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By Carl Benedicks

IT is well known by every one who has had to deal with boiler tubes that these are often seriously affected by a sort of corrosion, occurring as a local pitting, that frequently causes a perforation of the tube in a rather short time. The characteristic appearance of this corrosion is shown in Fig. 1. A very similar corrosion occurs in condenser tubes (Fig. 2).1 A study of the microstructure or local chemical composition of the metal (iron; 70 :30 brass) fails to reveal any cause for this pitting. Of course one might possibly assume the starting point-to be some oxide particle, causing an electrolytic local action, but this in no way explains the continued corrosion, progressing even when the assumed oxide particle must have disappeared. By the excellent work done by the Corrosion Research Committee of the Institute of Metals, and communicated, in October, 1923, to the Institution of Engineers and Shipbuilders in Newcastle-on-tyne, stress was laid on the fact that a content of entangled air has a very obnoxious effect. In the following correspondence, Sir George Goodwin stated that "engineers have, for a long time past, regarded air as the big enemy to be fought against in all questions of corrosion"2 and Kenneth Fraser pointed out that the most vital point is "the avoidance or removal of possibly the chief cause of present day corrosion, i. e. entrapped air and gases brought out of solution."' In their reply, however, the authors state that they had "never for a moment believed that entangled air was responsible for the beginnings of corrosion, and express the opinion that the gradual liberation of air could not account for localized corrosion."4 On consulting the many textbooks on corrosion, as that

Jan 4, 1925

By W. P. Z. German

Some attention should be given to definitions. The term "unit operation " may have at least two meanings. One meaning is the merging of titles and the development and operation of the unitized area, as if it were one tract of land held under a single oil and gas lease, according to a definite program intended to accomplish a maximum recovery from the pool as a whole at a minimum of cost. It is incomplete when the royalty owners do not also merge their titles to their oil and gas rights in the area, and is complete when they do. The other meaning is not accompanied by any merger of titles, but the development and operation of the area is in accordance, as nearly as reasonably practicable, with such a program. This second conception may be nothing more than a cooperative development and operation plan, but in this paper it is regarded as more than that. If there cannot be unit operation without a merger of titles, it would seem that the state cannot require unit operation, for it cannot require a merging of titles; but if it may consist in requiring each and all of the leaseholders to develop and operate or to submit to a development and operation according to some such common plan as is referred to above without at the same time requiring a merger of titles, it would seem that unit operation may be required by the state. Whether the states have this power is the subject to be herein considered. If the state can so bind the several lessees, it also can so bind the several lessors. The writer does not know what would be an ideal plan for the development and operation of a pool; but it takes into account the fact that the accumulation of gas and oil is not uniform throughout the formation; that often free gas, highly compressed, occupies the upper portions of the reservoir, the oil with compressed gas in solution coming next in order; that at places oil is not overlain by free gas, and sometimes there are peaks where free gas is not immediately underlain by any oil; and the fact that these substances are held under a uniformly distributed pressure, generally referred to as "rock pressure." It also recognizes that the most efficient utilization of this naturally existing reservoir pressure in the recovery of the oil requires that there be no operation of wells completed into areas where gas only has accumulated, for this diminishes the

Jan 1, 1931

By Jerry F. Fountain

Variations in ore grade, mineralogy, and copper pricing structures over the life of the Inspiration mine have mandated many modifications to the treatment methods to maximize process economics. In the 1970's, copper prices generally declined, while inflation, wages, and interest rates increased. A metallurgical treatment route had to be developed for this continuing economic climate which would be capable of minimizing labor, energy, and capital cost requirements. After many years of development, the patented "Ferric Cure" process was introduced to satisfy these requirements. This dump leach process for treatment of mixed oxide/sulfide ore includes: strict mineralogical control of ore placed for leaching, controlled leach pad construction, solution saturation and curing of the pads with higher acid concentrations, and, finally, rinsing of the cured pads for removal of dissolved copper. Leach solutions, high in sulfuric acid during the cure application and low in sulfuric acid during the rinse, contain sufficient ferric iron to enhance the leaching of chalcocitic sulfide minerals.

Jan 1, 1983

By N. Standish

Heat transfer coefficients have been measured in beds of various packings irrigated with mercury and molten fusible alloy countercurrent to hot gases. The measured coefficients for both systems were found to increase with gas velocities and liquid rates. Correlations were determined which show this dependence and also indicate that heat transfer in these systems is influenced by the liquid flow characteristics and the thermal conductivity of the gas and the solid packings. A heat transfer model has beer2 proposed which explains the various features of the experimental results. On the basis of this study, which gives an insight into the heat exchange in the melting zone of the blast furnace, it was concluded that by comparison with the furnace stack heat transfer coefficients are about 1.5 times higher in the melting zone. EACH year large tonnages of metal are produced in operations which, in part, involve liquid metal irrigation of "packings" countercurrent to hot gases. The melting zone in blast furnaces and in cupolas is a good example of packings irrigated with a liquid melt countercurrent to gases. In all instances of this kind large amounts of heat are exchanged and it is desirable to have some knowledge of heat transfer phenomena involved in these systems. So far the most common method of analyzing furnace efficiencies, fuel requirements, and the general thermal state of the furnace has been through the use of heat balances. As heat balances are essentially statements of the first law of thermodynamics they give no real indication of the factors which govern heat transfer between phases in the various zones of blast furnaces. Hence, rational improvement in production efficiency and the development of theoretical models is only possible if the heat transfer characteristics are known at every stage of the process and related to the important variables involved. This has been generally recognized for some time but it was only recently that Kitaev et al.' have produced a comprehensive treatment of heat transfer in solid-gas countercurrent systems such as the blast furnace stack and the packed bed regenerator. Using their treatment it is now possible to predict the effect of particle size, thermal conductivity, bed porosity, and the flow rates of both the gas and the solid material on the heat transfer in the blast furnace stack. However, the stack of a blast furnace is only one part of an integral unit for which the heat transfer analysis cannot be complete without also considering the heat exchange in the melting zone. The complexity of heat transfer processes in this region of the furnace has so far escaped quantitative description. Yet, the melting zone accounts for a greater amount of heat exchange than all the other zones of the furnace put together. Moreover, if the reduction of oxides in the melting zone proceeds in part in the liquid state the importance of heat transfer on furnace productivity and on the metal and slag temperatures is obvious. THEORY Heat transfer for two-phase flow in packed beds is a complex problem involving a number of heat exchange paths for which interphase areas are not known with any degree of certainty. Analytical solution is, therefore, difficult. This difficulty is emphasized by noting that Rabinovich~ and Luck have only recently solved the steady-state heat transfer for simplified two-phase heat exchangers of known area. However, useful progress can be made for the system considered by making a not unreasonable assumption that the usual heat transfer considerations apply and restricting treatment to the steady state. For these conditions the rate of heat transfer dq in a height dz of a packed bed of unit area is: dq = UaATdz [I.] Integration of Eq. [I] then gives the total heat transferred: assuming both U, the overall heat transfer coefficient, and a, the interphase area, to be independent of bed height. Since a, in these systems, is unknown it is convenient to combine this term with U. The group U, then represents the overall heat transfer coefficient on a volumetric basis. If AT is linear with q, then for a bed of unit volume Eq. [Z] can be integrated to give: is the log mean of terminal temperature differences. From Eq. [3] U, can be readily calculated as q and {AT)im are experimentally obtained quantities, but a difficulty arises in interpreting its meaning. Two approaches are possible depending on whether the effect of packing in the transfer of heat is neglected or not. If the packing is thermally decoupled then the resistance concept gives the relationship: which states that the overall resistance is the sum of the gas phase and the liquid phase resistances (assuming areas are equal throughout). Because the resistance to heat transfer in liquid metals is negligible by comparison with that of the gas,4 Eq. [4] can be simplified, i.e.:

