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By Arnulf Muan, Klaus Schwerdtfeger, L. S. Darken

The equilibrium ratios CO/CO, of. a gas pharse coexislitrg with selected oxide phase assemblages of the system "FeO"-MnO-SiO2 and metallic iron have been determined at 1150°C. The data obtained are combined wilh the thermodynamic data on fayalite (Fe2SiOi) and "FeO"-MnO solid solutions to derive the actiuity-coiHpQsiUon relations for the various oxide components of the olivine (Fe2SiO4-,lIn2Si04) and pyroxenoid (standard free energies of formation of ferrosilile (FeSiO,), tephroite , and rhodonite from their oxides have been evaluated. In the Appendicc~s by Darken and Schivcerdtjeger the ideal solution law for solid deri oed. THE quaternary system Fe-Mn-Si-0 is of interest in many important phases of iron- and steelmaking. For instance, reduction in the blast furnace of ores containing Fe-Mn silicates, deoxidation of liquid steel with Mn-Si alloys, formation and subsequent alterations of oxide inclusions in steels, and the oxidation of manganese- and silicon-containing steels during processing are all governed largely by the thermodynamic relations existing in the system Fe-Mn-Si-O. Although the equilibria between liquid iron and Fe-Mn silicates have been studied in detail previously,' experimental data are lacking for equilibria among the solid phases. The present paper provides such data for a selected temperature, 1150°C. I) PREVIOUS WORK The general feature of subsolidus phase relations in the system iron oxide-manganese oxide-silica under strongly reducing conditions is known.' Fig. 1 represents an isothermal section at 1150°C. The phases present, in addition to silica, are three solid-solution series, viz.. the oxide solid-solution series "Fe0"-MnO (manganowiistite), the orthosilicate solid-solution series Fe2SiO4-Mn2SiO4 (olivine), and the metasilicate solid-solution series FeSi03-MnSi03 (pyroxenoid). The "FeO"-MnO solid solution is continuous between the two end members wustite and manganositeV3 as is the orthosilicate series between the two end members Fe2SiO4 and Mn2 SiO4. 4 The metasilicate solid solution, on the other hand, extends only part way from the MnSi0.l end member toward FeSiO because the latter end member is unstable relative to the phase assemblage fayalite + silica. The letters a through m in Fig. 1 identify end members of the individual solid phases dealt with [for instance, c designates fayalite (FeZSiO4) in equilibrium with wustite, e designates fayalite in equilibrium with silica, and so forth]. In addition to the phase relations there are some thermodynamic data available for the end members of the silicate solid solutions and for the "FeO" -MnO solid solution. The free energy of formation of fayalite (Fe2Si04) from its oxide components has been studied by several investigators. Unfortunately, the data obtained show considerable discrepancies. According to recent tabulations by Kelley, the change in standard free energy Affn for the reaction

Jan 1, 1967

Arthur Yates, lecturer in the mining department of the Royal School of Mines, London, died at Blackpool, on Feb. 14, 1923, at the age of 47 years. My first acquaintance with him was made in 1902, when taking over the management of the Redjang Lebong gold mines in Sumatra, of which he was the responsible metallurgical officer. For that position he was well qualified by reason of his previous experience with the Rand Central Ore Reduction Co., in South Africa, and particularly by his early training with the Cassel Gold Extracting Co., owners of the MacArthur-Forrest patents, and the first commercial company formed to work the then recently discovered cyanide process; in this connection, Mr. Yates had the advantage of working under J. S. MacArthur himself. Our association in Sumatra was maintained for six years, when I left. Mr. Yates remained and was eventually promoted to the management of the neighboring Soelit mine. During those six years and in the close association inseparable from life in an isolated mining camp, the sterling qualities which made him so good a man were unmistakable: industry and interest in his work, patience with everybody, a quiet and unassuming demeanor. On the exhaustion of the mine to which he had been promoted, he returned to England in 1913. In 1914, the Mining Department of the Imperial College was fortunate in securing his services. Hardly, however, had he settled down when the war broke out and he spent some years in the Cleveland District promoting the efforts of the Government toward greater output. Returning to college in 1919, Mr. Yates met the full flood of Service students. The qualities which made him a man amongst men in the world made him a man among students in the college; a senior student if you like. But, unsuspected, a dread disease had fastened itself upon him, making itself felt for the first time during the summer course he was conducting in the South Wales coal field, in 1922. Against its relentless onset he opposed the bravest optimism, and when at last he realized that he was going under, and was in fact dying, his pronounced regret was that he was leaving the boys. In his death, at the age of forty-seven, staff and students in the Mining Department have experienced a great loss, that of a reliable friend, and their deepest sympathy goes out to the young widow and son in their irreparable loss. S. J. TRuBcott.

Jan 1, 1923

Arthur Yates, lecturer in the mining department of the Royal School of Mines, London, died at Blackpool, on Feb. 14, 1923, at the age of 47 years. My first acquaintance with him was made in 1902, when taking over the management of the Redjang Lebong gold mines in Sumatra, of which he was the responsible metallurgical officer. For that position he was well qualified by reason of his previous experience with the Rand Central Ore Reduction Co., in South Africa, and particularly by his early training with the Cassel Gold Extracting Co., owners of the MacArthur-Forrest patents, and the first commercial company formed to work the then recently discovered cyanide process; in this connection, Mr. Yates had the advantage of working under J. S. MacArthur himself. Our association in Sumatra was maintained for six years, when I left. Mr. Yates remained and was eventually promoted to the management of the neighboring Soelit mine. During those six years and in the close association inseparable from life in an isolated mining camp, the sterling qualities which made him so good a man were unmistakable: industry and interest in his work, patience with everybody, a quiet and unassuming demeanor. On the exhaustion of the mine to which he had been promoted, he returned to England in 1913. In 1914, the Mining Department of the Imperial College was fortunate in securing his services. Hardly, however, had he settled down when the war broke out and he spent some years in the Cleveland District promoting the efforts of the Government toward greater output. Returning to college in 1919, Mr. Yates met the full flood of Service students. The qualities which made him a man amongst men in the world made him a man among students in the college; a senior student if you like. But, unsuspected, a dread disease had fastened itself upon him, making itself felt for the first time during the summer course he was conducting in the South Wales coal field, in 1922. Against its relentless onset he opposed the bravest optimism, and when at last he realized that he was going under, and was in fact dying, his pronounced regret was that he was leaving the boys. In his death, at the age of forty-seven, staff and students in the Mining Department have experienced a great loss, that of a reliable friend, and their deepest sympathy goes out to the young widow and son in their irreparable loss. S. J. TRuBcott.

