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Who's Who in Mineral Engineering - The 1979 Directory of the Society of Mining Engineers of AIME

Jan 7, 1979

LIST OF THE MEETINGS OF THE INSTITUTE AND THEIR LOCALITIES FROM ITS ORGANIZATION Transactions Number Place Date Vol Page 1 Wilkes-Barre, Pa May, ?71 1 3 2 Bethlehem, Pa August, ?71 1 10 3 Troy, N Y November, ?71 1 13 4 Philadelphia, Pa February, ?72 1 17 5 New York, N Y May, ?72 1 20 6 Pittsburg, Pa October, ?72 1 25 7 Boston, Mass February, ?73 1 28 8 Philadelphia, Pa May, ?73 2 3 9 Easton, Pa October, ?73 2 7 10 New York, N Y February, ?74 211 11 St Louis, Mo May, ?74 3 3 12 Hazleton, Pa October, ?74 3 8 13 New Haven, Conn February, ?75 3 15 14 Dover, N J May, ?75 4 3 15 Cleveland, 0 October, ?75 4 9 16 Washington, D C February, ?76 4 18 17 Philadelphia, Pat June, ?76, 5 3 18 Philadelphia, Pa October, ?76 5 9 19 New York, N Y February, ?77 5 27 20 Wilkes-Barre, Pa May, ?77 6 3 21 Amenia, N Y October, ?77 6 10 22 Philadelphia, Pa. May, ?78 6 18 23 Chattanooga, Tenn May ?78 7 3 24 Lake George, N.Y. Oct. ?78 7

Jan 1, 1923

By J. C. Fisher

Nucleation theory is applied to martensite nucleation in substitutional iron alloys. Composition fluctuations are neglected, and a steady rate of nucleation is predicted for any composition and temperature. The maximum rate of nucleation (as a function of temperature) is shown to be measurable only for on extremely narrow composition range, being too great or too small outside this range. A number of experimental observations, including completely isothermal transformation in some alloys and composition-dependence of M. temperature in others, are compared with the calculated behavior. IN a previous report,¹ nucleation theory was applied to the formation of isothermal martensite in an Fe-Ni-Mn alloy. The experimental observations of Cech and Hollomon² were accounted for quantitatively. It now is of interest to examine the predictions of nucleation theory with respect to martensite transformation in substitutional iron alloys of other compositions. Since Fe-Ni alloys have received considerable attention, both as to their transformation kinetics and their free energies, they will be treated in detail, although the results apply with equal validity to other substitutional alloys. In substitutional alloys, where composition fluctuations can be neglected in volumes of critical nuclear size, the rate of nucleation of martensite in subcooled austenite is¹ n - Nv exp (—W*/kT) [I] where the free energy of formation of the critical size nucleus is W* = 8192 p (?² s³) [2] In the expressions for n and W*, the symbols have the following meanings: N is the number of atoms per unit volume; v, the atomic vibration frequency; 8, a function of the elastic constants of austenite and the shear angle of martensite; , the austenite/mar-tensite inter facial free energy; and ?fc is the free energy change per unit volume accompanying the transformation. Jones and Pumphrey² have determined the austenite to martensite free energy change as a function of nickel content and temperature for Fe-Ni alloys. Their expression is ?F = 2500 C + 1.25 (1 —C)?FFc cal per mol [3] where C is the atom fraction of nickel, and ?Ffe is the free energy change per unit volume for pure iron as tabulated by Zener4 (or, equivalently, Fisher"). From Eqs. 1 to 3, it is possible to calculate isothermal nucleation rates as a function of temperature and composition for Fe-Ni alloys. The only unknown parameter is (?² s³). The best value of this parameter for Fe-Ni alloys, determined from M. temperatures in a manner to be described shortly, is (?² s³)= 9.92 (10)21 cgs units [4] Taking this value of (?² s³), C-curves for isothermal nucleation were calculated for Fe-Ni alloys of several compositions, and are plotted in Fig. 1. It is evident from Fig. 1 that completely isothermal nucleation of martensite in Fe-Ni alloys can be observed experimentally for only a very narrow range of compositions. Cech and Hollomon find that a nucleation rate of about 10' nuclei per cc per sec is as fast as they can follow dilatometrically, and a rate of about 10-1 nucleus per cc per sec is about the slowest that can be measured conveniently. If the nucleation rate is to lie between the limits 10-1 10 the nickel content of an Fe-Ni alloy must fall in the atomic fraction range 0.299 5 C 5 0.302. Nickel contents lower than 0.299 correspond to nucleation rates too great to follow, and those higher than 0.302 to nucleation rates too slow to measure in a reasonable time.* In view of the narrow corn- position range in which successful isothermal measurements can be made, it is not surprising that only one substitutional alloy has been described' that comes close to being in the proper range.