Jan 1, 1969

By R. C. Earlougher

Based on laboratory tests conducted with the use of fresh core samples as well as a considerable amount of field data obtained from numerous water floods in northeastern Oklahoma, it appears that for any given oil saturation there is a critical maximum velocity above which the oil-recovery efficiency falls off very rapidly. In effect, when a water flood is operated above this critical velocity, the injected water-oil ratio rises extremely fast, thus shortening the economic life of the flood and reducing the ultimate oil recovery. This critical velocity apparently varies considerably with the percentage of oil saturation of the sand, so that in effect the higher the oil saturation at the beginning of a flood the higher the velocity that can be used successfully. In reviewing several of the earlier floods in the Mid-Continent area, it is concluded that most of the failures were due to two things: (I) too low an oil saturation, such as 30 per cent, and (2) too high water-injection rates, Although considerably more field data are necessary to establish definite limits, it would seem that the proper field injection rate for a 330 by 330 or 440 by 440-ft. spacing varies from approximately I bbl. per foot of sand per day where the oil saturation is as low as 30 per cent up to 5 bbl per foot of sand per day when the oil saturation is as high as 45 to 50 per cent, Introduction With secondary recovery by water-flooding receiving more and more attention throughout the industry, a greater working knowledge of multiphase flow under field conditions becomes more and more necessary A great deal of research has been carried on in highly idealized laboratory conditions, from which certain trends have been indicated, but with few exceptions no direct application to field use has been reported. widely varying conclusions have been drawn from the mass of idealized laboratory experiments and often this divergence apparently was due to the neglect of connate or interstitial water. Since interstitial water is such an important factor in water-flooding operations, it then follows that any laboratory flooding experiment must necessarily take it into account; and since it is difficult to set up laboratory models to allow for interstitial water, the next best procedure is to use fresh core samples for such tests. Even this procedure has its difficulties, inasmuch as it is possible to run only one flooding test on each sample, as each sample differs somewhat in character from all other samples. However, this disadvantage can be overcome to a large degree by the use of an extremely large number of samples. The next question that arises is: "IS it possible to get uncontaminated core samples having a true oil and water saturation like that existing in the reservoir?" If the sand under consideration is still in the primary stage of production, with a normal or relatively high amount of gas still in solution in the oil, probably it is not possible to get a nonflushed core. On the other

Jan 1, 1943

By R. C. Earlougher

Based on laboratory tests conducted with the use of fresh core samples as well as a considerable amount of field data obtained from numerous water floods in northeastern Oklahoma, it appears that for any given oil saturation there is a critical maximum velocity above which the oil-recovery efficiency falls off very rapidly. In effect, when a water flood is operated above this critical velocity, the injected water-oil ratio rises extremely fast, thus shortening the economic life of the flood and reducing the ultimate oil recovery. This critical velocity apparently varies considerably with the percentage of oil saturation of the sand, so that in effect the higher the oil saturation at the beginning of a flood the higher the velocity that can be used successfully. In reviewing several of the earlier floods in the Mid-Continent area, it is concluded that most of the failures were due to two things: (I) too low an oil saturation, such as 30 per cent, and (2) too high water-injection rates, Although considerably more field data are necessary to establish definite limits, it would seem that the proper field injection rate for a 330 by 330 or 440 by 440-ft. spacing varies from approximately I bbl. per foot of sand per day where the oil saturation is as low as 30 per cent up to 5 bbl per foot of sand per day when the oil saturation is as high as 45 to 50 per cent, Introduction With secondary recovery by water-flooding receiving more and more attention throughout the industry, a greater working knowledge of multiphase flow under field conditions becomes more and more necessary A great deal of research has been carried on in highly idealized laboratory conditions, from which certain trends have been indicated, but with few exceptions no direct application to field use has been reported. widely varying conclusions have been drawn from the mass of idealized laboratory experiments and often this divergence apparently was due to the neglect of connate or interstitial water. Since interstitial water is such an important factor in water-flooding operations, it then follows that any laboratory flooding experiment must necessarily take it into account; and since it is difficult to set up laboratory models to allow for interstitial water, the next best procedure is to use fresh core samples for such tests. Even this procedure has its difficulties, inasmuch as it is possible to run only one flooding test on each sample, as each sample differs somewhat in character from all other samples. However, this disadvantage can be overcome to a large degree by the use of an extremely large number of samples. The next question that arises is: "IS it possible to get uncontaminated core samples having a true oil and water saturation like that existing in the reservoir?" If the sand under consideration is still in the primary stage of production, with a normal or relatively high amount of gas still in solution in the oil, probably it is not possible to get a nonflushed core. On the other