Jan 1, 1923

By Waldemar Lindgren

CONTENTS. [ ] I. INTRODUCTION. THE precious metals, gold and silver, are the basis of the monetary systems of the world. It is, therefore, natural and inevitable that widespread interest should be manifested in their production and in the various classes of deposits in which they are contained. At times a great scarcity of the precious metals has prevailed; at other times the production has seemed so abnormally large that fears have been entertained regarding their ultimate retention as standards of value. Since most nations have adopted the gold standard, and the remaining ones appear likely to do the same in the near future, the question of available supply of gold for the present and future very naturally arises. This necessarily involves a consideration of the characteristics of the gold-deposits. After the absorption of the gold treasures of the New World by the conquistadores, the gold-placers of Brazil and Russia

Jan 1, 1913

By Alden Greninger

IN a recent study1 of the deformation of metastable beta copper-zinc and beta copper-tin crystals, it was established that the parallel markings that appear on the surface of these crystals after slight deformation represent lattice transformations. Stereographic analysis showed that in beta copper-tin, the poles of these markings deviated one or two degrees from poles of the form { 133 } . In beta copper-zinc the plane delineated by the markings corresponded to no one crystallographic plane of the matrix lattice; the marking poles deviated from 5° to 11° from poles of the form {110}, and were displaced only a few degrees from (110) zones. Inasmuch as the new transition lattices produced as the result of the deformation are different for each alloy, it was thought at first that the habits of the markings might be the result of a cooperation between matrix lattice and transformed lattice. (Both matrix lattices are body-centered cubic.) Such a cooperative effect is thought to obtain in the formation of Widmanstätten figures, for it is well known that the matrix lattice alone does not determine the habit assumed by a segregate phase. On the other hand, it is not inconceivable that the dissimilarity in mark-ing habit might be due to differences in deformation characteristics of beta brass and beta bronze. Barrett and co-workers2 have shown that slip-line habits in pure iron are markedly different from those in high-silicon ferrite; and although it has been repeatedly demonstrated that plates of a segregate phase do not necessarily form on the slip planes of the matrix lattice, deformation characteristics may be more intimately allied with plate formation when a transformation is made to occur as a result of plastic deformation. However, there is the fact that the orienta-tion of markings in metastable beta copper-zinc is the same whether the markings be produced by quenching, deformation, or liquid-air cooling; likewise, quenching and deformation markings in metastable beta copper-tin are oriented in the same way with respect to the beta matrix.

Jan 1, 1938

By E. J. Efsic, C. M. Wayman

The fcc to bcc y to a transformation in an Fe-24.5 at. pct Pt alloy was studied and found to be martensitic. Large martensite plates are formed in this alloy which are ideal for crystallographic studies; the Ms temperature is about -5°C. Ordering of the parent phase prior to transformation to martensite causes a pronounced lowering of the Ms temperature. For the first time in the case of alloys of iron, measurements of the habit plune, orientation relationship, and magnitude and direction of the shape stvain have been obtained on preselected martensite plates. It is shown that by measuring the initial and displaced (as a result of the shape strain) positions of three or more non-parallel fiducial scratches on one reference surfice the maguitude and direction of the shape strain and the state of distovtion at the parent-mavtensite interface can be determined with a reasonable degree of accuvacy. The agreement between the phenomenolog-cal crystallographic theory of martensitic transformations and the experimental results habit plune, orientation relationship, and nlagnitude and direction of the shape strain) is essentially perfect, and is thought to be the best reported to date for iron alloys. THE comparatively few investigations on binary Fe-Pt alloys have been concerned with magnetic properties, ordered phases, and the equilibrium diagram itself. Various investigations have shown that the equilibrium diagram is of the open y field type; in addition there is a peritectic transformation, a minimum melting point, and three ordered phases: Fe3Pt, FePt, and FePt3. The results of a number of investigators1-6 have shown that the temperature dependence of the y to a (and reverse) transformation in iron-rich alloys is reasonably well-established. The Fe3Pt phase was first noted by Kussman and Rittberg,7 and its existence was later confirmed by Franklin et al,8 Steijn and Donahoe,9 and Berkowitz et al.10 The FePt phase was reported by Isaac and amman' and later confirmed by a host of others.3,6,7,12,13 Kussman and Rittberg7 noted the existence of the superlattice FePt3. Prior to 1956, the 1 to a transformation in iron-rich Fe-Pt alloys was termed "irreversible". In 1957 Klokholm and Donahoe" termed this transformation martensitic, presumably because of its occurrence at temperatures well below those where diffusion normally takes place. This observation served as a point of departure for the present investigation, and in the very early stages of the work to be discussed it was readily verified that the y to a transformation in iron-rich Fe-Pt alloys is indeed martensitic. Quite large martensite plates exhibiting the well-known surface tilt were observed. These plates are ideal in the sense that the boundaries between the parent and product phases were usually very straight. It thus appeared that Fe-Pt martensites would be ideal for crystallographic studies, and this was the purpose of the present investigation. Details of the crystallography of martensitic transformations (particularly for iron alloys) and the phe-nomenological crystallographic theories15-l7 have been discussed many times and thus will require very little elaboration here. The end result of these theories, given in matrix form, is

