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Jan 1, 1943

By Robert A. Rapp, Jan E. Verfurth

From the measurement of internal-oxidation band widths in Ag-In and Cu-A1 alloys, products for the solubility No and the diffusivity Do of oxygen in silver and apparent NODo products in copper have been obtained over a range of temperature. The NODO products for silver are in agreement with the product of the individually determined No and Do values of Eichenauer and Müller. Although interstitial diffusion of oxygen in silver is expected, the temperature-independent factor Do of the diffusion coefficient does not agree well with the theory of Wert and Zener. For Cu-A1 alloys internal oxidation does not follow the expression derived for ideal kinetics, since the apparent NODo product calculated from internal-oxidation measurements is a function of the alloy content in the specimen. Thus, unequivocal values for No or DO or even the product NODO in copper are not available from the literature. RELIABLE values for the saturation solubility NO and diffusivity DO of oxygen in fcc metals are lacking and difficult to determine, partially because internal-friction measurements are not applicable. Permeability experiments and Sieverts7-type adsorption -desorption methods3 have met with difficulty; however, Eichenauer and Müller4 have recently reported on the solubility and diffusivity of oxygen in silver as determined by the latter technique . Rhines, Johnson, and Anderson,5 and independently Meijering and Druyvesteyn,' introduced the possibility of deriving values for the product NODO in a metal from measurements of the widths of internal-oxidation zones (subscales) formed during the internal oxidation of alloys. In addition to these authors, several other investigators7-9 have made such measurements in various silver and copper alloys at various temperatures, mostly using me- chanically polished specimen surfaces. The purpose of this investigation was to determine over a range of temperature the calculated products NODO in silver and copper from systematic measurements of the widths of internally oxidized zones in Ag-In and Cu-A1 alloys, using specimens with electro-etched surfaces. Consider the internal oxidation of a dilute solid-solution alloy in which the base metal is not oxidized. If diffusion of oxygen is the rate-controlling step, then the depth 5 of the internal-oxidation zone is given by where y is a dimensionless parameter and t the oxidation time. Based on the solution of the diffusion equation, wagnerl0 has shown that under certain conditions several mathematical simplifications may be used in the evaluation of y, so that Eq. [I] may be expressed for the case that y « 1, and y(Do/DB) 1, where N(so)the is the equilibrium solubility (mole fraction) of oxygen in the solvent metal for the given oxidizing atmosphere, is the mole fraction of the solute metal in the bulk alloy, 4 is the diffusivity of the solute in the base metal, and v is the ratio of oxygen atoms to solute atoms in the precipitated oxide BO,. Rearranging Eq. [2] Maak' has derived an expression analogous to Eq. [3] for the case that an external-oxide scale, in addition to an internal-oxidation zone, is formed. For this combined external and internal oxidation for the case that 5/2 where 5 is the distance of the internal-oxidation front from the original external s.urface, and X is the distance of the external oxide/metal interface from the original external interface. The function F is defined by the expression

Jan 1, 1964

By R. H. Tien

This paper presents an analytical solution of the problem of freezing of a semi-infinite slab with constant surface temperature; in this analysis accoz~nt is taken of the heat evolution during the solid-state transformations in the frozen skin. The regions where transformations occur are treated as plane isothermal heat sources; i.e., the rates of transformations are assumed to be infinite. In the model considered, three plane heat sources are assumed to be present in the frozen solid. The solution yields the temperature distribution in the solid, the rates of movement of the heat sources , and the rate of movement of the solidification front. It is shown that, although the sum of the heats of transformations in the solid is about 20 or 43 pct of the heat of fusion of iron or manganese, respectively, the effect of the heat evolution in solid-state transformations on the rate of solidification is insignzficant. IN several recent mathematical studies of solidification of liquid metals'-3 no account was taken of the heat evolution accompanying the solid-state transformations. In the case of, for example, steel, there are several phase transformations 6 -y, y -a, and the magnetic transformation. Whether or not a significant error is introduced into the mathematical simulation of solidification processes by the omission of the heat effects associated with these phase transformations is not known. The purpose of the present study is to investigate the effect of these phase transformations on the temperature distribution and the rate of solidification based solely on the heat transfer point of view. That is, for the sake of simplicity, freezing of a pure metal with solid-state transformations will be considered. The mathematical model which represents the present problem includes four moving heat sources representing freezing and phase transformations, 6— y — a — ferromagnetic. The thermal properties such as conductivity and specific heat, and so forth, are different from one phase to the other. But they are considered to be uniform over any particular phase. The usual Fourier heat flow law is employed. The concept of conservation of energy is applied at every heat source in order to estimate their rate of movement. The temperature distribution in the solid and the positions where transformations occur are expressed analytically in terms of error function solutions and four coefficients which are determined from four nonlinear algebraic equations. These coefficients can be calculated either by trial and error or by any numerical method. MATHEMATICAL ANALYSIS Fig. 1 is a schematic diagram showing the zones of different phases 1, 2, 3, and 4 in the solidified portion of a semi-infinite pure liquid metal. The heat is subtracted from the system at x = 0 which is maintained