Jan 1, 1943

By R. G. Garlick, H. B. Probst

Tungsten single-crystal specimens of various orientations were deformed in tension at room temperature. Slip traces indicated both (112)(111) and (110) (111) slip; however, about 10 pct plastic dejormation was required bejore these traces could he seen. Resolzled shear-stress considerations indicated that at least some of the particular systems observed were not those on which slip initiated hut were secondary systems. This is highly probable, considering the high plastic strains involved. Analysis of the stress data with respect to possible slip systems indicated that slip must have been initiated at stresses below the proportional-limit stresses measured. ALTHOUGH there is general agreement that slip deformation in fcc and hep metals takes place on the plane of close packing and in the direction of close packing, there is no such agreement for slip in bcc metals. It is generally agreed that the close-packed direction (111) is the slip direction, but investigations have led to conflicting descriptions of the slip plane. As Hoke and Maddin1 point out, there are essentially four points of view. 1) Deformation in bcc metals is composite shear on (112) and (110) planes or on nonparallel (110) planes, and any apparent slip on other planes can be accounted for completely by slip on these planes. Chen and Maddin have reported this to be the possible case for molybdenum." 2) Slip occurs in the (111) direction and is limited to {110), {112), and (123) planes (the three closest packed planes of the lattice). 3) Slip occurs in a (111) direction, but not necessarily on planes of close packing (banal slip). 4) Slip occurs in those directions and on those planes for which ß, the ratio of Burgers vector to interplanar spacing, is a minimum. The slip systems of the bcc metal tungsten have never been fully determined, although several investigators have reported pertinent results.3"7 The present work was initiated to determine the active slip systems in tungsten at room temperature, the critical resolved shear stresses associ- ated with these systems, and the orientation dependency of operative systems. These features of tungsten deformation at room temperature have never been reported in the literature. The authors find this somewhat surprising, particularly in view of the availability of tungsten single crystals since the advent of electron-beam zone-melting techniques and the widespread interest in refractory metals. It would seem apparent that such work has been attempted but the results have not been reported, possibly due to the conflict with deformation theory. The results of the present work conflict with any straightforward description of deformation based on the proposed explanations of slip in bcc metals. Although these conflicts have not been resolved, a presentation of the problem seems in order and should be of value to others working in this field. MATERIALS AND PROCEDURE Single-crystal tungsten rods of 1/8-in. diameter were grown from undoped commercial rod by one-pass electron-beam zone melting in apparatus previously described by witzke.8 Representative analyses of the rod before and after melting are given in Table I. There was no detectable zoning of impurities during melting. Buttonhead tensile specimens, as shown in Fig. 1, were machined from single crystals. Two flats 90 deg apart were ground in the gage length of each specimen. These flat surfaces facilitated the analysis of slip traces. No attempt was made to position these flats with respect to the crystal orientation. The worked surface layer of the machined specimens was removed by electrolytic polishing in a NaOH solution. Tensile-axis orientations were determined by standard Laue back-reflection techniques. The sharpness of the Laue spots indicated that the crystals were free of strain.

Jan 1, 1964

By Derek J. Cyr

Climate has an immense impact on the properties of Athabasca oil sands and the ease or difficulty with which it is excavated and extracted. During the winter months, exposed oil sands surfaces freeze. When hydraulic and electric shovels used in the various operations in the Fort McMurray area excavate the benches, large frozen lumps are created. These lumps are either destined for a lump dump where increased costs are incurred due to rehandle, or they are sent to the primary crushers where they can cause significant downtimes by jamming the crusher. The crusher down time can sometimes be in the order of hours of lost production. Studies on data from two consecutive winters at Syncrude Canada?s North Mine show a high correlation between climate and the generation of frozen oil sands lumps. Temperature, ground cover, traffic, bench exposure time, oil sands grade and moisture content all contribute to this problem. A 1D frost penetration model was used to predict the depth of frost expected in oil sands and the corresponding likelihood of frozen oil sands lumps. To combat the challenge of frozen lump generation, a number of proactive and reactive measures can be taken: artificial snow, shallow ponds, scheduling, blasting or ripping.

May 1, 2004

By M. Prats

This paper presents a method for obtaining the correct values of the breakthrough sweep efficiency of the staggered line drive, taking into account the proper shape of the breakthrough streamline. Results obtained were different from those previously published, which were obtained by using an inexact shape of the breakrhrough streamline. INTRODUCTION In Section 9.31 of Muskat's' The Flow of Hotnogeticous Fluids Through Porous Media, it is stated that in a staggered line drive flood "the streamline of highest average velocity [is] the line of centers between input and output wells" (see Fig. I). Muskat used this concept to determine the relationship between the breakthrough sweep efficiency and the geometry of the staggered line drive pattern. Although it is clear from symmetry considerations that the breakthrough streamline passes through the midpoint between input and output wells, it is equally clear, as shown in Fig. 239 of Ref. 1, that the breakthrough streamline is not represented very well by the straight line joining the input and output wells. Therefore, it is desirable to determine the proper relationship between the breakthrough sweep efficiency and the pattern geometry by using the proper shape of the breakthrough streamline. METHOD OF SOLUTION It was found that the effect of the geometry of the staggered line drive on the breakthrough sweep efficiency can be investigated easily by making use of the method developed in Ref. 2. With this method, it can be shown that the general complex potential for the staggered line drive, which can be considered as a rectangular five-spot, is given in the coordinate system of Fig. 1, by O(z) = In cn(z\m) = +(x,y) + i $(x, y) . (1) where z = x + iy, +(x, y) is the potential distribution and $(x, y) is the stream function. The function cn (zm) is a Jacobian elliptic function of parameter m and has simple zeros at z,. = (2n + 1) K + 21iK and simple poles at z, = 2nK + (21 + 1)iK. Thus, the complex potential behaves like a(z) = ln(z - zr.) in the neighborhood of the production wells and behaves like a(z) = - ln(z - Z,) in the neighborhood of the injection wells. Since (z - z1.v) = rll.ei, we note that the potential + has the proper logarithmic behavior near the two wells, while the stream function $ varies with the angle, decreasing clockwise around the production well and increasing clockwise around the injection well. The functions K(m) and K'(tn), related by K(m) = K'(m,), where m + m, = 1, are known as the complete elliptic integrals of the first kind. By use of other properties of the Jacobian elliptic functions, the general stream function distribution for the staggered line drive can be obtained from Eq. 1: From the Jacobian elliptic function values, sn(0lm) = 0 dn(O(m) = cn(0jm) = 1, and f[K'(m)Iml = 03, it follows that the stream function given by Eq. 2 satisfies the proper symmetry conditions near a production well P located at [K(m), 01 and an injection well I located at [0, K' (m)]. That is, the line IOP in Fig. 1 is a streamline with value G (0. 0) = -0. and the straight lines connecting I and P to the point [K(m), K' (m)] is a streamline of value $[K(m), K' (m)] = -7/2. Similar symmetry conditions are obtained near other wells. It should be nuled that for m = m1, = 0.5, Eq. 2 reduces to the stream function distribution of the regular five-spot given in Ref. 7. SHAPE OF THE BREAKTHROUGH STREAMLINE It is apparent, from symmetry considerations, that the breakthrough streamline ($,) passes through the point [K(m)/2, K' (m)/2]. Its value there is so that the shape of the breakthrough streamline $,, is given by