Jan 1, 1954

By W. R. McMillan, E. A. Gulbransen, K. F. Andrew

Annealed and electrolytically polished pure iron was oxidized between 650° and 850°C at oxygen pressures of 0.1 to 2 microns Hg. Electron optical studies showed that oxidation occurs discontinuously over the surface and orients crystallographically with the substructure of the metal grains. IN previous papers', " the authors described the formation of oxide films on high purity iron at norrnal pressures and at temperatures below 300°C. Electron optical studies showed that the oxide film consisted of many individual oxide crystallites having nearly random orientation on each metal grain. The size of the oxide crystallites depended upon the temperature and upon the extent of oxidation. In these studies the crystallite size varied from 250 to 1800Å. Recently, Bardolle and Benard3 studied the crystal habit of the oxide crystallites formed on Armco iron between 650" and 850°C in what might be defined as a "poor vacuum" atmosphere in which the pressure could be varied between 10-1 to 10-3 mm of Hg. Their results showed that, at 850°C and a vacuum of l0-2 to 10-3 mm of Hg, a few well oriented nuclei of oxide were formed on the metal grains. At pressures between l0-1 to 10-2 mm of Hg, many oriented nuclei of oxide were formed. At 750°C the metal surface was bright although an oxide was present. Unfortunately, the extent of oxidation, the oxygen pressure, and the influence of carbon in the metal were not determined, and it was, therefore, impossible to give a theoretical interpretation to the very beautiful light micrographs. Bardolle and Benard used the light microscope to determine the crystal habit of the oxide and X-ray diffraction to determine the orientation relationships. It was believed that the use of controlled amounts of oxidation at high temperature is an important method for the study of the initial stages of oxidation of metals at high temperatures. This paper presents the first results of an electron optical study of this problem for iron. Since the electron microscope and electron-diffraction methods using stripped oxide films and surface replicas yielded finer details of the crystal habit and structure of oxide film, these methods were used in this study. Two types of iron having different carbon contents were used: Puron and Armco* iron. A com- parison of the results for these materials made possible a study of the influence of the surface oxide-carbon reaction on the initial stages of oxidation. Before discussing the experimental results, the thermodynamic equilibria of 1—the oxidation reaction, 2—the surface oxide-carbon reaction, and 3—the solubility of oxygen in iron, will be considered. In addition, it is important to consider the kinetic-theory predictions on the rate of collision of oxygen with the iron surface. Thermodynamic and Kinetic-Theory Calculations Only one type of reaction is usually considered in the oxidation of iron at normal pressures at high temperatures: Fe(a) + 1/2O2(g) = FeO(s) 3Fe(a) + 2O2(g) = Fe3O4(s) 2Fe(a) +3/2O2(g) = a-Fe2O3(s). [11 However, two other reactions may occur: FeO(s) + C (solid solution in Fe) + Fe(a) + CO(g) [2] and Fe(a) + O2(g) e Fe(a) (solid solution of 0,). [ 3 ] In addition, iron will react with the higher oxide at certain temperatures to form FeO. For a complete interpretation of the oxidation of iron at low pres-