Jan 1, 1968

By H. B. Pulsifer

The unprecedented high price of zinc ore prevailing through the early months of 1915 caused great activity in the Joplin district of Missouri. The Media mill is conspicuous as one of the first of the new "big mills" of the district. The mill was built over a mine previously worked but abandoned in 1912 because of the leanness of the ore and the large quantity of water encountered. The ore prices prevailing—$100 a ton in June, 1915, as against $50 in 1912-—favored the new undertaking. The mill was designed for good recovery so that it might operate in times of depression. In design and equipment, the mill is exclusively local in conception and construction. Former Exploitation The tract of land is a part of the large Guinn holdings; 70 acres are comprised in this particular lot, which is situated just a mile north of the center of Webb City on the Alba line of the Southwest Missouri Electric Railway. The ore lies 242 ft. below the surface at the top of the knoll which is surrounded by the well known properties: Black Cat, Ground Floor, Florence, Hurry-Up, Electrical, and Mercantile. Since the abandonment, in 1913, of the Yellow Dog a bit farther to the north, the Black Cat, Ground Floor, and Florence workings had been flooded. However, as there was no cut through from this side into the area it was proposed to exploit, it was thought that moderate pumping facilities would take care of the water. Three shafts had already been sunk to the ore horizon during the previous operations; the ground was connected by wide drifts and possibly 10 acres mined out, principally about the two southerly shafts which at surface are 8 and 13 ft. lower, respectively, than the collar of the shaft at which the new mill was built. The former mill on the lease was known as the Bohemian Girl. This mill, built in 1910, was removed after some 3 years' work. A head frame and hopper still existed at the middle shaft, sometimes known as the lower Hold Out shaft, but at the most northerly

Jan 1, 1918

By J. W. Buch

IN THE FIELD of track haulage, interest has seemed to center on the question of larger mine cars both for handling material from loading point to shaft bottom or surface, and for shuttle service. Saving of time in car changing is obvious if larger cars are used. In addition, shorter trips result where car transportation is from face to opening without transfer. This also brings about side-track and equipment savings. Track shuttle service, using large automatic-dump cars (10 tons) between loading machines and trip loading point, has been a satisfactory solution for the operator who mechanizes a working mine regularly equipped with a large number of small mine cars. This development in track shuttle haulage, has made track installation and maintenance increasingly important, requiring closer supervision.

Jan 1, 1942

By A. M. Gaudin

It is only in recent years that substantial progress has been made in developing a physico-chemical picture of the solid state. The molecular concept, so useful in dealing with gases, was naturally carried over to the field of crystalline solids; it has resulted in the firm implanting of erroneous concepts that only now are being eradicated successfully. Two simply written and effective books on the subject are Crystal Chemistry by Stillwell' and An Introduction to Crystal Chemistry by Evans. A more complete treatment of the subject is available in a book by Wells. The monograph by Hucke14 also touches on a subject most easily perceived by reference to the brief introduction by Bragg; that master of the field. These texts make it clear that while some solids are built of molecules, many are built of ions, others of atoms connected in the form of giant molecules, and still others of cations and electrons. The various lattices in which these entities are systematically arranged, the joint use of several of these entities, and the transitional character of some of the bonds make for the great variety of crystalline solids. The purpose of this paper is to point out a most important corollary of present views on the structure of solids. In this connection the classification of solids in Table I is helpful.