Jan 1, 1957

By S. L. Lopata, E. B. Kula

A variation of yield and tensile strength with direction has been noted in heat-treated 4340 steel which had been warn-worked by rolling in the austenitic condition prior to quenching. Measurements by X-rays showed a preferred orientation of martensite crystals. Various ideal preferred orientations of martensite were calculated by assuming a preferred orientation for austenite and transforming this to martensite by the Kurdjumov -Sachs and Nishiyama relationships. Comparison with the measured preferred orientation showed that the ideal rolling texture for austenite in 4340 steel could be expressed as a (112) [111] texture with a component of (110) [112]. No evidence was found for any fiber axis in the rolling direction, or fop- a (123) [412] texture. The observed martensite pole figures can be adequately accounted for by these ideal austenite textures and by the Kurdjumou-Sachs or Nishiyama transformation relationships between austenite and martensite. ALTHOUGH preferred orientations are found in cold-rolled steel sheet and in many nonferrous metals, they are not generally encountered in wrought, heat-treated high-strength steels, since such steels are generally not cold worked sufficiently to develop a strong texture, and any texture that is present is removed during heat treatment by the phase transformations taking place. This report gives details on a preferred orientation found in warm-rolled and hardened 4340 steel. In a recent study, a special combination heat-treating and working technique was used in which 4340 steel was deformed in the austenitic condition, and before re crystallization of the austenite could occur, quenched to form martensite.' Since the austenite was unrecrystallized, it was cold worked and hence could have contained a preferred orientation which could be transmitted to the martensite on quenching, and this in turn could be manifested as a directionality of mechanical properties. Such a directionality of properties was found as a result of working, and this prompted an X-ray study of the preferred orientation. Literature Survey— Rolling Texture in Face-Cen-tered-Cubic Austenite—M a preferred orientation is found in a rolled and hardened steel, it is first appropriate to consider what texture existed in the austenite as a result of the rolling but prior to the transformation to martensite. The changes taking place as a result of the austenite-martensite transformation are then considered. In view of the instability of austenite in 4340 steel at low temperatures, no direct determination of the austenite texture was made. However, an estimate of the texture for austenite in 4340 steel may be made by considering the textures found for other face-centered-cubic metals. Barrett' has reviewed the rolling textures for many materials. The most common orientation in face-centered-cubic metals has the (110) planes parallel to the rolling plane and the [112] directions parallel to the rolling direction, or (110) [112]. Other orientations found are (112) [111], as well as (100) [001], (110) [001], and others. Beck and his co-workers, using quantitative pole figures, report that (123) [121],3 later corrected to (123) [412],4 better describes the ideal orientation. smallman5 reported that the ideal preferred orientation for high-purity face-centered-cubic metals is (123) [121], but that there is a transition to (110) [112] as solid solution elements are added. The latter texture tends to occur more readily at lower temperatures. This transition between the two textures was explained by differences in the slip characteristics with concentration or temperature. More recently, Jones and Fell6 concluded that the (123) [412] texture for face-centered-cubic metals could equally well be represented by a mixture of (110) [112] and (112) [111] textures, and hence it had no physical reality. From the above results it can be seen that there is no agreement on the "ideal" texture for fcc metals and, hence, no firm basis for assuming a texture for austenite in 4340 steel. Therefore, the orientations (110) [112], (123) [412], and (112) [111] have been considered in the following.* *The (123) [4121 is identical to the (123) [121] rotated 90 deg. Orientation Relationship between Austenite and Martensite—When martensite forms from austenite, certain crystallographic planes of the martensite are parallel to planes in the austenite. This orientation relationship was first determined by Kurdjumov and