Jan 1, 1955

By Kefton H. Teague

Attempts to locate domestic supplies of sillimanite have been unsuccessful until recently. This paper describes recent discoveries of sil-limonite-bearing schists in the Southeastern States, with emphasis on geology of the deposits, mineral composition, origin, and reserves. Statements concerning possible methods of mining, milling, and utilization of sillimanite are given. Results from refractory tests on a laboratory scale are summarized. SINCE 1917, when synthetic mullite was first used in spark plug porcelains, there has been a continued search for natural sillimanite. During the recent war this search was intensified, not only for sillimanite but also for any materials which could be used satisfactorily as a substitute for the imported kyanite from India. The Indian massive kya-nite does not decrepitate during calcination as does our domestic bladed kyanite, thus a coarse grog can be obtained from it. Some of the most promising domestic materials suited for high temperatures are limited in quantity. Massive topaz from Chesterfield County, S. C., showed promise of possessing desirable refractory properties; but the action of combined fluorine, liberated during calcination, upon equipment and surroundings, as well as a limited supply of ore and the presence of impurities discouraged its use. Residual lumps and boulders of massive kyanite, similar to the material imported from India, occur in Georgia. This material, like the massive topaz, is of limited quantity. Andalusite from California and dumortierite from Nevada are satisfactory high-temperature refractory materials. Their uses have been restricted to specialized products since the location and character of the deposits are such that large production is impractical. Sillimanite, like kyanite and andalusite, has the theoretical chemical composition of Al2SiO5. It has a hardness of 6 to 7; vitreous, silky to subadamantine luster; specific gravity of 3.2 to 3.3; and is gray to bluish gray in color. Under the binocular microscope, the crystals are transparent. The mineral may occur as dense, fibrous mats (fibrolite) composed of fibrous, sometimes radiating hair-like crystals in schist which are associated with igneous intrusions. Deposits of this type have widespread distribution, but none discovered to date appears to have commercial possibilities. Sillimanite also occurs as bundles of crystals disseminated in biotite schist, as noted in the Hart-Elbert-Madison County, Ga., area and in some of the South Carolina and North Carolina deposits. This type of material has been called prismatic sillimanite by the U. S. Bureau of Mines. Deposits of this variety appear to offer commercial possibilities. When heated above 1650°C, sillimanite expands about 6.5 pct and is converted into a mixture of mullite (3Al2O3 . SiO2) and vitreous silica. This is a stable mixture which has a specific gravity of about 3.15. General Geology: Sillimanite (fibrolite) is a mineral common to the pre-Cambrian metasedi-ments of the Southeast. It occurs throughout the crystalline schists which lie between the Fall Line on the southeast and the established Paleozoic rocks on the northwest (fig. 1). In addition to the meta-sediments, this area contains pre-Cambrian igneous

Jan 1, 1951

By Kefton H. Teague

Attempts to locate domestic supplies of sillimanite have been unsuccessful until recently. This paper describes recent discoveries of sil-limonite-bearing schists in the Southeastern States, with emphasis on geology of the deposits, mineral composition, origin, and reserves. Statements concerning possible methods of mining, milling, and utilization of sillimanite are given. Results from refractory tests on a laboratory scale are summarized. SINCE 1917, when synthetic mullite was first used in spark plug porcelains, there has been a continued search for natural sillimanite. During the recent war this search was intensified, not only for sillimanite but also for any materials which could be used satisfactorily as a substitute for the imported kyanite from India. The Indian massive kya-nite does not decrepitate during calcination as does our domestic bladed kyanite, thus a coarse grog can be obtained from it. Some of the most promising domestic materials suited for high temperatures are limited in quantity. Massive topaz from Chesterfield County, S. C., showed promise of possessing desirable refractory properties; but the action of combined fluorine, liberated during calcination, upon equipment and surroundings, as well as a limited supply of ore and the presence of impurities discouraged its use. Residual lumps and boulders of massive kyanite, similar to the material imported from India, occur in Georgia. This material, like the massive topaz, is of limited quantity. Andalusite from California and dumortierite from Nevada are satisfactory high-temperature refractory materials. Their uses have been restricted to specialized products since the location and character of the deposits are such that large production is impractical. Sillimanite, like kyanite and andalusite, has the theoretical chemical composition of Al2SiO5. It has a hardness of 6 to 7; vitreous, silky to subadamantine luster; specific gravity of 3.2 to 3.3; and is gray to bluish gray in color. Under the binocular microscope, the crystals are transparent. The mineral may occur as dense, fibrous mats (fibrolite) composed of fibrous, sometimes radiating hair-like crystals in schist which are associated with igneous intrusions. Deposits of this type have widespread distribution, but none discovered to date appears to have commercial possibilities. Sillimanite also occurs as bundles of crystals disseminated in biotite schist, as noted in the Hart-Elbert-Madison County, Ga., area and in some of the South Carolina and North Carolina deposits. This type of material has been called prismatic sillimanite by the U. S. Bureau of Mines. Deposits of this variety appear to offer commercial possibilities. When heated above 1650°C, sillimanite expands about 6.5 pct and is converted into a mixture of mullite (3Al2O3 . SiO2) and vitreous silica. This is a stable mixture which has a specific gravity of about 3.15. General Geology: Sillimanite (fibrolite) is a mineral common to the pre-Cambrian metasedi-ments of the Southeast. It occurs throughout the crystalline schists which lie between the Fall Line on the southeast and the established Paleozoic rocks on the northwest (fig. 1). In addition to the meta-sediments, this area contains pre-Cambrian igneous

Jan 1, 1951

By R. W. Baldwin

On page 309, column 1, the second equation should read: Ma-M1 = dlog_Pa M2-M1 d log P2

