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By Luis Elek

DEVELOPMENT of the cement industry in Mexico began some 40 years ago. It has gradually reached great importance in the economic life of the country and has contributed greatly to the technical and economical advances which have been so noteworthy, particularly during the last 15 years. From a modest start, the industry now comprises 18 cement-producing plants having a potential annual capacity of approximately 14 million bbl. About half the plants were built and equipped with secondhand machinery during the last world war when no new machinery could be procured. They will hardly attain full production before being modernized and reconditioned, a job now under way in several of the plants. At present, the yearly consumption is only about 8 to 9 million bbl but is steadily increasing. This is only a fraction of the cement consumed in the U.S.A., which is about 250 million bbl per year, although on the basis of consumption per capita per year, the figure is 1/3 bbl for Mexico and 1 2/3 bbl for the U.S.A. Cement consumption in Mexico is well above the average of all other Latin American countries, with the exception of the Argentine, and considering the potentialities and undeveloped riches of Mexico, the road construction and irrigation works, it is fair to assume that the Mexican cement industry will still prosper and expand in spite of temporary setbacks in the future caused by local events of economic or political nature. Portland cement is manufactured by burning a mixture of raw materials, one of which is mainly composed of calcium carbonates and the other of aluminum silicates. The most typical materials answering this description are limestone and clay, both of which occur in Mexico in many varieties. To be usable for cement manufacture limestone should contain at least 77 to 80 pct calcium carbonate. Lower grade limestone can be used for cement manufacture only if the lime content is increased by the beneficiation process, which has not yet been adopted by the Mexican cement industry. Most of the limestone used by Mexican cement plants has a calcium carbonate content of 90 to 95 pct and therefore requires addition of one or several correction materials. A typical composition of raw mix for cement manufacture is 85 pct limestone and 15 pct shale, clay or volcanic materials. Occasionally it is necessary to add a smaller amount of sand or other siliceous material to increase the silica ratio in the raw mix. Likewise, it is sometimes necessary to add 1 or 2 pct iron ore to facilitate fusion in the kiln and to obtain proper relation between alumina and iron oxide. After calcining and

Jan 1, 1953

By Luis Elek

DEVELOPMENT of the cement industry in Mexico began some 40 years ago. It has gradually reached great importance in the economic life of the country and has contributed greatly to the technical and economical advances which have been so noteworthy, particularly during the last 15 years. From a modest start, the industry now comprises 18 cement-producing plants having a potential annual capacity of approximately 14 million bbl. About half the plants were built and equipped with secondhand machinery during the last world war when no new machinery could be procured. They will hardly attain full production before being modernized and reconditioned, a job now under way in several of the plants. At present, the yearly consumption is only about 8 to 9 million bbl but is steadily increasing. This is only a fraction of the cement consumed in the U.S.A., which is about 250 million bbl per year, although on the basis of consumption per capita per year, the figure is 1/3 bbl for Mexico and 1 2/3 bbl for the U.S.A. Cement consumption in Mexico is well above the average of all other Latin American countries, with the exception of the Argentine, and considering the potentialities and undeveloped riches of Mexico, the road construction and irrigation works, it is fair to assume that the Mexican cement industry will still prosper and expand in spite of temporary setbacks in the future caused by local events of economic or political nature. Portland cement is manufactured by burning a mixture of raw materials, one of which is mainly composed of calcium carbonates and the other of aluminum silicates. The most typical materials answering this description are limestone and clay, both of which occur in Mexico in many varieties. To be usable for cement manufacture limestone should contain at least 77 to 80 pct calcium carbonate. Lower grade limestone can be used for cement manufacture only if the lime content is increased by the beneficiation process, which has not yet been adopted by the Mexican cement industry. Most of the limestone used by Mexican cement plants has a calcium carbonate content of 90 to 95 pct and therefore requires addition of one or several correction materials. A typical composition of raw mix for cement manufacture is 85 pct limestone and 15 pct shale, clay or volcanic materials. Occasionally it is necessary to add a smaller amount of sand or other siliceous material to increase the silica ratio in the raw mix. Likewise, it is sometimes necessary to add 1 or 2 pct iron ore to facilitate fusion in the kiln and to obtain proper relation between alumina and iron oxide. After calcining and