Jan 1, 1960

By Arnt Solbu, Jomar Thonstad

The reaction between CO, and aluminum in cryolite-alumina melts in contact with aluminum has been studied by passing CO2 over the melt. In unstirred melts a homogeneous reaction between dissolved metal and dissolved CO2 was observed. In stirred melts in which convection was induced by bubbling argon through the melt, the dissolved metal apparently reacted mainly with gaseous CO2. The rate of formation of CO increased slightly with increasing depth of the melt, and it did not depend on whether CO2 was passed over or bubbled through the melt. The rate of formation of CO increased with increasing area of the metal/melt interface and with the application of anodic current to the metal. It is concluded that the dissolution of metal into the melt is the rate-determining reaction. THE current efficiency in aluminum electrolysis is determined by the rate of the recombination reaction between the anode gas and the metal: 2A1 + 3CO2—A12O3 + 3CO [1] as originally stated by Pearson and waddington.1 The occurrence of this reaction in cryolite-alumina melts in contact with aluminum was first verified experimentally by Schadinger.2 Thonstad3 has shown that the reaction may proceed further to give free carbon: 2A1 + 3CO— A12O3 + 3C [2] Normally only a few percent of the CO formed undergoes such reduction. The mechanism of these reactions has not yet been clarified. Aluminum, as well as CO,, is soluble in the melt. The solubility of aluminum in cryolite-alumina melts at around 1000°C corresponds to 75 x 10- 6 mole A1 per cu cm,4 while that of CO2 is only 3 x 10-6 mole CO, per cu cm.5 Taking into account the stoichiometry of Reaction [I], the ratio between dissolved aluminum and dissolved CO2 available for the reaction in a saturated melt is about 40. Therefore, as will be shown in the following, the reaction probably mainly occurs between gaseous COa and dissolved aluminum. The dissolved aluminum presumably consists of subvalent ions of aluminum and sodium.4'6 Since the interpretation of the present results is not dependent upon the nature of this solution, the dissolved metal will be designated solely as Al+ in the following. The reaction can then be divided into four steps: A) dissolution of metal, e.g., 2A1 + Al3 — 3A1+ [3] B) diffusion of dissolved metal through a boundary layer; C) transport of dissolved metal through the bulk of the melt; D) Reaction [1]. If dissolved CO, takes part in the reaction, three additional steps embodying the dissolution and transport of CO2 must be added. schadinger2 observed, when bubbling CO2 through the melt, that the rate of formation of CO (in the following designated rfco) did not depend on the distance from the metal surface. The results also indicate that the rate of bubbling did not affect the rfco. When passing CO, over the melt, Revazyan7 found that the loss of metal did not depend on the depth of the melt above the metal or on the flow rate of CO2, and concluded that Step A is rate-determining. In an unstirred melt, however, Gjerstad and welch8 found that the rfCo decreased with increasing depth of the melt, indicating that step C was rate-determining. It thus appears that the rate control of the process depends on the experimental conditions, particularly on the convection. In the present measurements the reaction has been studied in unstirred as well as in stirred melts. EXPERIMENTAL AND RESULTS The experiments were carried out at 1000°C in a Kanthal furnace with a 10-cm uniform temperature zone (±0.l°C). The melts were made up of "super purity" aluminum (99.998 pct), hand-picked natural cryolite, and reagent-grade alumina. In experiments where alumina crucibles were used, the alumina content in the melt was close to saturation (13.5 wt pct9); otherwise it was 4 wt pct. Pure Co2 (99.85 pct) was passed over the melt, and the exit gas was analyzed for CO2 and CO by the conventional absorption method.3 From the weighed amount of CO (as CO2) the rfco was calculated as the number of moles of CO formed per min per sq cm of the surface area of the melt. The amount of carbon formed by Reaction [2] was not determined. As already indicated the rfco is much higher than the rfC, by Reaction [2]. Since the rfC probably is proportional to the rfco, the measured rfco should then the proportional to, but slightly lower than, the total rate of Reactions [I] and 121. In general the scatter of results obtained in duplicate measurements was ±5 to 10 pct, while within a given run a precision of ±3 to 5 pct was obtained. The various crucible assemblies that were used will be described below. Measurements in Unstirred Melts. When carrying out aluminum electrolysis in small alumina crucibles. Tuset10 observed that after solidification the lower part of the electrolyte was gray and contained free metal, while the upper part near the anode was white and contained no metal. One may test for the presence of free metal by treating with dilute hydrochlorid acid.

Jan 1, 1969

By N. A. Gokcen, John Chipman

SILICON is the most commonly used deoxidizer and an important alloying element in steelmak-ing; hence a detailed study of this element in liquid iron containing oxygen is of considerable interest. The equilibrium between silicon and oxygen in liquid iron has been studied by a number of investigators but generally with inconclusive or incomplete results. The variation of the activity coefficients of silicon and oxygen with composition is entirely unknown. Published investigations deal with the reaction of dissolved oxygen with silicon in liquid iron and the results are expressed in terms of a deoxidation product. For consistency and convenience in comparison of the published information, the deoxidation product as referred to the following reaction is expressed in terms of the percentage by weight of silicon and oxygen in the melt in equilibrium with solid silica: SiO (s) = Si + 2 O; K'l = [% Si] [% 012 [I] Theoretical attempts to calculate the deoxidation constant for silicon in liquid iron from the free energies of various reactions yielded results which were invariably lower than the experimental values. Thus, the deoxidation "constants" calculated by McCance,1,2 Feild,3 Schenck, and Chipman were of the order of 10, which is below the experimental values by a factor of more than 10. Experiments of Herty and coworkers" in the laboratory and steel plant resulted in an average deoxidation constant of 0.82x10 ' at about 1600°C. The technique employed in their investigation was crude and the reported temperature was quite uncertain. The concentration of silicon was obtained by subtracting silicon in the inclusions from the total. Since at least some of the inclusions resulting from chilling must represent a fraction of the silicon in solution at high temperatures, such a subtraction is not justifiable. Results of Schenck4 for K'1 from acid open-hearth plant data yielded a value of 2.8x10-5, which was later revised as 1.24x10 at 1600°C. Similarly Schenck and Bruggemann7 obtained 1.76x10-5 at 1600OC. The discrepancies and errors involved in the acid open-hearth plant data as compared with the results of more reliable laboratory techniques were attributed by these authors to the lack of equilibrium and the impurities in liquid metal and slag, and are sufficiently discussed elsewhere." Korber and Oelsen" investigated the relation between dissolved oxygen and silicon in liquid iron covered with silica-saturated slags containing varying concentrations of MnO and FeO. The deoxidation products obtained by their method scatter considerably, and their chosen average values of 1.34x10, 3.6x10-5, and 10.6x10-5 1550°, 1600°, and 1650°C, respectively, represent the best experimental results which were available until quite recently. Darken's10 plant data from a steel bath agree approximately with their data at 1575° to 1625°C. Zapffe and Sims" investigated the reaction of H2O and H2 with liquid iron containing less than 1 pct Si and obtained deoxidation products varying by a factor of more than 20. Inadequate gas-metal contact and lack of stirring in the metal bath should require a longer period of time than the 1 to 5.5 hr which they allowed for the attainment of equilibrium. Furthermore, their oxygen analyses were incomplete and irregular and confined to a few unsatisfactory preliminary samples. Their results did indeed indicate that the activity coefficient of oxygen is decreased by the presence of silicon, although they made no such simple statement. They chose to attempt to account for their anomalous data by the unlikely hypothesis that SiO is dissolved in the melt. Hilty and Crafts" investigated the reaction of liquid iron with acid slags under an atmosphere of argon, making careful determinations of silicon and oxygen contents at several temperatures. Despite erroneous interpretation of the data at very low silicon concentrations, their data represent the most dependable information on this equilibrium that has been published. In the range 0.1 to 1.0 pct Si, their data yield the following values for the deoxidation product: 1.6x10-5, 3.0x10- ', and 5.3x10 at 1550°, 1600°, and 1650°C, respectively. The purpose of the work described herein was to study the equilibrium represented by eq 1 as well as the following reactions, all in the presence of solid silica: SiO2 (s) + 2H2 (g) = Si + 2H2O (g);