Jan 1, 1961

AALL, Christian H.,(M'49), Asst Res Dir Monsanto Chemical Co Anniston, Ala AALSETH, Earl P ,(J,51), Amerada Petr Corp Geological Dept Williston N Dak AAMOT, Olav Crone, (M'29), Met Pacific N W Alloys, Inc , Box 6215, Hillyard P 0 Spokane 14, Wash AARING, Floyd D ,(J'48), Petr Engr P 0 Box 130, Calgary, Alta Canada AARCNSON, Hubert Irving, (S'47), Carnegie Inst of Tech., Pittsburgh, Pa ABADIE, Henry G ,(M'43), Asst to the Sup- of Operations, Long Beach Oil Development Co ,255 So Santa Clara Ave Long Beach, Calif ABBISS, H. J., (A'50), Min. Engr., Buchans Mining Co., Ltd.. Buchans, Newfoundland ABBOTT, Clarence Eugene, (M'04), 901 Insurance Bldg , Raleigh, N C ABBOTT, George, (S'52), Mass Inst of Tech Cambridge, Mass

Jan 1, 1952

By C. S. Sivaramakrishnan, Manjit Singh, Rajendra Kumar

Regarding liquid nzetals structurally as a suspm-sion of clusters , having derivated solid-state coordination, in truly liquid atoms, the recently developed Kuvlar-Samarin technique of centrifuging- in liquid state enabled the determination of the cluster sizes inAl-Cu mid Pb-Sn systems. It is shown that the colutne fraction of the clusters does not exceed 9 pct and the energy of their formation in Al-Cu is about 5.5 kcal per g-atom and in Pb-Sn eutectic alloys about 25 kcal per y-atoni. STRUCTURAL investigations of liquid state have principally followed the following three courses: i) studies with X-ray, electron, or neutron diffraction; these investigations have shown that there is a certain amount of regularity in the structure of liquid metals which can be defined by a coordination number and that the structure is a derived function of that in the solid state; ii) thermodynamical investigations which are based on the concept of ideal behavior; these describe the liquid state in terms of free-energy values and other thermodynamic functions; although these investigations are of help in the study of the general effects of alloying, they do not provide any structural insight into the precise atomic distribution in liquid state; iii) measurements of surface tension and viscosity; although it is natural to expect that the viscosity is related to the structure in liquid state, these investigations have so far only provided information which can be used by the foundry technologists and has been little utilized in formulating models of the structure of liquid state. As it happens, investigators in the three groups have worked almost independently of each other and there is practically no structural correlation between the results of one group with those of another. The purpose of the present paper is to indicate that the experimentally measured parameters of these three groups of research are closely related to the structure in the liquid state. STRUCTURE OF LIQUID METALS Although atomic distribution in solid and gaseous states is rigorously known, that of the liquid state is only appreciated on the fringes. There is no universal model of atomic distribution in liquid state, but two diverse models are at present hotly contested. The first, largely expounded by ~ildebrand,' regards the liquids as condensed gas since many of their properties and much of their behavior can be adequately described by regarding them as fluids. The second mode12j3 considers that some form of near-solid as- sociation of large number of atoms exists in the liquid state. On the other hand, ~ernal' was able to predict rather precisely the radial distribution functions in liquids on the basis of statistical geometric approach which considered that liquids are "homogeneous, coherent, and essentially irregular assemblage of molecules containing no crystalline regions or holes large enough to admit another molecule". He introduced the concept of pseudonuclei in the otherwise random structure as aggregates of closely packed tetrahedra which gradually merge into irregularity and continually replace each other. To what extent the pseudonuclei can be regarded as regions of near-solid association is indefinite but Bernal suggested that the concept of pseudonuclei can be compromised with the latter model if the near-solid associations are regarded as extremely dense and not necessarily crystalline. The difficulty in projecting the structure of liquid metals arises because they exhibit duplicity of character as some of their properties are closer to those of crystalline solids and others to fluids. There is an increasing tendency to discuss the structure of liquid metals in terms of the second concept according to which the structure of liquid metals may be conceived as consisting of i) clusters of atoms where the aggregation is a close derivative of that in the crystalline state, ii) individual atoms which behave like true liquids in respect to degrees of freedom and iii) excess number of vacancies. It is noteworthy that the introduction of only 5 pct vacancies is sufficient to transform crystalline matter into the liquid state. At any instant of time thermodynamic equilibrium exists between i, ii, and iii, but the relative proportion of the clusters and random atoms is not known. That this is so can be appreciated by the fact that, when liquid metal is rapidly cooled, liquid state vacancies may condense in the form of dislocation loops and vacancies in excess of their equilibrium number in solid state. These dislocation loops have been observed in thin foils of aluminum prepared from rapid cooled aluminum. As temperature increases above melting point the number and volume fraction of clusters decrease but those of vacancies and random atoms increase. Clusters are transient in nature. In pure metals the cluster is an aggregation of the metal itself. In alloys, however, the nature of the cluster largely depends on the interaction between solvent and solute atoms. If the interaction between unlike atoms is greater than between like atoms: the clusters are then aggregates of unlike atoms. Examples of this kind of system are A1-Cu, Mg-Pb, and so forth, i.e., systems which exhibit negative departures from the Raoult's law. In systems where the interaction between unlike atoms is smaller than be-