Jan 1, 1953

By R. F. Mehl, C. S. Barrett, A. G. Guy

INTRODUCTION IN the last few years this laboratory has published a series of papers on the mecha¬nism of age -hardening.14,1,6,11,20 Briefly stated it has been proposed that hardening is caused by lattice strains created by lat¬tice coherency between matrix and precipi¬tate; much experimental evidence has been advanced to support this thesis. The system Cu-Be is an attractive one to study. It is a system that exhibits marked age hardening; it ought to be subject to the type of analysis of structural changes hitherto explored and it is a prominent example of "discontinuous precipitation," which, though studied in other cases, 6,20 remains largely unexplained. This research shows that hardening in the Cu-Be system proceeds essentially as proposed earlier.14 Guinier-Preston zones have been observed to form on the {100) planes of the matrix; no transition lattice was found. Aging and overaging were ob¬served to occur most rapidly in the region of discontinuous precipitation-the grain boundary-apparently accelerated there by strain. The Constitution of the Cu-Be System The Cu-Be constitution diagram is shown in Fig I. The structure of the ? phase was determined by Misch16 as of the caesium-chloride type with a lattice con¬stant of 2.598 Å High temperature X ray photograms of 7.2 pct Be alloy made by Kossolapow and Trapesnikow13 led them to conclude that the structure of the P phase is simply disordered body-centered cubic with [ao] = 2.79 Å at 750°C. Previous Work The initial work on the age-hardening of Cu-Be alloys was that of Masing, Dahl, Holm, and Haase. Their numerous papers were published in book form in 1929, sub¬sequently translated.18 The effects of Be content, solution temperature, aging tem¬perature, and cold work on the hardness developed in these alloys were studied. An initial decrease in the electrical conduc¬tivity was observed when strips of a 2.5 pct Be alloy were aged at temperatures from 200 to 350°C; a wire of the same analysis failed to exhibit this decrease when aged at 350°C. A volume decrease of 0.6 pct oc¬curred during aging at 250°C. Microscopic investigations of quenched and aged alloys disclosed a regularly ori¬ented "striping" (ripples) on the a and on the ß grains. In the case of the ß the cause of the striping was held to be decomposition

Jan 1, 1948

By J. J. Gilman

WHEN a zinc crystal is immersed in liquid N, and then plastically bent, it is observed that it bends a certain amount and then fractures. This fracture occurs at a fairly reproducible radius of curvature, and the radius varies systematically with the crystal orientation. Because this phenomenon provides an unusually well-defined set of fracture conditions, it is possible to examine various possible fracture criteria and select the best one. Zinc crystals of various orientations were bent about axes lying in their glide planes (0001) and perpendicular to their glide directions [1210]. The crystals were 0.150 in. diam and had chemically polished surfaces. They were immersed in liquid N, while they were being loaded on an Instron testing machine. A three-point bending jig was used to load them. Table I lists the beam radius at which fracture occurred for each orientation. Each value is the average of at least six measurements. The normal stresses on the cleavage planes, at the time of fracture, were calculated as follows: First, from the fracture radius, R,, the orientation angle, x,, of the (0001) plane at the outer fiber was calculated. If x, = angle between the (0001) and the rod axis prior to bending, d = rod diameter, and X, = angle between the (0001) plane and a tangent to the bent crystal, then1 sinX, _ 2R, sin xn 2R, + d Since the glide shear strain is given by' y ' cot X, — Xo the glide strain at fracture, x,, can be calculated. Next, it is necessary to know the tangential stress in the outer fiber at fracture. This depends on the plastic flow curve, so a series of tensile tests were performed at —196°C on another set of zinc crystals. A curve of the average resolved shear stress versus glide strain was prepared. From this curve, shear stresses, r,, corresponding to the glide strains in the bend tests were taken. These values are listed in Table I. Then the normal stresses in the outer fibres, u,, were calculated from the relation U, = r, tan X, This analysis assumes that the fiber stresses in a bent beam are the same as the stresses in simple

Jan 1, 1959

By M. G. Corson

INFORMATION regarding the use of manganese alloys has hitherto been incomplete and available only from widely scattered sources. This paper attempts a systematic description of properties and uses of alloys other than manganese bronze, manganin and duralumin, which are probably the only non-ferrous alloys associated with manganese in the minds of most metallurgists.1 PROPERTIES OF MANGANESE Manganese can react either acid or basic; it is hard to obtain in the pure state; it has two different crystalline lattice structures, both of the cubic system, one stable above 850° C. and the other below 650° C., both coexisting in the intermediate range. Although the commercial product is hard and brittle, the pure metal seems to be ductile. In fact Zhemchuzhny, in Russia, was able to obtain ductile manganese and draw it to fine wires by the simple expedient of adding about 3 per cent. copper to the alumino-thermic product. Copper most probably brings the sili-cides, aluminides, nitrides and carbides present in the commercial product into a much less harmful form of distribution. One industrial use that can be foreseen for wrought manganese articles is as anodes for electrolytic processes in sulfate and nitrate solutions, particularly with high voltages. A practically insoluble skin of manganese peroxide is likely to form in such cases and an insoluble and strong anode material will be available.

Jan 5, 1927

By E. C. Reed

Oil was discovered in Nebraska on Nov. I, 1939, when the Pawnee Royalty Company's Boice No. I well, about 3 miles west of Falls City (NE 1/4 NE 1/4, sec. 18, T.r N., R.16 E., Richardson County) was drilled into the Hunton formation but the develop-ment of the area took place during 1940. After a pumping test lasting 18 days, the Boice well stopped producing and failed to qualify for the State bonus of $ 15,000 offered for the first oil well to produce go bbl. per day for 60 consecutive days. On May 9, 1940, the Pawnee Royalty Company's Bucholz No. I well was completed about M mile southeast of the discovery well and flowed at the rate of about 330 bbl. per day, easily meeting the State bonus requirements. In addition to the discovery well, which later was reconditioned, and the bonus well, 28 producers were drilled in the Falls City field during 1940. Of these wells, 23 are in sec. 20, two are in the northern part 'of sec. 29, two in the southwestern part of sec. 17 and three in the eastern part of sec.