Jan 1, 1953

SELWYN G. BLAYLOCK, who has been awarded the Douglas medal for 1927 for his achievements in the production of electrolytic zinc and the treating of complex lead, zinc and silver ore at the Sullivan mine, British Columbia, is a Canadian and one of the notable men who have come from McGill Uni-versity, where he graduated in 1899. As the medal was founded in 1922 by a group of James Douglas' friends to honor the memory of that distinguished Canadian metallurgist, who was an honorary LL.D. of McGill, it is extremely appropriate that it should be awarded to another Canadian metallurgist and McGill graduate, who has been notably successful in practice. Immediately after gradua- tion Mr. Blaylock obtained a position as chemist at the Trail smelter and two years later was made chief chemist and metallurgist. In 1907 he became superintendent of the Hall mines smelter and after a year became superintendent of the St. Eugene mine at Moyie. While there he was responsible for the purchase of the Sullivan mine and the use of methods of mining, especially sorting, which so improved the relative per- - centages of zinc and lead in the ore as to make it better material for blast-furnace smelting. The losses in zinc, both from sorting out and in the lead blast-furnace slag made a deep impression on him, and various methods of water concentration and the use of air-jigs and flotation to increase the recovery were tried under Mr. Blaylock's supervision as early as 1910. These were followed by experiments with direct fusion, volatilization in kilns, sulfite processes, and one similar to the Ashcroft proc-ess. In 1914 experiments were made with roasting, leaching, and electrolyzing the resultant zinc sulfate solution; the following year a plant was built at Tadanac which has been in successful operation since 1916, its capacity having been increased by successive steps to 275 tons of zinc per day. Experimental work continued on the feed for the zinc plant and a 150-ton mill to use the Horwood process was constructed, but as the results were not encouraging it was altered to wet magnetic concentration, which was successful and the plant was later increased in capacity to 600 tons per day. Meanwhile experiments with differential flota-tion showed promise and magnetic concentration was continued while flotation was developed to where it could be put into operation parallel to the magnetic plant. This flotation plant, started in 1920, was so successful that eventually the magnetic separation plant was abandoned. Lead smelting conditions at Trail were difficult on account of the necessity of mak-ing slags containing as much as 20 per cent zinc and because of the high percentage of fine flotation con-centrate. The improvements in sintering and smelt-ing made under Mr. Blaylock's direction have been notable. The Betts electrolytic refining process for lead was first used at Trail, and the plant has been brought to its present highly developed and efficient state under Mr. Blaylock's direction. The first com-mercial Cottrell plant in connection with lead smelt-ing was also built there. The capacity of the Tada-nac plant is now approximately 750 tons per day of refined metal, including lead, zinc, copper, antimony, cad- mium, gold and silver. All the work necessary for this nota- ble development has neces- sarily been the work of many hands, directed by Mr. Blay- lock. In 1924 he was awarded the McCharles Medal by the University of Toronto for his achievements in con- nection with the production of electrolytic zinc and the solving of the difficulty of treating the complex lead- zinc-silver ore of the Sullivan mine, and developing it from a small producer to one of the most important mines of the world, now producing 150,000 tons of lead and 90,000 tons of zinc annually. Having spent all his professional life in one remote place, Mr. Blaylock is relatively little known per-sonally to others of his pro-fession, and the award indi-cates the truth in Emerson's well known epigram about the mouse-trap.

Jan 2, 1928

By C. Dalton, H. L. McGill

The purpose of this study was to develop a method for predicting the time delay created by metering a fluid through an annular restriction with translational motion of the boundaries. This time delay is utilized to control the opening of valves in various down-hole oilfield tools and forms the basis for the "hydraulic jar". The hydraulic jar is used to give upward impact forces to tubing or other tools that become lodged down-hole. The design of these jars has primarily been by trial and error; varying the clearances, fluid viscosities and dimensions of the jar until a satisfactory time delay was achieved. Obviously, a better understanding of the fluid flow characteristics is required to produce designs that are satisfactory and to eliminate the trial-and-error approach. Previous studies of flow in annular spaces were based on constant length of the annular restriction. Any motion of the boundaries of the annular space was confined to a rotational motion, like that encountered in journal bearing design. Consideration of the effect of translational motion of one boundary with respect to the other was necessary in applying this previous work to a time delay device. A prediction method was developed that takes into account this relative translational motion. Equations were developed to predict the relative velocity, the flow rate, and the time delay in a concentric annular space. The effect of eccentricity also was included. Experimental data were obtained and closely correlated with the prediction method. This correlation is presented graphically in terms of predicted and actual relative velocities for various annular clearances and pressure drops. This extension provides design equations which predict the performance of the hydraulic jar, thereby eliminating trial-and-error solutions and reducing the development time required for satisfactory designs. INTRODUCTION The design of down-hole oilfield tools which use hydraulic delay systems based on flow through annular orifices with relative motion of the boundaries is usually a trial-and-error process. The annular clearances, fluid viscosities and dimensions of the mechanisms were varied until satisfactory delay times were obtained. The development of these tools has been expensive, and a better understanding of the characteristics of annular flow with relative motion of the boundaries could result in superior and less expensive designs. The purpose of this investigation was to provide a method of predicting the performance of down-hole tools which use annular flow and, in particular, the performance of a down-hole tool known as the "hydraulic jar". The hydraulic jar is used to free pipe, packers and other tools that become lodged down-hole. The jar, located in the tubing string between the surface and the object which is stuck, releases the object though the repeated application of upward impact blows. The jar is basically a slip joint that is restrained in a collapsed condition until the desired tubing tension has been developed. The slip joint is then released and accelerates rapidly until it shoulders, delivering an impact blow or jar to the object. The delay obtained by metering the fluid through the annulus formed by the jar valve and housing provides the time delay necessary to stretch and apply tension to the tubing or pipe. Fig. 1A gives a schematic diagram of the hydraulic jar and brief details of its operation. The metering of the hydraulic jar begins when the tension force being applied to the jar by the pipe creates a pressure differential across the valve that is approximately equal to the force divided by the displacement area of the valve. This pressure differential induces flow through the annular restriction formed between the valve and housing. The valve moves with respect to the housing as the