Jan 1, 1968

By Leroy U. Gardner

The human respiratory tract is an apparatus for the interchange of gases between the air and the blood. An important part of it are mechanisms to prevent the apparatus from becoming clogged with dust particles that are inhaled with the air. These mechanisms are adequate to protect the organ against most dusts, but silica and at least one of the silicates, asbestos, are tissue poisons which initiate changes in the connective tissues of the lung, incompatible with function. Silica is concentrated by the phagocytes in contact with the connective tissues of the lymphatic drainage system. An overgrowth of connective tissue occurs which interferes with the function of this system. More dust that may be inhaled can no longer be effectively eliminated from the lung. It accumulates in the functioning part of the organ and excites the formation of characteristic fibrous nodules and bands. These changes seriously impair the respiratory function. The shadows of such changes cast upon an X-ray film of the lung are discussed. The reaction to silica in the lung produces a marked increased susceptibility to tuberculous infection. It can be reproduced and studied in the experimental animal and has been observed repeatedly in human beings. Asbestos dust also causes fibrosis in the lungs but the mechanism of its development is different. The fibrous dust settles along the irregular walls of the terminal bronchioles. In this location it excites the formation of cuffs of scar tissue. This contracts and shuts down the tubes, resulting in a collapse of the air spaces distal to the obstruction. Such a condition in itself is a cause of fibrosis. The two causes, immediate reaction to the dust and collapse of the finer air spaces, bring about a generalized diffuse fibrosis. This reaction is not so regularly associated with increased susceptibility to tuberculosis as with silicosis. The case against sericite as a cause of silicosis has not been proved. Experimentally, sericite-free quartz will produce nodular fibrosis. Silicon carbide and aluminum oxide are quite inert in the normal animals. The former apparently increases susceptibility to tuberculosis in animals but whether the same is true in human beings awaits demonstration.

Jan 1, 1934

By P. Somasundaran

INTRODUCTION Large amounts of mineral values are discarded today as fines and ultrafines, because of inadequate technology to process them economically. Most conventional mineral processing techniques fail in the sub-sieve range. Fines respond poorly to processes such as flotation either due to change in mineralogy and surface composition or even simply due to the direct effect of their smallness in size on collision and adhesion rates between them and air bubbles. Indeed if the poor flotation is due to the smallness in size, a solution must rest in aggregating the fines. Inorganic electrolytes as well as polymers have been successfully used as flocculants in the past for obtaining increased flotation of colloidal material from waste water effluents. In mineral beneficiation, this technique can be profitably used if the process of flocculation can be made to take place selectively. The power of the selective flocculation technique has already been proven, with the successful application of it in the case of beneficiation of low grade iron ore by the Cleveland-Cliffs Iron Ore Company and potash ore by Cominco. The process holds tremendous potential when it is followed by flotation, elutriation, etc. Today its application is, however, limited to the above two cases and it has become clear that a full understanding of the process will prove helpful for developing solutions to various problems that exist both at the basic and applied levels. In this paper, principles that are known to govern selective aggregation processes such as selective flocculation, carrier flotation and spherical agglomeration will be examined and areas of uncertainties will be identified.

Jan 1, 1979

By J. B. Bassett, E. S. Rowland

The experimental work reported herein firas inspired by the publication of a paper by Grange and stewart, in which it was suggested that at low chromium contents the effect of this element on the Ma point was greater than at higher chromium contents, It was argued that, if a small increase of chromium in solution in austenite caused a sharp lowering of the M, point, it might lead to an explanation of occasional unsolved stress cracking of SAE 52100 during heat treatment. Commercial hardening is carried out at temperatures of incomplete solution, leaving carbides available to enrich the austenite during any inadvertent increase in temperature, such enrichment of the austenite in chromium content would lower the M, point nearer room temperature where cracking is more likely to occur. According, it was decided to investigate the effect of chromium, in quantities between o and 2 pet, on the M, point of commercial steels. Fig I summarizes the data available on chromium steels. For purposes of comparison, the M, temperature values were corrected by means of the Grange and Stewart formulas to (I) Hypoeutectoid compositions: 0.50 pct carbon and 0.80 pct manganese (z) Hsereutectoid compos-sition': 1." pet carbon and O.35 pct manganese. Only the steels having compositions reasonably close to these corrected values were included, because large adjustments inevitably introduce increased error such as are experienced in using the formula. The straight lines of Fig I were drawn by the authors. These data obviously do not settle the question Of the effect Of chromium On the Md Oint, particularly at low chromium contents. While it is fairly well established that chromium causes the M, to be lowered when present in quantities of I pet Or more, Grange and Stewart1 have suggested that in small amounts (less than 1 pet) it is more effective in lowering the Ma point, while Klier and Troiano2 have suggested that in small amounts it is less effective in lowering the Ma point. Payson and Savage3 concur with Klier and Troiano and further suggest that the effect is not linear at these concentrations. Rose and Fischer4 report that small amounts of chromium actually raise the Ma point of a 0.20 carbon steel. Material Two series of 35 Ib induction heats were melted for this work, the analyses of which are given in Table I. One series was aimed at 0.50 pct carbon and 0.80 pct manganese with chromium additions in 0,25 pet increments from o to 1.5 pct with a single heat at 2.0 pct Cr. This series was considered necessary because the commercial heat treatment of SAE 52100 does not generally introduce more than about 0.60 pct carbon in solution in the austenite. The high