Jan 1, 1941

By E. C. Reed

Oil was discovered in Nebraska on Nov. I, 1939, when the Pawnee Royalty Company's Boice No. I well, about 3 miles west of Falls City (NE 1/4 NE 1/4, sec. 18, T.r N., R.16 E., Richardson County) was drilled into the Hunton formation but the develop-ment of the area took place during 1940. After a pumping test lasting 18 days, the Boice well stopped producing and failed to qualify for the State bonus of $ 15,000 offered for the first oil well to produce go bbl. per day for 60 consecutive days. On May 9, 1940, the Pawnee Royalty Company's Bucholz No. I well was completed about M mile southeast of the discovery well and flowed at the rate of about 330 bbl. per day, easily meeting the State bonus requirements. In addition to the discovery well, which later was reconditioned, and the bonus well, 28 producers were drilled in the Falls City field during 1940. Of these wells, 23 are in sec. 20, two are in the northern part 'of sec. 29, two in the southwestern part of sec. 17 and three in the eastern part of sec.

Jan 1, 1941

By R. Ehrlich, F. E. Crane

A consolidated porous medium is mathematically modeled by networks of irregularly shaped, interconnected pore channels. Mechanisms are described that form residual saturations during immiscible displacement both by entire pore channels being bypassed and by fluids being isolated by the movement of an interface within individual pore channels. This latter mechanism is shown to depend strongly on pore channel irregularity. Together, these mechanisms provide an explanation for the drainage-imbibition-hysteresis effect. The calculation of steady-state relative permeabilities, based on a pore-size distribution obtained from a Berea sandstone, is described. These relative permeability curves agree qualitatively with curves that are generally accepted to be typical for highly consolidated materials. In situations where interfacial effects predominate over viscous and gravitational effects, the following conclusions are reached. 1. Relative permeability at a given saturation is everywhere independent of flow rate. 2. Relative permeability is independent of viscosity ratio everywhere except at very low values of wetting-phase relative permeability. 3. Irreducible wetting-phase saturation following steady-state drainage decreases with increasing ratio of nonwetting- to wetting-phase viscosity. 4. lrreducible wetting-phase saturation following unsteady-state drainage is lower than fir steady-state drainage. 5. Irreducible nonwetting-phase saturation 101lowing imbibition is independent of viscosity ratio, whether or not the imbibition is carried out under steady- or unsteady-state conditions. Experiments qualithtiveIy verify the conclusions regarding unsteady-state residual wetting-phase saturation. Implications of these conclusions are discussed. INTRODUCTION Natural and artificial porous materials are generally composed of matrix substance brought together in a more or less random manner. This leads to the creation of a network of interconnected pore spaces of highly irregular shape. Since the geometry of such a network is impossible to describe, we can never obtain a complete description of its flow behavior. We can, however, abstract those properties of the porous medium pertinent to the type of flow under consideration, and thus obtain an adequate description of that flow. Thus, the Kozeny-Carmen equation, by considering a porous medium as a bundle of noninterconnecting capillary tubes, provides an adequate description of single-phase flow. With the addition of a saturation-dependent tortuosity parameter in two-phase flow to account for flow path elongation, the Kozeny-Carmen equation has been used to predict relative permeabilities for the displacement of a wetting liquid by a gas. 1-5 It has long been recognized that relative permeability depends not only on saturation but also on saturation history as we11.6,7 Naar and Henderson8 described a mathematical model in which differences between drainage and imbibition behavior are explained in terms of a bypassing mechanism by which oil is trapped during imbibition. Fatt9 proposed a model for a porous medium that consisted of regular networks of cylindrical tubes of randomly distributed radii. From this he calculated the drainage relative permeability curves. Moore and slobod,10 Rose and Witherspoon,11 and Rose and Cleary12 each considered flow in a pore doublet (a parallel arrangement of a small and large diameter cylindrical capillary tube). They concluded that, because of the different rates of flow in each tube, trapping would occur in one of the tubes; the extent of which would depend upon viscosity ratio and capillary pressure. They limited

Jan 1, 1970

By F. W. Hillnhutter

In plant tests with a 9.7 m hearth diameter high top pressure blast furnace the influence of disintegration of sinter during low-temperature reduction on blast furnace performance was evaluated. The blast furnace burden during the test period consisted of 74% self-fluxing sinter with a basicity of CaO/Si02 = 1.3, 15% pellets, 6% lump ore, and 5% recirculated slags. The sinter for the test was produced in a modern sinter plant. By changing the fuel rate and/or the MgO content at a constant basicity CaO/Si02 sinters with different low-temperature disintegration properties could be produced. The blast furnace was equipped with pressure monitoring devices at medium height of the furnace stack wall. This device provided in addition to the normal operating data readings of pressure losses in the upper and lower part of the furnace. The basic physico-chemical factors determining low-temperature disintegration are explained. The testing devices and the extent of quality control measures of sinter during the test period are outlined. Conclusions are drawn from the plant test in relation to sinter properties.