Jan 1, 1969

By R. Schuhmann, E. J. Michal

Experimental measurements are reported for the oxygen pressures of iron-silicate slags in equilibrium with solid silica. CO2-CO mixtures were bubbled through the slags in silica crucibles to find equilibrium values of p co2/p co over the entire composition range of silica-saturated slags at 1250°, 1300°, and 1350°C. From the data, the activity vs. composition relationships were calculated for O, FeO, and Fe. SLAGS composed primarily of silica and iron oxides have particular practical importance in copper smelting,' in acid steelmaking, and in accounting for the service behavior of silica refractories. These slags all contain both ferrous and ferric iron, so that, strictly speaking, they are ternary or three-component liquid solutions. For convenience, the components may be taken as the three oxides, FeO, Fe2O3, and SiO2. The constitution of the FeO-Fe,O,-SiO, system at slagmaking temperatures has been studied in a recent investigation described in a separate paper.' This work showed the compositional ranges of iron-silicate melts at temperatures up to 1450°C and also the temperature-composition relationships for melts in equilibrium with various solid phases, including iron, wüstite, magnetite, and silica. Broadly speaking, the compositions of iron-silicate melts at a given temperature should be thought of as varying over a two-dimensional field. In the first place, the silica/total iron oxide relationship varies from maximum silica for silica-saturated melts to minimum silica for wüstite-saturated melts or, at higher temperatures, to zero silica for straight iron oxide melts. In copper smelting, for example, the converter slags approach the low silica limits while the reverberatory-furnace slags have intermediate silica contents, perhaps approaching silica saturation in some circumstances. Liquids formed in the pores of silica refractories presumably are close to silica saturation. The second type of composition variation is in the ferric/ferrous relationship, which depends on how oxidizing or how reducing the process conditions are. Relatively reducing slags, such as acid-steelmaking slags, are lower in ferric oxide and ap- proach saturation with metallic iron. Oxidized slags, such as copper-smelting slags, contain larger percentages of ferric oxides and approach or reach saturation with magnetite. Since these two kinds of compositional variations are closely related to two general properties of interest for all metallurgical slags, basicity, and oxidizing power, it is hoped that the thermodynamic study of iron-silicate slags eventually will throw further light on the significance and nature of these long-recognized but as yet poorly understood slag properties. Measurements of oxygen activity as a function of slag composition, using CO-CO2 gas mixture to fix oxygen activities, afford an experimentally convenient approach to the study of the thermodynamic properties of iron-silicate slags. In a preceding investigation,³ his approach was used in a systematic study of iron-silicate slags in equilibrium with solid iron. The present paper gives the results of a similar study of the iron-silicate slags in equilibrium with solid silica. The experimental work consisted in the determination of CO2: CO ratios in gas mixtures at equilibrium in the system: gas: liquid slag: silica Determinations were made at temperatures from 1250° to 1350°C for slags ranging in composition from iron saturation to magnetite saturation. Also, equilibrium CO,: CO ratios and slag compositions were determined for the univariant systems: gas: liquid slag: silica: iron gas: liquid slag: silica: magnetite Experimental Methods The experimental procedure was essentially the same as that used in the previous study of iron-silicate slags saturated with solid iron," but in order to work with the silica-saturated slags an all-silica crucible assembly was used. A liquid slag was prepared from pure prefused stock materials and brought to equilibrium with the silica crucible at the desired temperature. Then a mixture of CO2 and CO was continuously bubbled through the melt

Jan 1, 1953

By G. Baralis, P. Gondi, I. Tangerini, G. Scandola

The precipitation behavior of Zn-0.5 pct A1 alloy single crystals was studied by means of electrical resistivity measurements and by optical and electron microscopy. The single crystals for the resistivity measurements were prepared by an original method in - 100-p -thick sheets. The order of the precipitation kinetics ranged between 1 and 1.5. The dislocations play a relevant role in the first-order kinetics. Precipitation always occurs both on dispersed particles and on dislocations. Statistical examinations have shown that the first-order kinetics can have two different activation energies; i.e., the precipitation can have dz;fferent mechanisnrs which could not be identified, however, in the course of the research. During the tnetallographic exanzination of the precipitation structures a specific process of dislocation decoration was obsereed. The main purpose of this work was to study the contribution of dislocations to the precipitation. A number of authors have observed precipitation on dislocations and reference might be made to several monographs on the ubject.'' The possibility that dislocations also accelerate precipitation has been considered by Turn-bull3 and Fischer et al.4 The studies described in the present paper were carried out on zinc, chosen as a base metal owing to the ease with which dislocations can be introduced into it and because of the absence of excess vacancies after quenching in conditions where phenomena of accelerated precipitation still occur. Aluminum was preferred as alloying element because of the accelerated precipitation phenomena that resulted in a preliminary reearch. EXPERIMENTAL METHODS The observations refer to a Zn-0.5 pct A1 alloy. The zinc was 99.995 pct pure; a typical spectroscopical analysis is given in Table I. As a rule the alloy was subjected to homogenization, quenching, or slow cooling and annealing. Homogenization was carried out by heating at 390" to 410°C for 24 hr. From the homogenization temperature, some specimens were quenched and some slowly cooled at a rate of 2°C per sec. At this rate no precipitate was detectable under the optical microscope just after cooling. Quenching was carried out simply by dropping the specimens into water, aqueous ethylene glycol solution at -30" c, or liquid-nitrogen baths placed close to the homogenization oven. Vaseline oil baths were used with a thermal stabilization of 10-20 for both the aging treatments and the measurements; aging was generally carried out at 90" or 130°C. To avoid oxidation phenomena during heating, the vaseline oil baths had to be frequently renewed. The precipitation kinetics were studied by means of electrical resistivity measurements, using ans potentiometric method (reproducibility ± 5 x 10 5 v, that is 0.5 pct of the total voltage decreases on the specimens during precipitation). First, various types of specimens were tested, i.e., polycrystals, single crystals grown in capillary quartz tubes, and thin single-crystal sheets prepared by means of an original method requiring no container except for the natural oxide. Even if fully annealed, the polycrystals and the capillary grown single crystals showed resistivity in -creases, most probably due to dislocations introduced in the course of the measurements. Similar resistivity increases in pure zinc were noticed by another author. Only the single-crystal sheets showed no resistivity change; thus they were chosen for the subsequent tests. As already mentioned, these single crystals were obtained by using, as a container, the natural oxide on the zinc surface; the oxide strength is sufficient to maintain the original shape during melting with sheets up to 500 p thick. An initial zone melting and subsequent zone leveling, which led also to formation of the single crystals, were thus carried out on rolled sheets of the required thicknesses (- 100 p) and shape, lying on a flat silica surface. The resistivities were first evaluated by measurements at the liquid-nitrogen temperature. This method gave poor reproducibility, however, and this was attributed to the thermal cycles which had to be operated. To avoid cycles and handling, it was therefore decided to make measurements directly in the annealing oil baths; this required thermal stabilization at ilo-' "C. In this way only the resistance changes were measured. Specimens of pure zinc and of completely annealed alloy were always examined as controls together with those under consideration; only those measurement runs were taken into account where the reference samples showed no resistance increases. Again, the main inconvenience was due to oxidation and this was avoided by renewing the oil baths; even so data reproducibility was poor and the observations were therefore carried out on a large number (many hundreds) of specimens so as to provide indications of statistical value. For the transmission observations under the elec-