Jan 1, 1949

By J. B. Bassett, E. S. Rowland

INTRODUCTION THE experimental work reported herein was inspired by the publication of a paper by Grange and Stewart,1 in which it was suggested that at low chromium contents the effect of this element on the [M,] point was greater than at higher chromium contents. It was argued that, if a small increase of chromium in solution in austenite caused a sharp lowering of the [M,] point, it might lead to an explanation of occasional unsolved stress cracking of SAE 52100 during heat treatment. Commercial hardening is carried out at temperatures of incomplete solution, leaving carbides available to enrich the austenite during any inadvertent increase in temperature. Such enrichment of the austenite in chromium content would lower the [ M,] point nearer room temperature where cracking is more likely to occur. Accordingly, it was decided to investigate the effect of chromium, in quantities between o and 2 pct, on the[ M,] point of commercial steels. Fig I summarizes the data available on chromium steels. For purposes of comparison, the [M, ] temperature values were corrected by means of the Grange and Stewart formula§ to (I) Hypoeutectoid compositions: 0.50 pct carbon and 0.80 pct manganese (2) Hypereutectoid compositions: 1.00 pct carbon and 0.35 pct manganese. Only the steels having compositions reasonably close to these corrected values were included, because large adjustments inevitably introduce increased errors such as are experienced in using the formula. The straight lines of Fig I were drawn by the authors. These data obviously do not settle the question of the effect of chromium on the [M,] point, particularly at low chromium contents. While it is fairly well established that chromium causes the [M,] to be lowered when present in quantities of I pct or more, Grange and Stewart1 have suggested that in small amounts (less than I. pct) it is more effective in lowering the[ M,] point, while Klier and Troiano2 have suggested that in small amounts it is less effective in lowering the []M,] point. Payson and Savage3 concur with Klier and Troiano and further suggest that the effect is not linear at these concentrations. Rose and Fischer4 report that small amounts of chromium actually raise the-[M,] point of a 0.20 carbon steel. MATERIAL Two series of 35 lb induction heats were melted for this work, the analyses of which are given in Table I. One series was aimed at 0.50 pct carbon and 0.80 pct manganese with chromium additions in 0.25 pct increments from o to 1.5 pct with a single heat at 2.0 pct Cr. This series was considered necessary because the commercial heat treatment of SAE 52100 does not generally introduce more than about 0.60 pct carbon in solution in the austenite. The high

Jan 1, 1948

By N. H. van Lingen

A laboratory stud], has been made to determine what factors affect the penetration rate of roller bits, diamond bits and drag bits in rock drilling with clay /water muds. The rather simple relations that exist when pressures in and around the borehole are equal become more conzplicated when under down-hole conditions the penetration rate is hampered by the existence of a pressure differential between the mud at the hole bottom and the pore liquid at cutting depth. Expressions that have been derived for both the penetration rate and the magnitude of the pressure differential in permeable rock together fully account for operating, rock, mud and bit variables. In impermeable rock a similar pressure differential is caused by the bit action itself. In all cases, the pressure difierential and the reduction in penetration rate increase with the effectiveness of the plastering at the bottom of the hole by mud particles. Where bits are employed whose action is largely that of crushing, however, the plastering may become even more effective owing to the addition of rock particles rubbed into the pores of the rock. With roller bits, a plastically hehaving layer may be formed, which causes a further reduction in penetration. In the case of bits whose action is chiefly scraping, moreover, penetration may be arrested by the bit's becoming balled-up. The various adverse effects are reduced by thorough scavenging of the hole bottom. This paper shows how with jet bits the efficiency of such scavenging may he improved by suitable choice of the position of the nozzles. INTRODUCTION The reduction in a bit's penetration rate with increasing depth of hole has been the subject of many investigations. Various investigators ',' have independently reached the conclusion that this reduction occurs not so much because the rock-breaking process becomes more difficult as it does because the lifting of the rock fragments is impaired by a fluid pressure differential holding the fragments down. When such a pressure differential can be avoided, as in air drilling and to a smaller extent in water drilling, penetration rates remain high. Although the range of applicability of these techniques is being extended, most oil wells still have to be drilled with mud. In this paper we present the results of laboratory experiments carried out to determine what factors govern the hold down effect encountered in mud drilling. In the course of this investigation, the well known importance of bottom scavenging came more and more into prominence. Not only may it reduce the magnitude of the hold-down forces, but also it appeared to be a means of preventing the accumulation of a plastic mass of cuttings and mud on the hole bottom and bit which may cause penetration to cease almost completely. So that the effects of fluid pressures may be more readily understood, the factors that govern penetration rate in the absence of these pressures will first be discussed. The effect of down-hole pressures will then be assessed for the case of permeable rock where fluid pressures are well defined, and it will be demonstrated how rock strengthening due to confining can be accounted for. Subsequently, fluid pressures in less-permeable rock will be examined; we will show that in impermeable rock it is the bit action that governs fluid-pressure distribution and hold-down. In the case of poor scavenging and/or high bit load. cutting cake manifests itself. The effect, like various others. appears to depend on the type of bit used. From the very beginning, therefore, we shall base our discussion on the three main types of bits used in rotary oil-well drilling— roller bits, diamond bits and drag bits. Since space is limited, it will be impossible to make more than a passing reference to many aspects of the problem. Moreover. certain relations that are not of primary irnportance to our argument will unavoidably have to be stated in a somewhat dogmatic fashion, and the experimental data on which these are based necessarily must be omitted. EQUIPMENT The drilling experiments were performed on three machines, of which one has been designed for the realistic simulation of down-hole pressure conditions. HIGH-PRESSURES MACHINE In this machine (diagramed in Fig. 1) the mud, pore and confining pressures can all be adjusted independently. The foil-covered rock sample contained in the inner pressure vessel is confined by oil that is pressurized by means of a hand pump. The pore space of the watersaturated sample is connected to an arrangement which keeps the pressure in the pore space constant regardless of the rate of filtrate flow through the sample.