Jan 1, 1977

By P. D. Rao, H. B. Charmbury, D. R. Mitchell

As a result of a changing market pattern for anthracite, there is now an increasing demand for steam size and a decreasing demand for domestic sizes. To help the producer meet this new demand, the authors present the technical aspects of the problem of crushing domestic sizes to steam fineness and size. The market pattern for anthracite coal has changed considerably in recent years. The demand for domestic sizes has been gradually decreasing and the demand for the steam sizes has been increasing. The companies however aim for a maximum production of domestic sizes, since these sizes command premium prices. To meet the market demands, particularly in certain periods of the year, further size reduction of the coarse clean coal is necessary. The present practice of multistage crushing in toothed rolls leads to complicated flow arrangements and is high in cost. Data presented herein indicate that crushers with high reduction ratios could be used with a resulting simplification of crushing flows and an appreciable reduction of capital and operating costs. The different types of crushing equipment investigated included the rotary-type breaker, the jaw crusher, the impactor-type crusher, and the Aerofall mill. CURRENT PRACTICE The standard sizes of anthracite are presented in Table I and market specifications require that any given size be maintained with only a limited amount of oversize and undersize material. The 1958 prices of the various sizes also are presented, so it may be seen that size reduction is only performed when dictated by market demands. At the present time the general practice of crushing anthracite consists of removing the top size and crushing it in a toothed double roll crusher to the next largest size. Consequently, to reduce the domestic egg, stove, and nut sizes to steam sizes of pea, buck, rice, and barley, the original material must be screened to produce the three top sizes and each size must be crushed in three separate rolls to the next largest size. Each crushed product must then be rescreened to remove the oversize for re crush ing. Thus a typical operation would consist of scalping the egg size from a mixture, crushing it to stove size, and rescreening the product. This same cycle would be repeated for the stove and nut sizes requiring three screens and three crushers as well as conveying equipment to handle the crushed products. This results in an expensive series of operations to make a product which sells for a lower price. If the three top sizes are crushed in one operation to the smaller sizes then the yield of steam sizes is low and the production of Nos. 4 and 5 sizes is large. These sizes sell for lower prices than the steam sizes. A typical operation is presented in Fig. 1. From the figure it may be seen that the original cleaned anthracite contains 67.4 pet domestic sizes, 26.4 pct steam sizes, and 6.2 pct fines. After multistage crushing of the domestic to steam sizes the composition of the product is 0.6 pct domestic sizes, 89.6 pct steam sizes, and 9.8 pct fines. From a technical standpoint these results are reasonable but the handling and crushing costs are

Jan 1, 1961

By D. I. Bardos, Paul A. Beck

The 1100°c isothermal, sections of the V-Fe-Si, V-Co-Si, and V-Ni-Si systems were studied at silicon contents between 0 and 40 at. pct. The single-phase fields in the 30 and 50 at. pct Mn sections of the 1100°C tetrahedron of the V-'Wn-Fe-Si system were also determined. The direction of extension of the elongated O, R, D, and a-Mn Phase fields suggests that the stability of these phases is determined largely by the electron concentration. The peculiar shape of the above ternary a phase fields, as well as of the a phase fields in the V-;Mn-Si and Cr-MTZ-Si systems is accounted for on the assumption that in manganese-(iron-, coball-, nickel-) rich alloys silicon atoms do not exclude d electrons , while in alloys low in the above components they do. This assumption also leads to the expected electronconcentrations for q and ß-Mn phases formed by transition metals with aluminurn. In earlier work it was shown that in ternary alloy systems of transition elements the a a and certain other phases with complex structure, such as the p and R phases,3 form elongated phase fields extending in a direction corresponding to a constant electron concentration. Recently similar behavior was observed in manganese-rich ternary ß-Mn solid solutions with another transition element and with silicon, germanium, or tin,4 confirming earlier indications3 that ß-Mn is also an electron phase. The alloying behavior of silicon in these manganese-rich alloys sug- gested that the four outside electrons of silicon participate in the bonding and that the predominantly d-like bonding electrons are not excluded from the silicon sites. Presumably, some of the normally unoccupied 3d states associated with the silicon atoms are in these alloys lowered to the Fermi level;4 thus silicon behaves as if it, too, were a transition element. The manganese-rich boundary of the a phase in the V-Mn-Si system,4 as well as in the Cr-Mn-Si sys-tem,4,5 extends approximately parallel to the ß-Mn phase boundary, corresponding to the transition ele-mentlike behavior of silicon described above. However, at lower manganese contents (i.e., in the high-vanadium or -chromium region) the a phase field in both ternary systems mentioned extends in a direction roughly perpendicular to that of its manganese-rich boundary, a phenomenon that is apparently inconsistent with the behavior of silicon in the manganese-rich alloys. A similar, although somewhat less pronounced, extension of the a phase occurs also in the high-vanadium (low-iron) region of the V-Fe-Si system at 1175C, but reportedly not in the V-Co-Si or V-Ni-Si systems at the same temperature.5 The present work was undertaken to investigate in more detail the extension of the a phase (as well as of other electron phases that may be present) in the last three systems and to elucidate this phenomenon, which has not been satisfactorily explained previously. EXPERIMENTAL PROCEDURES Most of the alloys were melted in an arc furnace, using a water-cooled copper crucible under helium atmosphere. The transition metals were of better than 99.9 pct purity and the silicon used was 99.98 pct pure. Alloys containing less than 20 pct V were induction-melted in recrystallized alumina crucibles under argon atmosphere.