Jan 1, 1968

Masjid-i-Su1aiman.—There have been no new developments in the Masjid-i-Sulaiman oil fields during the year 1938. In spite of the age of this field, the fall in dome pressure shows no appreciable variation from the low rate of about 0.3 lb. per sq. in. per million tons net production. Drilling has been limited to deepening old wells and to new wells required for maintenance of production and general reservoir control. The rate of offtake has been reduced over the past few years, partly because of depletion of the oil column, and it is expected that future offtake from the Masjid-i-Sulaiman field will be stabilized for some years at around the present figure of 3,000,000 tons per annum. Haft Ke1.—An exploratory well to test deeper formations in the Haft Kel field has proved the existence of productive conditions in the Eocene, which underlies the Asmari limestone (the main producing horizon). Drilling to the northwest in the white-oil springs area has revealed the presence of a separate structure with productive potentialities. One well with a satisfactory production rate has been completed. Offtake from the Haft Kel field has steadily increased since it first came on to production in 1929. Naft-i-Shah.—Production from this field has continued to supply market requirements in northwest Iran. The policy of returning surplus products to the reservoir, which was adopted at the beginning of 1936, has been continued.

Jan 1, 1939

Masjid-i-Su1aiman.—There have been no new developments in the Masjid-i-Sulaiman oil fields during the year 1938. In spite of the age of this field, the fall in dome pressure shows no appreciable variation from the low rate of about 0.3 lb. per sq. in. per million tons net production. Drilling has been limited to deepening old wells and to new wells required for maintenance of production and general reservoir control. The rate of offtake has been reduced over the past few years, partly because of depletion of the oil column, and it is expected that future offtake from the Masjid-i-Sulaiman field will be stabilized for some years at around the present figure of 3,000,000 tons per annum. Haft Ke1.—An exploratory well to test deeper formations in the Haft Kel field has proved the existence of productive conditions in the Eocene, which underlies the Asmari limestone (the main producing horizon). Drilling to the northwest in the white-oil springs area has revealed the presence of a separate structure with productive potentialities. One well with a satisfactory production rate has been completed. Offtake from the Haft Kel field has steadily increased since it first came on to production in 1929. Naft-i-Shah.—Production from this field has continued to supply market requirements in northwest Iran. The policy of returning surplus products to the reservoir, which was adopted at the beginning of 1936, has been continued.

Jan 1, 1939

LIST OF THE MEETINGS OF THE INSTITUTE AND THEIR LOCALITIES FROM ITS ORGANIZATION Transactions Number Place Date Vol Page 1 Wilkes-Barre, Pa May, ?71 1 3 2 Bethlehem, Pa August, ?71 1 10 3 Troy, N Y November, ?71 1 13 4 Philadelphia, Pa February, ?72 1 17 5 New York, N Y May, ?72 1 20 6 Pittsburg, Pa October, ?72 1 25 7 Boston, Mass February, ?73 1 28 8 Philadelphia, Pa May, ?73 2 3 9 Easton, Pa October, ?73 2 7 10 New York, N Y February, ?74 211 11 St Louis, Mo May, ?74 3 3 12 Hazleton, Pa October, ?74 3 8 13 New Haven, Conn February, ?75 3 15 14 Dover, N J May, ?75 4 3 15 Cleveland, 0 October, ?75 4 9 16 Washington, D C February, ?76 4 18 17 Philadelphia, Pat June, ?76, 5 3 18 Philadelphia, Pa October, ?76 5 9 19 New York, N Y February, ?77 5 27 20 Wilkes-Barre, Pa May, ?77 6 3 21 Amenia, N Y October, ?77 6 10 22 Philadelphia, Pa. May, ?78 6 18 23 Chattanooga, Tenn May ?78 7 3 24 Lake George, N.Y. Oct. ?78 7 25 Baltimore, Md. Feb. ?79 7