By John C. Calhoun, R. C. Newman

A report is made of experimental work performed on the capillary retention of water within porous solid systems, the displacement being accomplished with air and various organic liquids. A portion of the experiments were designed to measure the lowering of vapor pressure of water within a porous solid with subsequent conversion of such vapor pressure data to capillary pressure values. The form of the capillary pressure curve at high capillary pressures has been elucidated from this data. Certain theoretical approaches are presented to indicate the correlation between work done by previous investigators. The present work is correlated also with theory. Surface area values are calculated for the various core systems studied. INTRODUCTION Leverettl in 1941 presented a paper which gave the essential concepts of capillary behavior in porous solids. His presentation included both theoretical and experimental aspects of the problem. He defined the term "capillary pressure" and applied it to an ideal porous system. His work included the definition of a dimensionless quantity which was a function of fluid saturation and which could be correlated with porosity and permeability for clean, unconsolidated sands. His experimental work was performed by the drainage of water from packed columns of unconsolidated sands. Subsequently, other authors have presented experimental techniques which permit the determination of capillary pressure data on small core samples. Data have been presented on porous systems other than unconsolidated sand and with the use of liquids other than water. Notable among these are the works of Hassler, Brunner and Deahl,2 Bruce and Welge,³ Amyx and Yuster, and Purcell. Others have indicated the applicability of such data to field problems without regard to the theoretical aspects of the capillary pressure saturation function. Within the recent published literature there have also been reported studies of the correlations between capillary pressure data and other fundamental properties of porous solids. It was the intent of the present reported work to investigate the behavior noted by water and various other liquids within porous systems in an attempt to amplify existing correlations between capillary properties, surface properties, and other fundamental characteristics of porous systems. The experimental work described here was performed as two different investigations but due to its nature it is reported as separate phases of the same general topic. CAPILLARY PRESSURE AND VAPOR PRESSURE LOWERING It has long been recognized that the vapor pressure above the curved surface of a liquid is a function of the curvature of the liquid surface." The capillary pressure is also a function of the curvature of the liquid surface. Both capillary pressure values and vapor pressure lowering are, therefore, functions of the liquid saturation of a porous solid. A quantitative relationship between the vapor pressure lowering and the capillary pressure can be simply developed by considering a porous solid system containing water in equilibrium with its vapor. The capillary pressure at any height within the system is defined as Pc= Pv -P1.......(1) where PI is the pressure in the vapor phase and PI is the pressure in the liquid phase. Consider that both the water and its vapor are continuous phases within the system and that at any point the two phases are in equilibrium. The gradients in the liquid and vapor columns within the porous system are: PI = plgdh dPv = pvgdh By integrating these gradients from the point where h = 0 to the height h, values of PI and PI at the point h are found. Let the point where h = 0 be that where Pc = 0. At this point also Pv is equal to Pve, the equilibrium vapor pressure of the liquid above a flat surface. From the first of these integrations since p is independent of height: P = p1gh + P, From the second, by substituting pv = PvM/RT, where M is the molecular RT weight: Pv M Pvo- RT gh By combining the two last equations to eliminate h, one obtains: P1 RT Pv Substituting, values for Pv and Pi in equation (1) gives PyRT RT Pv which is approximately Pc=RT/Mp1 In Pvo/Pv .......(2) This equation relates the vapor pressure above a curved surface with the capillary pressure across the curved surface in terms of measurable quantities. The equivalent of this equation is given by Freundlich."

Jan 1, 1949

By John C. Calhoun, R. C. Newman

A report is made of experimental work performed on the capillary retention of water within porous solid systems, the displacement being accomplished with air and various organic liquids. A portion of the experiments were designed to measure the lowering of vapor pressure of water within a porous solid with subsequent conversion of such vapor pressure data to capillary pressure values. The form of the capillary pressure curve at high capillary pressures has been elucidated from this data. Certain theoretical approaches are presented to indicate the correlation between work done by previous investigators. The present work is correlated also with theory. Surface area values are calculated for the various core systems studied. INTRODUCTION Leverettl in 1941 presented a paper which gave the essential concepts of capillary behavior in porous solids. His presentation included both theoretical and experimental aspects of the problem. He defined the term "capillary pressure" and applied it to an ideal porous system. His work included the definition of a dimensionless quantity which was a function of fluid saturation and which could be correlated with porosity and permeability for clean, unconsolidated sands. His experimental work was performed by the drainage of water from packed columns of unconsolidated sands. Subsequently, other authors have presented experimental techniques which permit the determination of capillary pressure data on small core samples. Data have been presented on porous systems other than unconsolidated sand and with the use of liquids other than water. Notable among these are the works of Hassler, Brunner and Deahl,2 Bruce and Welge,³ Amyx and Yuster, and Purcell. Others have indicated the applicability of such data to field problems without regard to the theoretical aspects of the capillary pressure saturation function. Within the recent published literature there have also been reported studies of the correlations between capillary pressure data and other fundamental properties of porous solids. It was the intent of the present reported work to investigate the behavior noted by water and various other liquids within porous systems in an attempt to amplify existing correlations between capillary properties, surface properties, and other fundamental characteristics of porous systems. The experimental work described here was performed as two different investigations but due to its nature it is reported as separate phases of the same general topic. CAPILLARY PRESSURE AND VAPOR PRESSURE LOWERING It has long been recognized that the vapor pressure above the curved surface of a liquid is a function of the curvature of the liquid surface." The capillary pressure is also a function of the curvature of the liquid surface. Both capillary pressure values and vapor pressure lowering are, therefore, functions of the liquid saturation of a porous solid. A quantitative relationship between the vapor pressure lowering and the capillary pressure can be simply developed by considering a porous solid system containing water in equilibrium with its vapor. The capillary pressure at any height within the system is defined as Pc= Pv -P1.......(1) where PI is the pressure in the vapor phase and PI is the pressure in the liquid phase. Consider that both the water and its vapor are continuous phases within the system and that at any point the two phases are in equilibrium. The gradients in the liquid and vapor columns within the porous system are: PI = plgdh dPv = pvgdh By integrating these gradients from the point where h = 0 to the height h, values of PI and PI at the point h are found. Let the point where h = 0 be that where Pc = 0. At this point also Pv is equal to Pve, the equilibrium vapor pressure of the liquid above a flat surface. From the first of these integrations since p is independent of height: P = p1gh + P, From the second, by substituting pv = PvM/RT, where M is the molecular RT weight: Pv M Pvo- RT gh By combining the two last equations to eliminate h, one obtains: P1 RT Pv Substituting, values for Pv and Pi in equation (1) gives PyRT RT Pv which is approximately Pc=RT/Mp1 In Pvo/Pv .......(2) This equation relates the vapor pressure above a curved surface with the capillary pressure across the curved surface in terms of measurable quantities. The equivalent of this equation is given by Freundlich."