Jan 1, 1967

Jan 1, 1888

By Paul F. Kerr, Donald M. Hausen

Fine colloidal gold near Carlin, Nevada is disseminated in leached carbonate strata of the Roberts Mountains Formation in the Lynn "window" of the Roberts Mountains thrust fault. The ore body is generally stratiform and is more or less conformable to altered beds near the top of the formation, underlying Devonian limestones. Two sequences of mineralization are recognized: ( 1) an earlier base metal-barite assemblage related to early Cretaceous intrusives (121 ± 5 m.y.), and (2) a later low temperature Au-As-Hg-Sb assemblage of near surface emplacement. The earlier sequence consisting of sparse galena and sphalerite in barite with anomalous amounts of zinc, lead, nickel and copper, associated with dikes of dacitic composition, is of little economic importance. The later sequence of gold, realgar, cinnabar, and stibnite associated with extensive silicification and argillic alteration of limestone beds, has resulted in important deposits of gold. Argillic alteration of hydrothermally leached carbonate strata has provided the environment in which the most prominent gold deposition took place. Carbonate minerals in the limestone host rock have been replaced by microcrystalline quartz and chalcedony to form stratiform silica masses and recrystallized lenses of euhedral quartz. Zones of porous silicification are light gray to white, elliptical in shape, and more or less follow bedding. Silicification is bordered by argillic alteration and pyritization. Deposition of gold usually lies in a zonal pattern that encircles chimney areas of silicification.

Jan 1, 1968

By C. H. P. Lupis, Henri Gaye

There are m -I conditions for the stability of a solution of m components with respect to infinitesinzal flucturations. However, in most cases, only one of these conditions has to be considered to determine the domain of instability and the existence of this more restrictive condition greatly simplifies the calculations. It may be used advantageously for the prediction of miscibility gaps and the method is illustrated in details for the case of the Ag-Pb-Zn system. THE thermodynamic conditions for the formation of a miscibility gap may be viewed as a necessary consequence of the conditions for spinodal decomposition. A previous article1 has examined in detail the form of these conditions for multicomponent systems. There is only one condition for the stability of a binary system (with respect to infinitesimal fluctuations), but there are two conditions for a ternary system, and m — 1 conditions for an m-component system. The probability of violating a stability condition, and thus forming a miscibility gap, obviously increases with the number of components, a result which is rather intuitive since the atoms of the solution have now many more ways of redistributing themselves and introducing complexities in the form of the free energy hy-persurface. It is of interest to take advantage of this possibility of precipitating new phases and to examine which stability condition is the likeliest to be violated, that is, which stability condition is thermodynamically the most restrictive. The finding of such a condition would greatly simplify the application of the stability criteria since only one condition could then be considered, instead of m - 1. In Ref. 1, coherency strain energy terms were neglected, thus restricting the applications of the treatment to solutions where they are negligible, such as liquid alloys. In the following study the same assumption will be made. To generalize the treatment to systems where the strain energy terms are sizable, the reader is referred to Cahn's classical article on spinodal decomposition.2 Let us designate by Gij the second derivative of the Gibbs free energy with respect to the number of moles ni and n j. There are several equivalent sets of m — 1 stability conditions.' The one considered here expresses that the successive diagonal determinants of order 1, 2, ... m — 1, associated with the symmetric Gij matrix (for 2 5 i, j 5 m) are positive.' For a binary solution 1-2, the condition for stability is: O(u=G22^0 [1] For a ternary system 1-2-3, the condition [I.] is re- tained (the value of G22 will differ, of course, according to the concentration of 3) and another condition is introduced: £>(21 = G22G33 - Gl3 ^ 0 [2] In a composition diagram, these two conditions define two domains of instability. Starting at a point where the solution is stable (for instance at a point where the solution is very dilute) we gradually change the composition until the condition [I] or [2] is violated. As already noted in the literature, e.g., in the work of Prigogine and Defay,3 it is the boundary of the domain (2) which is first crossed. For if we assume that the boundary of the domain (1) is reached first, at this point G22 = 0 and the second condition is necessarily violated (D(2) = -& 5 0), in contradiction with our original assumption. An exhaustive study of the ternary regular solution case may be found in the work of Meijering.4 Moreover if the boundaries of the two domains have a common point, they also have a common tangent. For if the two lines were to cross each other as is illustrated in Fig. 1(a) any point M in the line QP would be such that £> = 0 and 0"' > 0 which, as shown above, are incompatible results. Thus, the two lines must be tangent at their common point Q as illustrated in the example of Fig. l(b). The reasoning of Fig. l(a) implies that the point Q is not a "singular" point for either boundary line. This singularity may be of two types. First, the lines meet without crossing each other and without being tangent. Second, the tangent at Q for D"' or 0"' is not single-valued. Other types of singularity are unlikely because of the usual analytical forms of D"' and 0"'. The exception to the common tangent requirement due to the first type of singularity was pointed out by John Morral;5 it occurs when the common point, Q' or (3" in Fig. l(b), is located at a boundary of the composition diagram, e.g., at the line X3 = 0. It may also be noted that at the common nonsingular point Q of D(1) and D(2), Fig. 1(b), G23 is necessarily equal to zero, whereas at a point such as Q' or Q", this conclusion is no longer valid because the product G22G33 is now indefinite (of the form 0. a). The exception to the common tangent requirement due to the second type of singularity occurs when two branches of the same boundary line intersect, for example when D(1)or D(2) decomposes into a product of functions, at a point which belongs to the boundary of the other condition. It is possible to show by a simple analytical calculation that, in this case, if Q is a singular point of D(1), then it is necessarily a singular point of D(2), and that the reciprocal is true except if G33 = 0 at Q. For the present article, however, more elaboration on these singularities appears to be unwarranted. To generalize the previous results to an m -component system, we use the mathematical theorem stating that if the diagonal determinant D(r) = 0, then