Jun 1, 1955

By John V. Beall

Many Americans will judge the energy crisis by the picture shrink on their TV screen. And they are right to make this assessment considering the large areas of the country with marginal generating capacity, (See Fig, 1). The Federal Power Commission (FPC) recommends 20-25% reserve generating capacity above peak summer loads and 15-20% as minimal. The New York metropolitan area is the most concentrated power service area in the United States, and a spot check with Consolidated Edison, serving this area, revealed that on Friday, August 18, the company was operating at 5% reserve.

Jan 10, 1972

By R. Philip Hammond

Monazite has had a Cinderella-like history. Although nearly go per cent pure rare-earth compound (rare-earth phosphate) it was sought at first not for the rare earths but for the sake of a minor constituent—thorium. The thorium, essential for the Welsbach gaslight mantle, was present in only small quantities and the principal constituents, the rare earths, were largely discarded. Gradually, however, the rare earths have developed uses of their own and today have left the thorium far behind in value. Occurrence Monazite was first produced commercially about 1886, in North Carolina, where it was collected in small sluices by farmers who found it in stream beds on their land. The deposits were later exploited on a larger scale, but were mostly abandoned in a few years, when monazite from Brazil came upon the market in far larger quantities. Domestic production ceased entirely in 1906. The Brazilian source is still active, together with Indian, Dutch East Indies, and Australian deposits. Several other localities in the United States have yielded monazite, but none of these has produced commercially as yet. Monazite occurs originally in pegmatite~ and gneisses, through which, unfortunately, it is scattered in highly dispersed form. All commercially useful deposits consist of transported monazite sands liberated by erosion and concentrated by the action of water, which has sluiced away lighter materials and concentrated the heavy (D = 5.0 to 5.2) grains of monazite, together with ilmenite, zircon, garnet, and other dense minerals. The Carolina deposits were in stream beds; most of the other deposits mentioned are on or near the seashore, where the action of the waves has served to concentrate the monazite. In most cases today, the sands are worked to obtain the ilmenite and zircon, as well as monazite. The minerals are separated by means of sluices, dry tables, and magnetic separators, and each is finally obtained nearly pure. No crushing or grinding is necessary. The concentrates are shipped in fiber bags. Composition of Monazite As Table I illustrates, monazite is the anhydrous orthophosphate of the cerium Table i.—Typical Analysis of a Monazite Sand (India). Per Cent Thorium oxide............................. 8.1 Cerium oxide.............................. 30.6 Lanthanum oxide........................... 15. 7 Neodymium oxide.......................... 10.5 Praseodymium oxide........................ 2. 9 Samarium oxide............................ 1.0 Europium. gadolinium, and terbium oxides.... 0.7 Yttrium oxide.............................. 0.4 Dysprosium, holmium, erbium. thulium, ytterbium. and lutecium oxides................. 0. 1 Silicon oxide............t................... 2.4 Calcium, aluminum, and iron oxides.......... 1.0 Uranium oxide............................. 0.3 Phosphorus pentoxide....................... 26. 2 a The values given for the rare earths following samarium are approximate. being based upon analyses of concentrated fractions derived from monazite. The composition given represents Travancore monazite carefully freed from other minerals. goup of rare-earth elements. A small amount of yttrium and terbium group phosphate is also present.* All the rare-