Jan 1, 1949

By H. E. Lee, D. Ingvoldstad

AT Bunker Hill the original charge storage and preparation system was installed in 1917 to accommodate lead-silver gravity mill products. Only minor tonnages of wet fines such as vanner and flotation concentrates were received. Charge flux and diluent requirements were provided by an ample supply of siderite middlings and coarse lime-rock. While oversize material was crushed through %-in., the use of roll crushers in series resulted in a more or less granular, free-running charge of adequate porosity. Under such conditions, receipts could be proportioned directly from receiving bins, and suitable blending was obtained by passing the resultant layered composite through a small Stedman disintegrator. This elementary system served well for production and smelting of an extremely lead-rich sinter, in the low column blast furnace. Here sinter physical quality is less critical, and appreciable quantities of raw flux and oxidized ore may be charged directly to the blast furnace without seriously impairing furnace capacity. Prior to 1938 the relative proportions of zinc receipts were low and extraneous flux requirements at a minimum. However, subsequent war-inflated zinc demands brought marked increase in fine concentrate and slimy zinc leach residue receipts and an abrupt introduction to smelting a more refractory zinciferous charge. The higher temperature demands of the more refractory zinciferous charge required a higher smelting column and the higher column, in turn, rendered the blast furnace less receptive to improperly prepared feed. Inadequate presinter processing facilities prevented the production of acceptable sinter, and blast furnace production declined to 50 pct of former capacity. In view of a prevailing contention among lead metallurgists as to the deleterious action of high zinc slag on blast furnace capacity, it was natural to overstress this factor and to concentrate on possible changes in furnace design. Another interpretation was that primary correction should be sought through expanded sintering facilities. This divergence of opinion, together with the extreme material shortages of the 1940's, delayed corrective

Jan 1, 1957

By Herbert Dumont

Since 1947 Preussag AG Metal1 has used a process for fuming zinc- and lead-containing dump slags and residues from vertical retorts in a half-shaft furnace at their Hüttenwerk Harz at Oker. Contrary to the classic shaft furnace, only one side of the half-shaft furnace is fitted with tuyeres. The opposite side is a bricked slope. The upper shaft section is piped. There zinc vapor and combustion gases are burned by sucked-in air. Gases and fume enter a boiler located on the rear length of the furnace via a piped fire bridge. The gases are then cooled in an air preheater prior to dedusting in a bag filter. The furnace is charged with briquettes of metal-bearing materials, coal and pitch. The leaded zinc oxide fume is comparatively rich in both lead and zinc. The copper in the feed is recovered in low-copper matte. The slag can be discarded. The Oker plant comprises 13 furnaces of 2.9 to 4.9 m length in the tuyere area. Two other plants in Italy and Spain are processing zinc leach residues by this technique. Fuming of zinc-lead-oxide ores as well as partially roasted sulfide- zinc-lead-copper bulk concentrates will be possible.

Jan 1, 1970

By Ian W. Wark, Keith L. Sutherland

IT has been shown' that in the absence of heavy metal salts, the nature of the alkali used to promote differential flotation-whether caustic soda, lime or sodium carbonate-is unimportant. The hydroxyl ion is the active depressant upon which differentiation depends, and the pH value determines whether a film of collector forms on any given mineral surface. Even when sodium cyanide is used in conjunction with alkalies, it is the pH value and not the nature of the alkali or its concentration that is important, for upon the pH value alone depends the fraction of the added sodium cyanide that is present as cyanide ion, which is the true depressant. When heavy metal salts become dissolved from partly oxidized ores, or are added intentionally as activators, conditions are different, and metallurgists have found that lime and sodium carbonate do not give identical results, even when added in amounts sufficient to produce the same pH value. In the few instances in which we had attempted to confirm this view, we had failed to do so, for, with nothing to guide us, we had inadvertently chosen solutions that gave contact curves of a "standard type," which correspond to conditions of ready floatability. Now, however, we find that, in the presence of copper salts, and within a restricted range of reagent concentrations, the nature of the anions present is important, and that sodium carbonate does influence the results, apart from the usual effect due to its influence on pH value. With the recognition of this anion effect, and with the control of temperature already introduced,2 it appears that the factors of major importance in connection with this set of reagents have been taken into consideration, and that the results obtained and the conclusions drawn from contact tests will be of more immediate value to the operator. It is not difficult to suggest an explanation for the influence of the carbonate ion in the presence of copper sulphate. The works of Picker-

Jan 1, 1939

As far as rapid determination of oxygen in liquid steel by means of a galvanic cell is concerned, I should like to summarize in a few words the activities of Centre de Recherches Metallurgigues (CRM) in Belgium. This work has been conducted both in a laboratory (Tammann and Induction furnaces) as well as on an industrial scale (converter and ladle). The galvanic cells developed by CRM are of two kinds: one with an air reference and one with a solid reference. As far as galvanic cells with air reference are concerned, we have tested numerous solid electrolytes (zirconia, spinel, and alumina). We finally chose zirconia sheathed with quartz. In order to be in a position to accurately determine the time when thermal equilibrium is reached, it was deemed useful to fit the galvanic cell with a Pt/Pt, Rh thermocouple, so as to follow the temperature variations at the interface of the solid electrolyte, until the temperature becomes equal to that of the bath. In actual fact the solution is highly interesting since it is possible to determine both the oxygen activity and the temperature of the bath with a single cell.