Jan 1, 1970

By H. M. Davis, T. S. Jones

A methodfor accelerating the reduction of a metal oxide by carbon monoxide is to incorporate in the reduction system a nonreducible oxide which has a strong affinity for carbon dioxide and will remove it from the product gases. The effectiveness of this method was investigated by veduction experiments on specially prepared powder mixtures of SrO-ZnO ("active'.) and SrCO3-ZnO (reference). Measurements at 750o and 677°C showed that the rate of reduction of ZnO by CO was as much as an order of magnitude greater in the presence of SrO. Under the experimental conditions at least as much CO2 as generated by veduction was absorbed when SrO was present. Enlzancernent of the veduction rate by SvO resulted from modification of' gaseous djfitsion processes. THE specific question posed in this investigation was whether the reduction reaction CO + ZnO - Zn(g) + COa [1] could be accelerated by incorporating strontium oxide into the oxide charge undergoing reduction. Provided the strontium oxide was active enough, it could remove carbon dioxide from the product gases of ( 11 and form strontium carbonate, thus modifying Reaction [ 1] to CO + ZnO + SrO = Zn(g) + SrCO3 [ 2] This study of the comparative rates of Reactions [ I] and [2] can be considered as a particular case of a general scheme for increasing the rates of reduction of metal oxides by carbon monoxide. The limits of applicability of this scheme are indicated in the simple thermodynamic analysis presented in the appendix. This analysis primarily dictated the choice of the system, CO-ZnO-SrO, employed in this investigation. In addition, it was thought that a study of this scheme by use of the CO-ZnO-SrO reaction system would be of special interest in view of indications in the literature1-3 that the gaseous reduction of zinc oxide is prone to rate control by diffusion in the gas phase. The distinction should be pointed out between this and other efforts to increase the rates of reduction reactions through the use of addition agents. Additions of a wide range of chemicals have been tried with de- grees of apparent success varying from slightly negative to highly positive. The reasons for making additions have included the use of salts to produce effects akin to catalysis,4, 5 the alteration of the microstruc-tural details of the reduction process (including solid-state diffusion),6-8 and the conversion of an en-dothermic reaction into one that is exothermic or autogenous.9-12 The means used to attempt alteration of the enthalpy change has commonly been to incorporate lime into the charge, so that heat is generated by reaction with either of the reaction products, carbon dioxide or water. The use of lime in this way makes endeavors such as that of Edstrom and Wiberg similar to the present one. Furthermore, the basic principle behind the present work has previously been set forth.13 However, a detailed investigation of the type of reaction described in this work does not appear to have been conducted. EXPERIMENTAL PROCEDURE From both conceptual and physical standpoints, Reaction [2] is to be considered as the sum of two reactions:

Jan 1, 1968

By K. A. Pauly

(Wilkes-Barre Meeting, June, 1911.) COMPRESSED air has been and is still very extensively used in connection with mining-operations, but its application in the past has been almost entirely confined to supplying power to underground machinery. Its introduction was due to the difficulty of taking care of the steam which is exhausted underground, rather than to any advantage in efficiency to be gained by its use. The ease with which electric power may be carried to the remotest parts of the mine and the high efficiency of the electric motor have long been appreciated by mine-operators, and electric power is now extensively used underground in the more recent developments, while many of the compressed-air engines in the older workings are being rapidly replaced by electric motors. Recently, however, it has been suggested to use compressed air for driving the large shaft-hoists, the air for the engines being supplied by electrically-driven compressors, and an installation of this character is being erected at Butte; Mont. It is the object of this paper to compare the compressed-air system of hoisting with the various electrical systems, from the stand-points of first-cost and cost of operation. However, before entering into a discussion of the various systems, it will be well to consider briefly the conditions affecting the choice of a system of hoisting in which electricity is the ultimate source of power. The power required by a mine-hoist is extremely intermittent and fluctuates between very wide limits, the all-day average consumption of power not exceeding from 5 to 15 per cent. of the maximum demand during hoisting. The cost of supplying power for such a fluctuating load is necessarily higher than that for supplying an equal amount of