Jan 1, 1923

Jan 1, 1967

Jan 1, 1944

Jan 1, 1944

By Shiou-Chuan Sun

DISCUSSION shiou-chuan sun (author's correction) - Too late for revision, the author realized that the data on stability of froth presented in this paper were not based on the same height of froth column. It is recommended herein that the stability of froth is better calculated by dividing the time elapsed until the froth disappeared by the volume (in cu cm per sq cm) or height of the froth column, and is expressed in sec per cm. The stability data in Tables I, II, and III of this paper were recalculated, in accordance with this recommendation, and the results are shown respectively in the accompanying Tables VII, VIII, and IX. Compared with Tables I, II, and III of the paper, the stability data of Tables VII, VIII, and IX are more reliable in disclosing the persistence of froth of various frothers having different frothabilities. For example, the conclusion given in the paper that the stability of froth is generally proportional to the volume of froth becomes invalid when the stability of froth is expressed in sec per cm, as shown in Tables VII, VIII, and IX. Table VII shows that both the stability and volume of froth increase with the addition of small amounts of n-hexyl alcohol, and that further additions of n-hexyl alcohol decrease the stability but increase the volume of froth. Table VIII indicates that the stability of different types of frothers is governed by their chemical composition and is difficult to predict from their frothability. Table IX shows that the stability of different frothers with similar nonpolar groups tends to increase with a decrease of the hydro- philic property of their polar groups, and consequently with the decrease of their solubilities. This is further substantiated by the fact that the stability of frothers, as listed in Table IX, is generally lowered by the solvent effect of absolute ethyl alcohol. Table IX shows also that the stability of froth tends to increase with the decrease of the volume of froth* provided the frothers used have similar nonpolar groups and dissimilar polar groups.

Jan 1, 1953

By Shiou-Chuan Sun

DISCUSSION shiou-chuan sun (author's correction) - Too late for revision, the author realized that the data on stability of froth presented in this paper were not based on the same height of froth column. It is recommended herein that the stability of froth is better calculated by dividing the time elapsed until the froth disappeared by the volume (in cu cm per sq cm) or height of the froth column, and is expressed in sec per cm. The stability data in Tables I, II, and III of this paper were recalculated, in accordance with this recommendation, and the results are shown respectively in the accompanying Tables VII, VIII, and IX. Compared with Tables I, II, and III of the paper, the stability data of Tables VII, VIII, and IX are more reliable in disclosing the persistence of froth of various frothers having different frothabilities. For example, the conclusion given in the paper that the stability of froth is generally proportional to the volume of froth becomes invalid when the stability of froth is expressed in sec per cm, as shown in Tables VII, VIII, and IX. Table VII shows that both the stability and volume of froth increase with the addition of small amounts of n-hexyl alcohol, and that further additions of n-hexyl alcohol decrease the stability but increase the volume of froth. Table VIII indicates that the stability of different types of frothers is governed by their chemical composition and is difficult to predict from their frothability. Table IX shows that the stability of different frothers with similar nonpolar groups tends to increase with a decrease of the hydro- philic property of their polar groups, and consequently with the decrease of their solubilities. This is further substantiated by the fact that the stability of frothers, as listed in Table IX, is generally lowered by the solvent effect of absolute ethyl alcohol. Table IX shows also that the stability of froth tends to increase with the decrease of the volume of froth* provided the frothers used have similar nonpolar groups and dissimilar polar groups.