Jan 1, 1948

By R. Philip Hammond

Monazite has had a Cinderella-like history. Although nearly go per cent pure rare-earth compound (rare-earth phosphate) it was sought at first not for the rare earths but for the sake of a minor constituent—thorium. The thorium, essential for the Welsbach gaslight mantle, was present in only small quantities and the principal constituents, the rare earths, were largely discarded. Gradually, however, the rare earths have developed uses of their own and today have left the thorium far behind in value. Occurrence Monazite was first produced commercially about 1886, in North Carolina, where it was collected in small sluices by farmers who found it in stream beds on their land. The deposits were later exploited on a larger scale, but were mostly abandoned in a few years, when monazite from Brazil came upon the market in far larger quantities. Domestic production ceased entirely in 1906. The Brazilian source is still active, together with Indian, Dutch East Indies, and Australian deposits. Several other localities in the United States have yielded monazite, but none of these has produced commercially as yet. Monazite occurs originally in pegmatite~ and gneisses, through which, unfortunately, it is scattered in highly dispersed form. All commercially useful deposits consist of transported monazite sands liberated by erosion and concentrated by the action of water, which has sluiced away lighter materials and concentrated the heavy (D = 5.0 to 5.2) grains of monazite, together with ilmenite, zircon, garnet, and other dense minerals. The Carolina deposits were in stream beds; most of the other deposits mentioned are on or near the seashore, where the action of the waves has served to concentrate the monazite. In most cases today, the sands are worked to obtain the ilmenite and zircon, as well as monazite. The minerals are separated by means of sluices, dry tables, and magnetic separators, and each is finally obtained nearly pure. No crushing or grinding is necessary. The concentrates are shipped in fiber bags. Composition of Monazite As Table I illustrates, monazite is the anhydrous orthophosphate of the cerium Table i.—Typical Analysis of a Monazite Sand (India). Per Cent Thorium oxide............................. 8.1 Cerium oxide.............................. 30.6 Lanthanum oxide........................... 15. 7 Neodymium oxide.......................... 10.5 Praseodymium oxide........................ 2. 9 Samarium oxide............................ 1.0 Europium. gadolinium, and terbium oxides.... 0.7 Yttrium oxide.............................. 0.4 Dysprosium, holmium, erbium. thulium, ytterbium. and lutecium oxides................. 0. 1 Silicon oxide............t................... 2.4 Calcium, aluminum, and iron oxides.......... 1.0 Uranium oxide............................. 0.3 Phosphorus pentoxide....................... 26. 2 a The values given for the rare earths following samarium are approximate. being based upon analyses of concentrated fractions derived from monazite. The composition given represents Travancore monazite carefully freed from other minerals. goup of rare-earth elements. A small amount of yttrium and terbium group phosphate is also present.* All the rare-

Jan 1, 1948

By L. E. Tanner

A study was made of the transformation kinetics of the commercial titanium-base alloys, Ti-2.5Al-16V and Ti-4A1-3Mo-1V, using two different heat treatment cycles: 1) step-quenching to aging temperatures from a ß solution anneal and 2) water-quenching from an a+ß solution anneal followed by reheating to aging temperatures. Metallographic examination and hardness testing provided the major portion of the data, while electrical resistivity, dynamic elastic modulus, and X-ray diffraction techniques were also used to obtain critical or confirnzatory data. TTT diagrams were constructed from these results. The sheet alloys, Ti-2.5Al-16V and Ti-4Al-3Mo-lV, are of current interest to the Department of Defense. As an aid to the planning of their respective heat treatments, a program was carried out to determine the transformation kinetics of these alloys using ß and a + ß reference states. This paper presents the TTT diagrams constructed from data obtained by metallographic examination and hardness testing, as well as by X-ray diffraction, electrical resistivity, and dynamic elastic modulus determinations. EXPERIMENTAL PROCEDURE Materials—Sheets of the alloys were obtained from the producers in the "mill anneal'' condition and were tested prior to shipment to assure their meeting mill specifications. Chemical analyses were also supplied and are presented in Table I. Heat Treatment—The majority of the data presented in this study were obtained from hardness testing and metallographic examination. Sample coupons were cut from the alloy sheets and heat treated on a mass scale. The annealing cycles were operated in the following manner: 1) The ß solution anneals were carried out in a horizontal tube furnace with the bare samples protected by a dynamic helium atmosphere. Following this treatment, the samples were quickly transferred to lead, solder, or oil-bath furnaces for aging. After prescribed times at the various reaction temperatures they were water-quenched. 2) The second cycle simulated commercial practice, which requires the alloys be quenched to room temperature following the a + ß sotution anneal. This anneal was carried out in a muffle furnace with a dynamic helium atmosphere. The specimens were then reheated from room temperature to the reaction temperatures in lead, solder, or oil-bath furnaces, followed by water-quenching after prescribed times at these temperatures. Information concerning the critical temperatures of the alloys was obtained from the literature and solution treatments were based on these values. A summary of the solution annealing treatments is found in Tables II and 111. The aging temperatures for the (a - ß alloys ranged in 50°C intervals from 200°C (392oF) to approximately 50°C below the ß/a + ß transus in the first cycle and approximately 50°C below the a + ß solution temperature in the second. The transformations in these alloys were known to be rather rapid, and thus aging times started at 0.5 min and went to a maximum of 7000 min. Hardness Testing and Metallographic Preparation— Heat-treated samples were sheared and mounted in Bakelite with their cut edges exposed. After a flat surface was ground, the hardness was determined in Vpn on an Armstrong-Vickers machine utilizing a 20-kg load. Three to four impressions were made on each specimen. After this procedure, the hardness impressions were removed and the edge surfaces of the specimens were prepared for metallographic examination in the usual manner. The etchant was 20 pct HF and 20 pct HNO3 in glycerine. Electrical Resistivity—It has been shown that the isothermal reactions in titanium-base alloys can be followed by measuring the changes in e1etrical resistivity attending these transformations. As mentioned earlier, the reaction kinetics of a-ß alloys are rather rapid; thus, it would be expected that resistivity data obtained from these alloys would be more significant if measurements were made continuously at the respective aging temperatures. To accomplish this end a special apparatus, based on the current-potential principle, was assembled. Its design was derived from earlier devices constructed by Colner and zmeska1 4 and Levinson.5 The set-up provided for the heat treatment zof machined specimens (approximately 2 x l0-4in. in cross section by 3 in. in length) and the determination of their relative