Dec 1, 1911

By Laurence Pellier

Electron microscopical studies were made of the effect of sensitization at 1200oF on a Type-.104 stainless steel with high carbon and low nitrogen and oxygen contents, after solution annealing and after cold working. The loci of the carbide precipitates in the early stages of sensitization were followed in dry stripped plastic replicas. Some observations were made by direct electron transmission on thinned films. Intragranular dislocations showed a high degree of stability through the annealing necessary to produce sensitization. I HE present work was undertaken to determine the effect of sensitization, at 1200°F, for 1/2 hr, on the electron microstructure of a Type-304 stainless steel with high carbon, and low nitrogen and oxygen contents, after solution annealing and after cold working. Many electron microscopical studies of sensitization of 18-8 stainless steels have already been made. Most of them utilized extraction replicas, from which the morphology and composition of the precipitated carbides could be established.'-" ry stripped replicas were seldom used for such studies, although it was demonstrated that they are applicable, in general, to EurveYs of the general microstructure of many alloys' and, in particular, to the observation of precipitated carbides in austenitic stainless steels.3

Jan 1, 1963

Page The Cobaltchromium Binary System (paper by A. R. Elsea, A. B. \Yesterman, and G. K. Manning, Met. Tech. June, 1948, Mechanism of Precipitation in a Permanent Magnet Alloy (paper by A. H. Geisler and J. B. Newkirk, Met. Tech. Aug. 1948, Tp 2444)................................................................................................. 300 Some Effects of Applied Stresses on Precipitation Phenomena (~aper by W. L. Finlay and W. R. Hibbard, Jr., Met. Tech. Sept. 1948, Tp 2470)....................................................................................... 301 Diffusion of Carbon in Austenite with a Discontinuity in Composition (paper by L. S. Darken, Met. Tech. Sept. 1948, TP 2443) 304 An Electron Diffraction Study of Oxide Films Formed on Nickelchromium Alloys (paper by J. W. Hickman and E. A. Gul- bramen, Met. Tech. June 1948, Tp 2372)..................................................................... 305 An Electron Diffraction Study of Oxide Films Formed on Copper-nickel Alloys at Elevated Temperatures (paper by J. W. Hickman and E. A. Gulbransen, Met. Tech. June 1948, TP 2391)................................................ 307 Decarburization of Chrome Nickel Alloys by Their Surface Oxides in High Vacua and at Elevated Temperatures (paper by E. A. Gulbransen, W. S. Wysong, and K. Andrew, Met. Tech. Sept. 1948, TP 2438)................................ 307 Fractographic Study of Cast Molybdenum (paper by C. A. Zapffe, F. K. Landgraf and C. 0. Worden, Met. Tech. Aug. 1948, TP 2421)................................................................................................. 308 Effect of Composition on Grain Growth in Aluminum-magnesium Solid Solutions (paper by L. J. Demer and P. A. Beck. Met. Tech. June 1948, TP 2374)............................................................................. 309 Effect of a Dispersed Phase on Grain Growth in Al-Mn Alloys (paper by P. A. Beck, M. L. Holzworth and P. Sperry, Met. Tech. Sept. 1948, TP 2475)................................................................................. 310 Statistical Rate Theory of Metals—Mechanism of Flow and Application to Tensile Properties (paper by J. W. Fredrickson and H. Eyring, Met. Tech. Aug. 1948, TP 2423)............................................................... 315 Nucleation of Slip Bands (paper by J. G. Leschen, R. P. Carreker, and J. H. Hollomon, Met. Tech. Sept. 1948, TP 2476) and.. 318 Transient Plastic Deformation (paper by R. P. Carreker, J. G. Leschen, and J. D. Lubahn, Met. Tech. Sept. 1948, TP 2477).. 318 Plastic Deformation of Large Grained Copper Specimens (paper by W. R. Hibbard, Jr., Met. Tech. Sept. 1948, TP 2469). ... 323 Plastic Flow in Anisotropic Sheet Steel (paper by L. R. Jackson, K. F. Smith, and W. T. Lankford, Met. Tech. Aug. 1948, TP 2440)................................................................................................. 323 The Effect of Thermal-mechanical History on the Strain Hardening of Metals (paper by J. E. Dorn, A. Goldberg, and T. E. Tietz, Met. Tech. Sept. l948, TP 2445)....................................................................... 325 The Room and Elevated Temperature Properties of Some Sand Cast Magnesium-base Alloys Containing Zinc (paper by T. E. Leontis, Met. Tech. June 1948, TP 2371)..............................................................., 327 The Low Temperature Properties of Tin and Tin-lead Alloys (paper by H. S. Kalish and F. J. Dunkerley, Met. Tech. Sept. 1948, TP 2442)............................................................................................335 Thermal and Electrical Properties of Ductile Titanium (paper by E. S. Greiner and W. C. Ellis, Met. Tech. Sept. 1948, TP 2466).................................................................................................... 335 Property Changes during Aging (paper by A. H. Geisler, Met. Tech. Aug. 1948, TP 2436)............................... 337 Factors Affecting the Tensile Notch Sensitivity of Magnesium Alloy Extrusions (paper by I. Cornet, Met. Tech. Aug. 1948, TP 2419)................................................................................................. 338 Effect of Grain Size on Tensile Strength, Elongation and Endurance Limit of Deep Drawing Brass (paper by H. L. Walker and W. J. Craig, Met. Tech. Sept. 1948, TP 2478)............................................................. 339 A Copper-base Alloy Containing Iron as a High-strength, Highconductivity Wire Material (paper by W. Hodge, R. I. Jaffee, J. G. Dunleavy, and H. R. Ogden, Met. Tech. Aug. 1948, TP 2422).............................................. 340 A High Strength-High Conductivity Copper-silver Alloy Wire (paper by W. Hodge, R. I. Jaffee, J. G. Dunleavy, and H. R. Ogden, Mel. Tech. June 1948, TP 2366)...................................................................... 340 The Effect of Chronlium on the Ma Point (paper by J. B. Bassett and E. S. Rowland, Met. Tech. Aug. 1948, TP 2417.... 341 The Kappa Eutectoid Transformation in the Copper-silicon System (paper by W. R. Hibbard, Jr., G. H. Eichelman, Jr., and W. P. Saunders, Met. Tech. Sept. 1948, TP 2441).............................................................. 343 Stabilization of the Ausknite-martensite Transformation (paper by W. R. Harris, Jr. and M. Cohen, Met. Tech. Sept. 1948, TP 2446)................................................................................................ 344 Secondary Hardening of Tempered Martensitic Alloy Steel (paper by W. Crafts and J. L. Lamont. Mel. Tech. Sept. 194,8, TP 2439)................................................................................................. 345