Jan 1, 1972

By Ursula E. Wolff

The precipitation of carbides from an alloy containing 33 pct Ni, 21 pct Cr, balance iron, was investigated electron microscopically by means of extraction replicas and thinned metal foils. Annealing temperatures ranged from 565°to 870°C and up to several thousand hours. M23C6 precipitated in pain boundaries, incoherent and coherent twin boundaries in that sequence. The orientation relationship between carbides and austenite matrix was determined and correlated with the morphology of the carbides and with the type of boundary in which precipitation occurred. In large-angle grain boundaries, as well as in coherent twin boundaries, the carbides had the same orientation as one of the adjacent pains. These carbides formed sheets of individual flakes with shapes related to the orientation of the boundary. In incoherent twin boundaries carbides precipitated in ribbons composed of pavallel rods. An unidentified subcarbide was found to precede precipitation of M23C6 in these boundaries. The M 23 C6 rods had a kind of fiber texture with (110) parallel to the long dimension of the rods and ribbon, and with orientations of both of the adjacent twin-related austenite crystals Predominant in the texture of the carbide. A hard sphere crystal model has been used to discuss orientation and morphology of the carbides in terms of free volume and vacancies available in the boundaries. A number of papers have dealt with the morphology of chromium carbide (M23 C6) precipitated in austenitic stainless steels.1"7 In all these investigations, the carbides were examined in the electron microscope by means of extraction replicas. With this technique, the carbides retain the spatial distribution they had in the bulk sample. However, since the matrix is dissolved in the process, the particles can turn in an unpredictable way; and the orientation relationship between matrix and carbides cannot be established. In this paper the results of studies on extraction replicas and on thinned metal foils are reported. These studies were undertaken to determine the matrix-to-car bide orientation relationship, and to correlate the orientation of the carbides with their morphology. PROCEDURE The material used was an austenitic alloy with 33 pct Ni, 21 pct Cr, balance iron, containing approximately 0.05 pct C. Coupons of 1.25-mm sheet were first solution-annealed at 1050°C for 15 min and air-cooled. Then, to precipitate the carbides, samples were isothermally annealed in the range from 565" to 870°C for times up to several thousand hours. All further specimen-preparation procedures were carried out after the final anneal. Carbon extraction replicas from polished and etched surfaces were made with 10 pct bromine in methyl alcohol.' Thin foils were prepared from punched-out 3-mm-diam disksg which fit into the electron-microscope holder. The disks were prethinned by grinding to approximately 0.5 mm thickness, and then electro-polished in a polytetrafluoroethylene holder1' with a solution containing 5 pct perchloric acid in acetic acid to which 10 g per 1 Cro3 and 5 g per 1 nickel chloride were added (etchant modified from that of Briers et al."). This solution dissolves neither the carbides nor the austenite around the carbides preferentially. By using extraction replicas, electron micrographs and selected-area electron-diffraction patterns were taken from the same carbide arrays. By using thin foils, electron micrographs were made from a grain boundary area containing carbides. Electron-diffraction patterns were then taken from the same area and from each of the adjacent grains separately. In this manner, the orientation of each grain could be determined without interference by the carbide pattern. A peculiarity of extraction replicas should be pointed out. After the matrix is etched away, the carbide arrays float freely in the etching and washing solutions, and are held in place only at the anchoring points in the carbon replica. When the replica is picked up with a screen the carbide arrays tend to flip to one side. Thus, while the surface features are preserved, the original arrangement of the carbides may severely and unpredictably be disturbed whenever the specimen contains large amounts of interconnected carbides. Nevertheless, it is possible to correlate the different morphologies of the carbides with the type of boundary in which they have precipitated. RESULTS 1) Extraction Replicas. Fig. 1 shows that the grain boundaries usually are curved, multicornered surfaces of random orientation. The coherent twin boundaries (which are (111) planes) cut a grain into parallel slices. Incoherent twin boundaries occur at the ends and on the steps of twins and are often narrow, parallel-sided strips which are much longer than they are wide. Different morphologies can clearly be distinguished for the M23Ce carbides precipitated in each of these types of boundaries, and agree well with those observed by kinzel.2 The kinetics of this precipitation has been investigated." The first carbides precipitate in junctions of three grain boundaries and fan out from there into the adjoining boundary surfaces, Fig. 2(a). These carbides are oriented randomly, Fig. 2(b), and become coarser and thicker as annealing time increases. The large-angle grain boundaries are next to fill