Jan 1, 1962

By L. S. Darken

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By J. H. Wernick, J. E. Kunzler

HIGHLY pure metals are needed for low-temperature electron transport studies in progress. Recent improvements in purification techniques, such as zone refining, have made it possible to obtain metals with improved purity. For some metals, the improvement has been to the extent that ordinary analytical techniques are inadequate and special methods are needed.1 For other metals purification is more difficult, so that simple but rapid analytical methods are desirable as an aid in evaluating the effectiveness of purification procedures. Furthermore, it is desirable to be able to determine the impurity level of the sample or ingot with the minimum of physical disturbance of the material. In order to aid in the preparation of purer metals, techniques involving the measurement of electrical resistance at liquid-helium temperatures have been devised for studying impurity distributions in zone-refined ingots and other bulk samples without destroying the ingot or its geometry. The method yields information on the variations in purity along the length of the ingot or sample and provides a measure of the overall purity of the material. Compared with ordinary analytical methods, the resistivity method is rapid, sensitive, and does not require significant physical disturbance of samples with reasonable shapes. It has the disadvantage that resistance measurements are not specific, i.e., they do not identify the impurity. However, this disadvantage is offset by the advantage of being able to establish a measure of the overall purity so far as electrically active" impurities are concerned. METHOD AND ITS BASIS The method is based on the well-known fact that the resistivity, at Liquid helium temperatures, of a reasonably pure metal containing no regions with additional phases decreases with increasing chemical purity or a decrease in the number of physical defects. It is convenient to separate the total resistivity into three parts: where is the resistivity due to the scattering of the conduction electrons by the lattice vibrations or phonons, p is the contribution due to physical defects, and originates from the effect of chemical impurities in the metal. Insofar as Matthiessen's rule is obeyed,2 pphys and pchem are independent of temperature. Except possiblyin the very purest metals, ptherm is negligible at liquid helium temperatures and For zone-refined metals, which normally are well annealed and consist of large grains, at the chemical purity levels thus far attained the available data indicate that pphys is negligibly small or at least constant throughout the ingot. Assuming that the effect of physical defects is negligible for isotropic metals, This assumption appears consistent with most of