Jan 1, 1953

By J. E. McDonald, J. G. Eberhart

A model is discussed from which the work of adhcslon .tor liquid transition metals on aluminum oxide surfaces can he calculated, A close-packed (00011 oxygen surface on A12O3 is assumed with two different types of surface sites: one type involving metal-oxygen bonds and the other man der Waals into actions. The work of adhesion is thus expressed as the sum of these two bonsding free energies. Calculated works of adhesion for nickel, titanium, chromium, and zirconium on sapphire agree well with the experimentally determined quantities. The model is extentled to the calculation of the work of adhesion and shear stress required to remove a thin metal film from a sapphire substrate and is in good agreement with experimental values. The obsewed dependence of the work of adhesion on the free energy of oxide formation of the metal is shown to also provide an interpretation of the tittle dependence of thin-film adhesion. THIS paper presents a model for the type of bonding which occurs across a metal-A12O3 interface. The model is used to explain the results of two types of experiments in which such an interface exists: 1) the adhesion of thin metal films on Al2O3 substrates and 2) the wetting of A12O3 by liquid metal drops. The adhesion of thin films to various substrates has been the subject of a variety of investigations.'-' Benjamin and weaver3 and Bowie,6 using the scratch test developed by Heavens,10 studied the adhesion of metallic films to glass substrates. Their observations for noble-metal film adhesion agree well with an adhesion model involving a van der Waals type of bonding between the film and the substrate. For films of metals whose free energy of oxide formation. ?F°f, has a negative value. Benjamin and weaver3 and Bowie6 found a time-dependent adhesion with an initial value that can be interpreted in terms of van der Waals interactions but a larger terminal value which was related to ?F°f, Karnow-sky and Estill7 deposited films on sapphire at elevated temperatures and noticed no time dependence of film adhesion but a similar correlation with ?F°f. Because of the kinetic problems associated with thin-film adhesion it is desirable to examine adhesion in an equilibrium system. The wetting behavior of liquid-metal drops on Al2O3 provides such a system. Systems of this metal-ceramic type have been studied extensively.11 Humenik and Kingeryl2 have measured the wetting of A12O3 (and other substrates) by several metals and have pointed out that the wetting ability of these metals increases with increasing values of -?F°f. It is thus seen that thin-film adhesion and metal wetting on A12O3 are both related to the tendency of the metal to react with the surface oxide ions of the Al2O3 substrate and, because of this, both phenomena should be explainable by an appropriate model for the metal-Al2O3 interfacial bonding. In the sections that follow, wetting and adhesion data on A2O3 are reviewed and a model is presented by which these phenomena can be interpreted. ANALYSIS OF WETTING EXPERIMENTS In an equilibrium system involving a liquid-metal drop on a solid Al2O3 substrate, the work of adhesion, WAD, is defined by the Dupre, equation as WAD = ?s + ?L -?sL [1] where ?s and ?L are the surface free energies of the solid substrate and the liquid drop, respectively, and ?sL is the interfacial free energy. The work of adhesion is the work required to separate a unit area of the solid-liquid interface into two surfaces. The work of adhesion is usually determined from a sessile-drop experiment in which yL and the contact angle, ?, are measured. The Young-Dupr6 equation is then used to calculate WAD Wad = ?L (1+ cos ?) [2] The literature of this subject has been examined and Table I shows work of adhesion data for various liquid metals as measured on A12O3 substrates. The standard free energy of oxide formation of the metal at the temperature of the wetting experiment, ?F°f . is also tabulated in kcal per g-atom of oxygen. The data is grouped according to the gaseous atmos-

Jan 1, 1965

By J. D. Sudbury, J. E. Landers, D. A. Shock

The external corrosion of casing is one of the most important problems facing the present day production man. A 1953 NACE report' estimated the annual cost of casing corrosion at $2,200,000 in 22 fields studied. The fields represented only 10 per cent of the wells in the United States. It was significant that 77 per cent of the failures reported were due to external corrosion. A variety of means for combatting the casing corrosion problem have been discussed in papers such as the NACE survey' mentioned previously. No attempt to revicw these will be made in this paper. Thc scope of this paper has been limited to a discussion of the following major items: (I) an instrument for studying external electrolytic corrosion; (2) use of this instrument to determine the quantity of protective current required to prevent corrosion of casing; and (3) problem of accelerated external corrosion of the oil string at the base of the surface string. ELECTROCHEMICAL MECHANISM OF CORROSION It IS gcncrally belleved that one major cause of external corrosion is the existence of electrolytic cells operating between various formation waters. A theoretical discussion of the role of earth potentials in casing corrosion has been presented by L. de Witte and F. J. Radd.2 A brief picture of the electrolytic corrosion action between two differcnt formations (A and B) is presented in Fig. I. This picture is a review to many but is given to insure clarity. In the anode area, oxidation takes place as iron ions go into solution in formation A as a product of corrosion. In the cathode area. reduction takes place and hydrogen atoms are formed at the boundary between the pipe and formation B. The flow of electrons. as indicated. is into the pipe at the anode or corroding area and out of the pipe into the formation at the cathode. In order to conform with regulations of this journal, the flow of a conventional current (I! is also indicated in this sketch. All subsequent references will be to this so-called conventional current flow and will be indicated by the symbol (I). As this action takes place the layer of hydrogen developed on the cathode offers a resistance to the flow of current in the cell. It is said (hat the cathode has been polarized. This polarizing film can be rcmoved by addition of a so-called dcpolarizing agent which reacts with and removes this hydrogen film. Such an agent must be present in ordcr for this corrosion reaction to go at a rate sufficient to cause a severe corrosion problem. The two common depolarizing agents are: (I) oxy-sen. which readily reacts with hydro gen to form water, and (2) certain bacteria which use atomic hydrogen as part of their life process. It is not difficult to explain the presence of these agents. Oxygen may be present in some very shallow formations. Sulfate reducing bacteria are found to exist in nearly any ground where mud pits might be dug. THE CASING POTENTIAl-PROFILE Instrumentation A sketch of the equipment* uscd in determining casing potential profiles is shown in Fig. 2. The tool is run in the hole using a hoist truck with a three-conductor cable. This tool must be run with tubing and rods out of the hole and should be run with the flow line disconnected. By proper choice of electrode size it can be run in any size casing. The electrodes must be run in an open hole or a hole filled with oil. Measurements cannot be made while immersed in water. The tungsten carbide-tipped knives serve as the electrical robes and arc spaced 25 ft apart. The potential difference along a 25-ft section of casing is measured with a potentinmeter to an accuracy of about 5 mv. Current flowing in the pipe can then