Jan 1, 1967

By D. F. Stoneburner

The thermoelectric power and electrical conductivity of a series of liquid alloys of thallium were determined in order to study the relation of chemical bonding to semiconduction in liquids. The results indicate metallic behavior for the alloys of thallium with arsenic, antimony, and bismuth, while the sulfides, selenides, and tellurides indicate semiconduction. The results are compared with the Properties of the same alloys in the solid state. This work supports the observation that long-range order is not a necessary requirement for semiconduction. PREVIOUS work1,5 has shown that some sulfides and oxides behave as semiconductors in the liquid state. Although the band theory has been of great help in understanding the properties of solid semiconductors, its quantitative application to liquids is difficult. The very existence of liquid electronic semiconductors shows that ascribing the discrete structure of the energy spectrum to strict lattice periodicity, or long-range order, is not always satisfactory. Rather, the short-range order determines the structure of energy levels and the width of the forbidden gap and, consequently, the concentration of free holes and electrons. This is borne out by the analysis of data accumulated by Regel and coworkers.6 The similarity of electronic structure of liquid and solid phases of certain liquid metals was pointed out by Knight et a1.,7 who examined nuclear resonance in solid and liquid Li, Na, Rb, Cs, Mg, Al, Ga, Sn, and Bi. They found noticeable changes in the electronic structure upon melting only in the cases of bismuth and gallium. They concluded that "a liquid metal possesses a band structure which is very like that of the solid, provided the short-range structure is not altered during melting." In semiconductors in which the near-neighbor arrangement remains the same on fusion, the material would be expected to retain its semiconducting properties. The quantum theory of semiconductors, with its band structure of energy levels, is linked exclusively to long-range order. Furthermore, it has limited usefulness in predicting new semiconductors. Many sulfide8-12 have made comparisons of properties on the basis of crystal structure or the position in the periodic table, both methods involving the same factors as chemical bonding. Mooser and Pearson8"10 have pointed out that crystal structure depends on chemical bonding, and that this bonding is a property of the atoms themselves. As the periodic arrangement of the atoms offers an easy comparison of such factors as atomic weight and number of valence electrons it provides clues to expected similarities of bonding for various elements or groups of elements. This approach has led Mooser and Pearson to formulate their valence-bond theory of semiconduction, in which they define a semiconducting bond. These authors state that "semiconductivity is the result of the presence in a solid of predominantly covalent bonds. These lead, through the process of electron sharing, to completely filled s and p orbi-tals in the valence shells of all atoms of elemental semiconductors while in semiconducting compounds only one atom of any two bonded together need acquire closed s and p orbitals. The presence of empty 'metallic' orbitals in some atoms of a compound does not destroy the semiconductivity provided that these atoms are not bonded together; it may, however, give rise to pivoting resonance in

Jan 1, 1965

By Murray F. Hawkins, W. J. Ainsworth

In all types of subsurface pressure gauges the extension which occurs in the pressure-sensitive element is a function of the difference between the external (well or calibration) pressure and the internal pressure within the gauge, rather than a function of the external pressure only. The internal pressure is near atmospheric and depends upon (a) the quantity of air sealed within the gauge at the time of calibration or measurement, (b) the quantity of moisture (liquid water), if any, sealed within the gauge, and (c) the temperature at which the calibration or well measurement is made. Part of this correction for the change of internal pressure with temperature is taken care of by the customary temperature coefficient of the gauge. However, part of it is not, and while this portion may be only a few psi, it is nevertheless predictable or preventable, and should be considered in precision measurements. ERROR NO. 1 If air is sealed in the gauge at the same temperature and pressure for both the calibration and the well measurements, the usual temperature correction will take care of any difference between calibration and well measurement temperatures. However, if air is sealed within the gauge at temperature T1 and pressure P1 at calibration but at temperature T2 and pressure P2 for a well measurement, because different amounts of air are sealed within the gauge in each case, the internal pressure at. or corrected to, calibration temperature Tr will he different by where all temperatures and pressures are absolute. The calibration temperature is used, and not the well measurement temperature, because the usual temperature correction reduces the well measurements to calibration temperature. The correction term as calculated by the above equation is separate from. and in addition to, the usual temperature correction. Example: T, = 540°R, sealing temperature at calibration P, = 14.7 psia, sealing pressure at calibration T2 = 460°R, sealing temperature at well P2 = 14.7 psia, sealing pressure at well Tr = 660°R, calibration temperature AP = 660 [14.7/460 — 14.7/540] = 3.1 psi While this error is small even under these somewhat maximal conditions, it nevertheless represents a practical situation which did occur, and which as a matter of fact gave rise to this note. Where AP is positive, as above, the correction is added to the measured pressure; where negative, subtracted from the measured pressure. This correction should also be considered in successive calibration runs where the gauge, for example, may be warm from a previous calibration at an elevated temperature. ERROR NO. 2 Where a small quantity of moisture (liquid water) is sealed within the gauge at atmospheric conditions, the increased vapor pressure of the water at higher well or calibration temperatures will cause an increase in internal pressure. This moisture will come presumably from condensation within the gauge following temperature changes, from moisture on the operator's hands, and from atmospheric moisture (rain, mist, fog, etc.). Calculation shows that approximately 0.2 cc of water (three to four drops) is sufficient to saturate the air within an Amerada RPG-3 Gauge at 160°F, at which temperature the vapor pressure of water is about 5 psia. As the vaporization occurs in a sealed volume, the increase in internal pressure will be in excess of this 5 psi. At higher temperatures the pressures will be higher; however more water will be required to saturate the air within the gauge. Some experimental work was carried out with an Amerada RPG-3 Gauge at 200°F fitted with a 1,000 psi element, both with a dry recording chamber and with a small amount of water added. The results directly proved the existence of the error due to the presence of moisture, and, it is felt, indirectly, due to the differences in sealing temperatures and pressures, as both effects may be ascribed simply to an increase in the moles of gas within the recording chamber. SUMMARY In precision measurements the error introduced by sealing the gauge during a well test at a different temperature and pressure from that of calibration may be corrected for by using the equation presented, or it may be prevented by taking care always to seal the gauge at near calibration conditions. The error introduced by sealing moisture in the gauge may be prevented by taking care to keep moisture out of the gauge, or by removing the moisture by either warming or evacuating the gauge. Both of these errors are independent of the range of pressure measurement and the type of gauge, and are in addition to the usual temperature correction. ACKNOWLEDGMENT Appreciation is expressed to W. B. Kendall, Geophysical Research Corp., Tulsa, Okla., who pointed out the error from differences in sealing temperatures during some winter work in Canada. ***

Jan 1, 1956