Jan 1, 1959

By W. B. Daly, A. S. Richardson

The application of artificial refrigeration, or air-conditioning, to the ventilation of deep, hot mines has long been a subject of interest to the operators of such properties. Artificial cooling of the air in theaters, railroad coaches, and various industrial plants has been so successful within recent years that it has been natural to assume that the adoption of similar methods would afford a ready solution to the difficult problem of mine ventilation. It should however, be obvious, that although there may be nothing technically impossible in the application of this process to mine ventilation there is a great economic distinction between the maintenance of a high standard of comfort for a large number of people in a relatively small space such as a theater and the cooling of air to improve working conditions for miners scattered throughout the extensive workings of a large mine. Many methods of air-conditioning have been considered by the management of the Anaconda Copper Mining Co. at various times, but until the development of the process to be described in this paper none has seemed economically practicable. The Ventilating Problem at Butte The main obstacle to satisfactory ventilation in the Butte mines is the normally high temperature of the granite country rock. In the present operating zone, rock temperatures as high as 120' F. have been noted, and in some parts of the district the rate of increase of temperature with depth has ranged as high as 3.5" F. per 100 ft. Other factors, such as the decay of mine timber and the oxidation of sulfide minerals in the ore bodies, contribute to raise the temperature of the air in the working places but, particularly in the development of the mines to greater depth, the naturally high temperature of the rock is of predominant importance. In few other places, probably, are the ordinary ventilating measures more hindered than at Butte. At an operating depth now exceeding 3000 ft., all of the air required for ventilation must pass through timbered shafts which, because of heavy ground, are of small size and offer great resistance to the flow of air. Shaft compartments are rarely more than 4.5 X 5 ft., and the shaft area open to the flow of air usually does not exceed 65 sq. ft.; in only two shafts is the area as great as 85 sq. feet.

Jan 1, 1934

By Maurice Ewing

THE purpose of this paper is to present the results of the application of the earth-resistivity method of subsurface investigation to the problem of locating seams of anthracite coal beneath a mantle of soil and subsoil. Details are given of the successful use of this method in locating the outcrops of anthracite seams in actual prospecting. The presence of the outcrop of an anthracite seam is indicated at points where electrical resistivity tests showed relatively low readings. The reason for this is that in some localities the resistivity of anthracite was found to be about 0.0001 megohm-cm. compared to 1 to 200 megohm-cm. for shales and sandstones. For two reasons it is believed that the data sum-marized in this paper should be of particular interest. In the first place, most of the interpretations of the resistivity survey have been checked by subsequent drilling and some by the removal of the overburden and the exposing of the anthracite seams. It is infrequent that the oppor-tunity for checking results so thoroughly is given. In the second place, the fact that recent commentators1,2,3 on the application of geophysical methods to mining have concluded that direct prospecting for anthracite and other types of coal is not promising makes the good results obtained more significant. So far as the authors can learn, the only previous experiment with electrical methods in the Pennsylvania anthracite field was one made by Sherwin F. Kelly in 1922, when he used the self-potential method at Wilkes-Barre4. The profile he made does not show a very marked correlation with the geologic cross section. Kelly points out that stray currents from electric motors in the mines undoubtedly affected his results, but the experience of the present authors with stray currents from mining machinery suggests the possibility that the potentials measured by Kelly were due almost entirely to this effect.

Jan 1, 1936

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.' The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of ' However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-' have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h') formed by the reaction where, accorhng to the notation of Kroger and Vink,6'7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i' and Fe3' ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.'-' A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i' and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By RUSSELL C. FLEMING

THE important advances that have been made of recent years in mining and milling methods and in mechanical equipment at mines need no re- telling, but there has been a remarkable growth in one type of equipment which has gone nearly unnoticed. That is the increasing use of storage-battery locomotives underground. Since the war the number of these locomotives and their field of use have increased tremendously; their growing acceptance represents an al- most complete reversal of opinion from an earlier period when they were generally looked upon as in- adequate for the strain of mine service. At the time when storage-battery powered units were first making their bid for recognition, the use of power in haulage had already passed through several phases; hand tramming, rope haulage, compressed air locomotives, even gasoline locomotives, had all been used, ending finally in the general adoption of the electric trolley locomotive for practically all power-haulage requirements. It was, and is, conceded that the trolley loco- motive met more adequately the varied and severe conditions of mine service than any previous type of haul- age unit. Subsequent developments have had to endure comparison and surpass in performance that type of haulage before changes would be considered.

Jan 1, 1930

By A. L. Field, P. H. Royster

Bureau of Mines Technical Paper 189 consists of a record of the scientific data obtained in the iron blast-furnace slag investigation which is reported in Technical Paper 187, "Slag Viscosity Tables for Blastfurnace Work." It includes a description of the method of preparing the synthetic melts, construction of an improved electric furnace, and refinements in laboratory methods of measurement. Only the general features of the work and the conclusions drawn from the experimental data can be given attention here. Silicates in the Liquid State In the manufacture of refractories, Portland cement, glass, and porcelain, and in pyrometallurgical operations, importance attaches to the behavior of-silicate compounds at temperatures beyond the range of common experience. This field of research has not been investigated as carefully as its scientific and industrial importance would seem to warrant. Probably the most important of the unsolved problems in the chernistry of silicates is the question of their stability in the liquid state. That little progress toward the solution of this problem has been made is not strange if there be borne in mind the difficulties attending experiments made at temperatures at which silicates become fluid, and the comparatively short time since it became possible to measure these temperatures. On the other 'hand, considerable progress has been made in the study of the compounds in the solid state because of the directness and simplicity of methods of optical examination. Important advances have been made by the Geophysical Laboratory at Washington in recent years. An extended study has been made there of saturated solutions representing a considerable number of binary and ternary systems of the more common refractory oxides. The methods