Jan 1, 1956

By B. C. Mariacher

EXTRACTION of uranium from ores is being ac-complished by processes which. for the most part, subject the entire ore to acid or carbonate leaching. Ore deposits with a U 3 O 8 content below 0.10 pct U 3 O 8 are seldom considered suitable for treatment by leaching. A preliminary concentration that would enrich the uranium content of an ore by a simple, low cost process based on physical properties of the ore might result in some low grade deposits becoming commercial ores. In addition, the process might be employed in existing operations to reduce transportation and leaching costs and to increase capacity of existing leaching plants. A study to attempt the development of a preliminary concentration process for primary uranium ores was undertaken by the Colorado School of Mines Research Foundation under sponsorship of the U.S. Atomic Energy Commission. The objective of this work was to produce concentrates containing 0.25 pct U3O8 from the low grade ores tested. Ores Tested: The main effort was devoted to the low grade primary uranium ores from northwestern Saskatchewan. Samples were obtained from the Beaverlodge operation of the Eldorado Mining & Refining Ltd. Additional primary ores, obtained from deposits in Gilpin County, Colo., contained from 0.07 to 0.10 pct U3O8. Summary of Concentration Tests: The Beaverlodge ore was tested to determine amenability of the ore to concentration by magnetic, electrostatic, gravity, and scrubbing processes. None of these produced satisfactory results. Both gravity and magnetic processes produced fairly good concentrates when closely sized fractions of the ore were treated, but on the basis of treating the total ore, recovery was poor. Preparation of sized fractions and the low capacity of equipment for suitable concentration made these methods impractical. As flotation offered the advantage of treating the total ore without intermediate sizing, the main effort was in this direction. A flotation process was developed that fulfilled the concentration objectives as set by the AEC. Pilot plant testing was used to verify results obtained from laboratory batch testing. Mineralogy: A petrographic examination of the Beaverlodge ore included a study of polished sur- faces and identification of the radioactive mineral by autoradiograph and X-ray diffraction. Approximate quantitative mineral identification was as follows: quartz, 60 pct; orthoclase feldspar, 20 pct; chlorite, 10 pct; carbonates, 5 pct; and miscellaneous minerals, 5 pct. Included in this last group were plagioclase feldspar, pyrite, mica, chalcopyrite, pyroxene, sericite, magnetite, galena, and uraninite. The most general occurrence of uraninite was in the form of crusts and thin coatings on limonite-stained grains of pyrite, quartz, and pyrite-quartz intergrowth. At least 90 pct of the uraninite was still attached to other minerals in a 100 by 200-mesh size fraction. The uraninite crusts were as small as 10 to 20 µ diam, and 5 to 10 µ thick. The Flotation Process Petrographic examinations of the Beaverlodge ore had indicated the impracticability of attempting to concentrate the uranium by floating individual grains of uraninite. Liberation of the uraninite required grinding to sizes below those suitable for flotation. However, there was preferential association of the uraninite with some minerals while others were free of uraninite attachment. The approach to the development of a flotation process was, therefore, based upon an attempt to concentrate the uraninite by floating carrier minerals. The following paragraphs discuss the various stages of the process with regard to the factors tested and the conditions under which best results were obtained. Grinding: The most effective size range for flotation was —150 mesh + 13 µ. The —13 µ material in the final concentrate had a higher U3O8 content than the total ore, but not as high as the average concentrate; however, rejection of slimes before flotation was prohibitive because of the loss in uranium carried in the —13 µ fraction. Grinding techniques which contributed to a minimum production of fines, such as stage grinding, were then employed. Quartz and Silicate Depression: These minerals represented approximately 80 pct of the ore and were free to a large degree of uraninite attachment. Significant improvement in the grade of the concentrate was obtained by depression of these minerals with hydrofluoric acid or sodium fluoride. Promoter: Selective stage flotation of uraninite carrier minerals was simplified by development of a single promoter mixture. The mixture consisted of an emulsion of a fatty acid, fuel oil, and a petroleum sulfonate and was selected after a comprehensive series of tests. It contained three parts by weight of an oleic and linoleic acid such as Emersol 300,

Jan 1, 1957