicate that the coal industry is holding its own reasonably well. However, 93.4 pct of the new homes built in 1951 were heated by gas or oil. Oil-burning equipment was installed in 37.8 pct and gas equipment in 55.6 pct of the new homes. This indicates that the public prefers gas when it is available, and that oil is second choice, with all forms of solid fuel apparently used when it is unavoidable. It must be pointed out, however, that during the period of rapid expansion of gas pipelines gas has been sold for house heating at prices that are in some cases actually lower than coal prices, or very nearly on a par. Gas has been sold at wells at far below the comparable price for oil produced from the same wells, and far below its actual worth. This situation is being remedied at the present time by increases in gas prices at the wells. For example, the wellhead price of gas in Texas averaged 7.494 per Mcf in 1952. In 1949 it was 4.59c per Mcf. This increase in price is being reflected in pipeline gas prices, and in most of the markets served by the pipelines the tendency is to get it out of the bargain basement type of sales. The American Gas Association estimates that at the end of 1952 there were in the United States about 11 million customers for gas house-heating, and the Association expects additional gains each year until around 18 million homes will be heated by gas in 1975. By 1975 there should be 60 million dwelling units to be heated in the United States, if dwelling units increase at the same rate as the population. If the gas industry heats 18 million dwelling units by that time, this still leaves 42 million units to be heated by some other fuel. If oil is used to heat 18 million dwelling units in that same year, 24 million would of necessity be heated by coal, coke, wood, electricity, or another fuel. The total number of dwelling units using coal listed in the 1950 Census was 18,776,000, so it would appear that coal has a chance at least to stand still in the tonnage sold for domestic use. In the first quarter of 1953, 2044 domestic stokers

Jan 1, 1955

By B. H. Bergstrom, Will Mitchell, T. G. Kirkland, C. L. Sollenberger

IN a previous article' the authors outlined a study of the variables in rod milling and also reported data from a series of open circuit grinding tests on a massive limestone in a 30-in. x 4-ft end peripheral discharge rod mill. As a second part of the experimental program, an analysis is now presented for the 30-in. x 4-ft overflow rod mill grinding under identical conditions, except that discharge ports on the periphery of the mill shell have been sealed so that the products from the present series overflowed through a 9-in. diam .opening in the center of the end plate. A variance analysis has been made of the combined data for the two experiments, and performances of the two mills are compared here. Included in the first report' were descriptions of feed preparation, rod mill circuit, instrumentation and controls, and techniques used to evaluate data. Dependent and independent variables were defined, and variance analyses were made to test the relative significance of variables and to establish magnitude of error for the experiment. Significant data were plotted in various combinations, and conclusions were drawn from the graphs. The procedure and analysis in this series of tests follows the first tests and is not repeated. Data from the second series are recorded in Table I. Listed in the first three columns are the independent variables of feed rate (1000, 2000, 3000, 4000, and 5000 1b per hr), mill speed (50, 60, 70, 80, and 90 pct of critical), and pulp density (50, 60, 70, and 80 pct). The dependent variables, Pso, P100, reduction ratio, slope of the log-log sieve analysis curve, power demand, and Bond work index follow. Of these, only the reduction ratio and the Bond work index were analyzed for significance. Production of new surface as calculated from sieve analyses has not been included for this series because of the questionable assumptions that have to be made to satisfy the formulas involved. The large number of products obtained during the runs precluded the use of surface measurement techniques by the gas adsorption methods at this time; however, samples of all products have been stored for future reference. To test the consistency of the reporting of the sieved products, an averaged sieve analysis was calculated from the wet-dry plots obtained from the three product samples of each run. The resulting averaged analysis was plotted and the P80, selected. The relative deviations of the P80's from each of the three product samples with respect to the P80 of the averaged analysis were then calculated. In only two sets were the relative deviations (6.2 and 9.9 pct) considered excessive. In each of these two sets, one sieve analysis was obviously out of line; hence that analysis was ignored and new averages were computed. This reduced the relative deviations to 1.2 and 2.7 pct respectively. The relative deviations of the product analyses with respect to their averages ranged from 0.1 to 1.4 pct at 1000 lb per hr, 0.0 to 1.1 pct at 2000 lb per hr, 0.2 to 3.0 pct at 3000 lb per hr, 0.3 to 4.3 pct at 4000 lb per hr, and 0.5 to 5.2 pct at 5000 lb per hr. The relative deviation of the 80 pct passing point for 96 dry sieve analyses of the feed with respect to that of the averaged analysis was 7.6 pct. This slightly higher percentage can probably be attributed to a greater proportion of tramp oversize in a crusher product than is ordinarily found in a rod mill product. The last column on Table I lists the adjusted work index, which has been used as the measure of efficiency for the various combinations of operating conditions investigated. Efficiency increases as the index becomes lower. It was reported in the previous paper that the work indexes for the Waukesha limestone used in these experiments decreased as the product size decreased (as calculated from Bond grindabilities). That is, this limestone becomes easier to grind as the material becomes finer. This is unusual, because the work index for most materials as calculated from the Bond grindability has remained constant as the product size decreased or has increased slightly. Table II lists the results of Bond grindability tests at all mesh sizes from 3 to 200 and the work indexes calculated from them. To remove this variation of work index with product size from the data so that results would apply to any material of constant work index, the work index values shown in Table II were plotted against product size on log-log paper. From this curve (a straight line function in this case), the expected work index for the product size for each of the runs of the experiment was obtained. The work indexes as calculated from the reduction ratio and energy consumption were then divided by the corresponding expected work index. The results obtained are reported in percentages on Table I as adjusted work index and are actually percentages of the work index for the Waukesha limestone at the size in question. Multiplication of the work index value for a material of constant index by these percentages should allow the application of the adjusted work index curves to the material. Only the adjusted work index values, not the actual experimental values, were used for the variance analyses and for the graphs.

Jan 1, 1956