Jan 1, 1950

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

By Strathmore R. B. Cooke

On the basis of experiments conducted on quartz using a bubble pick-up method, it was shown in an earlier paper1 that this mineral will preferentially adsorb hydrogen, calcium, or sodium ions, depending on the relative concentrations of those ions in the solution in which the quartz is immersed. For quartz particles ranging in size from 0.2 to 1 mm, it was demonstrated that the concentration of calcium in solution (assumed present as ions) necessary to completely activate quartz for flotation is given by the expression: Ca++ = [H+] X 106 + [Na+] X 10-3 In this expression, ionic concentrations are in mols per liter. It was further shown that the pick-up method is apparently more sensitive to changes in reagent concentration than the standard captive-bubble method, and that induction times are apparently much reduced. Since completing these earlier tests, a new type of cell has been constructed; this is shown in Fig 1 and 2. In Fig 1, A is a ground joint, B is a central tube reaching to within a few millimeters of the bottom of the cell, and C is a stopper which may be removed for reagent addition, and serves the further purpose of excluding carbon dioxide from the air during the test. The entire cell is constructed of Pyrex glass, and does not give the trouble experienced with the earlier cell, in which activating ions were released from the glass at high pH values. The only critical factor in the construction of the cell is the clearance between the central tube and the bottom of the cell. This clearance should be sufficiently small that the bubble can be pressed directly on the mineral grains lying on the bottom of the cell. In the pick-up tests to be described in this paper, the reagents used were all of C. P. grade, except the sodium oleate, which was Merck's "neutral powder." The quartz employed was water-clear vein quartz, sized on screens, cleaned with both hydrochloric acid and sodium hydroxide, and given a thorough final washing with distilled water. Experimental procedures were the same as described in the earlier paper. EFFECT OF SIZE OF QUARTZ ON PICK-UP To ascertain the effect of particle size on the adsorption of calcium ions, the quartz was sized from minus 14 plus 20 mesh through the intervening screen sizes to minus 270 mesh plus 400 mesh. Each size was thoroughly cleaned, and then tested in the cell at different calcium chloride and sodium hydroxide concentrations, and at a constant sodium oleate concentration of 20 mg per liter. All particles, within the size range given, exhibited complete pick-up within the curve expressed by the equation above. This presumably means, when the conditions imposed by the equation are satisfied, that this maximum is independent of particle size. However, it was found that the range through which partial particle pick-up occurred progressively broadened as particle size decreased. This is shown in Fig 3, in which curves B, C, and D show the limits at which pick-up just commences (as the pH is increased) for particles of minus 14 plus 28 mesh, minus 65 plus 100 mesh, and minus 270 plus 400 mesh size, respectively. These results indicate that for satisfactory activation, at any given pH, a lower calcium ion concentration is required for fine particles than for coarse particles. EFFECT OF HIGH ALKALINITY ON PICK-UP At calcium concentrations of between 1 and 10 mg per liter, and at high alka-linities, it was noticed that pick-up ceased as soon as calcium hydroxide commenced to precipitate. This effect was investigated at other calcium concentrations, with the same results. Solutions of calcium chloride, containing 105, 104, l03, and l02 mg of calcium per liter were made alkaline with sodium hydroxide until calcium hydroxide just started to precipitate, according to the following equation: CaCl² + NaOH -+ Ca(OH)2 + 2NaCl The beginning of precipitation was taken as that point at which either a faint opalescence appeared in the solution, or a Tyndall cone became ap-

Jan 1, 1950