Jan 1, 1969

The design, specification, and performance evaluation of the Communications and Location portions of a Coal Mine Rescue and Survival System are described. The work was performed as part of a nine month effort to develop a mine rescue and survival system using existing technology and state -of-the -art hardware as recommended by the National Academy of Engineering. Three basic subsystems were developed, one for survival, one for communications/location and one for rescue. This report and related equipment manuals describe only the Communications/ Location Subsystem which was designed, fabricated, and tested by the Westinghouse Georesearch Laboratory in Boulder, Colorado. Two basic technologies were used. Electromagnetic signals propagating through-the-earth provide voice downlink and coded beacon up-link communications. Seismic methods were developed to provide means for locating trapped miners. Seismic signalling also provides a backup means for communications. Parallel development programs for the electromagnetic and seismic portions of the system were conducted. The resulting hardware and software have been partially tested in coal mines and under simulated emergency conditions in order to evaluate system performance. The results of these tests are discussed. Further testing is recommended in order to establish quantitative performance limitations tinder a variety of environmental conditions and to develop methods for improving system performance.

Jan 1, 1971

By Joseph Gersic

In 1989-90, the Bureau of Mines appraised selected high resource potential areas containing gold, rare-earth-element, or pegmatite deposits in or near the Black Hills National Forest. Available mineral resource data were used to construct mine and mill models and to compute discounted cash-flow rate-of-return analyses. Using this information, the economic feasibility of possible operations and probability (in the nonmathematical sense) of exploration and development within the next decade were assessed. High exploration and development probabilities are forecast for gold deposits around existing and permitted mine areas near Lead-Deadwood and west of Galena. The area east of Galena has low to moderate exploration and development probability; the Rochford area has low to high exploration probability and low to moderate development probability; the Keystone area has low to moderate exploration probability and low development probability; the Medicine Mountain area has moderate to high exploration and low to moderate development probabilities. Exploration probability in the Bear Lodge Mountains area is high for rare-earth elements and gold; development probability is low. Exploration probability for gold in the Mineral Hill area is low to moderate; development probability is low. The current level of activity associated with pegmatite mining in the Black Hills would probably not change significantly in the next decade; both exploration and development probabilities are low to moderate.

Jan 1, 1990

By H. W. Busch

In the course of examinations by representatives of the Bureau of Mines of several compressed-air systems in which explosions had occurred, samples were obtained of the carbon deposits that are formed normally in various parts of the systems by decomposition of the compressor lubricating oil. Experimentation with these carbon deposits has demonstrated that they contain a "carbon-oxygen complex" similar to that formed on coal and on other carbonaceous materials and generally recognized as being the cause of spontaneous heating of coal. The exothermic properties exhibited by such a complex are considered significant in relation to the possible initiation of combustion reactions that may lead to explosions or formation of carbon monoxide in compressed-air systems. This report discusses the occurrence of explosions and formation of carbon monoxide in the use of compressed air and presents results of experimentation conducted with carbon deposits from air compressors.

Jan 1, 1949

Dr Wark said: I have not come to Broken Hill to tell you how to conduct flotation operations; indeed, during my short stay here I have already learned much concerning the process, of the many difficulties which have been overcome, and of those still awaiting solution. My purpose tonight is rather different. All who have been concerned with the operation of the flotation process must have wondered, like myself, why the process is possible at all. In particular, why can minerals which are heavier than water be made to l10at to its surface; why do certain minerals float while others do not; and what are the functions of the added chemicals?I have been asked to describe tonight some of the ways which have been adopted in the Melbourne University laboratory in an endeavour to find answers to these. questions. Knowing that you are just as interested in them as we are and, furthermore, appreciating that were it not for the co-operation of the Broken Hill companies our researches would not have been possible, I regard it as a high privilege that I should have been invited to tell you of our work. Before doing so, I would like to tell you the reasons why the work was started and for whom it has been carried out. Soon after the flotation process had been successfully exploited on a commercial scale a number of investigators sought to determine the theoretical basis upon which it rests, and our knowledge of the function of the added chemicals has been considerably broadened by the published accounts of many workers, particularly in recent years of those working in American universities.The Australian metallurgist played, as you know, a part second to none in the early development of the process, and Australia's mining fields had already reaped such rich rewards from it that, late in 1929, it was felt by some of the leaders of the industry that we should take a larger part in the efforts being made to extend the knowledge of the principles upon which the process is based.Accordingly, several companies - the Broken Hill South, the North Broken Hill, The Zinc Corporation, the Electrolytic Zinc and the Mount Lyell Companies - established a laboratory in the chemistry department of the University of Melbourne for the purpose of investigating the principles underlying flotation.Subsequently another British company, the Burma Corporation Ltd, expressed a desire to co-operate.

Jan 1, 1994