Jan 1, 1918

By Edwin Ludlow

EDWIN LUDLOW, president of the American Institute of Mining and Metallurgical Engineers for the year beginning Feb. 15, 1921, is a well-known figure in the state that was the birthplace of the Institute-Pennsylvania-although he was born and educated in New York and is again one of its residents, after years of active work in the field. Mr. Ludlow was born at Oakdale, Long Island, and was graduated from the School of Mines at Columbia University with the class of 1879. After graduation, he became a civilian worker with the U. S. Engineer Corps under General William Ludlow, his brother, and for two years did river and harbor surveying along the New Jersey coast.

Jan 1, 1921

By S. Korman, S. B. Tuwiner

THE purpose of this study is to investigate the effect of agitation upon the flotation of chal-cocite. It is believed that the concentration of collector which is required to produce a water-repellent surface upon the mineral is determined among other things by the rate of collector diffusion through an impeding film of more or less stagnant fluid. Its thickness depends upon the intensity of agitation. In the first part of this study a method is developed for determining the thickness of the fluid film upon a polished surface of synthetic chalcocite. The film thickness is then determined as precisely as possible under three readily reproducible condi-tions of agitation intensity. These determinations serve as a quantitative evaluation of agitation. In Part 2 it is demonstrated that in solutions of lime at PH 10.5 and in the absence of air or dissolved oxygen the concentration of collector required to develop water-repellency upon the surface in any given time is a function of the fluid film thickness, and that after about 10 min the relation becomes linear. This points to the possibility that the collector ions may be involved in a diffusional process through the fluid film. In Part 3 it is shown that where air is present more collector is required to produce water-repellency than for the case in which air is excluded. Next, it is shown that for the latter case the most minute amount of sodium sulphide suffices to preclude development of water-repellency. Both oxygen and sulphide are in a sense, therefore, depres- sants for chalcocite in a lime solution at PH 10.5. When oxygen and sulphide are present simultaneously there is a region of minimum critical collector concentration for water-repellency which is very markedly lower than the concentration where oxygen alone or where sulphide alone is present. Moreover, this minimum appears to be identical with the collector concentration which is required where sulphide and oxygen are both excluded. This would appear to indicate that in certain ranges of concentration of oxygen and sulphide, each cancels the effect of the other. The range of concentration of solution for this effect in solutions saturated with oxygen is a function of the agitation intensity. Thus we are led to believe that a chemical reaction involving sulphide and oxygen occurs at the surface of the chalcocite. Part 4 of this study is a further development of this idea and some of its consequences from an electrochemical standpoint, while in Part 5 the disappearance of sulphide from pulps of several minerals is noted with an indication that both dissolved oxygen and the mineral are necessary, the reaction being catalytic or pseudocatalytic. Part 1. Determination of Fluid Film Thickness The Fluid Film Concept: The hindrance to the diffusion of collector to the surface of the chalcocite is a barrier of stagnant fluid in the vicinity of the surface. It is the same barrier that limits the rate of transfer of heat, the rate of solution of dissolving crystals, or any of the other rates pertaining to chemical engineering unit operations in which the film resistance to diffusion plays a principal role.' Fluid films are present upon the surface to an extent which varies with the geometry and intensity of agitation. They result from the fact that in the region within the fluid near a surface, motion is entirely parallel to it. From the standpoint of transfer to or away from the interface the effect is as though the fluid were stagnant. Outside of the film, movement of the fluid may be streamline or turbu-

Jan 1, 1951

By S. Korman, S. B. Tuwiner

THE purpose of this study is to investigate the effect of agitation upon the flotation of chal-cocite. It is believed that the concentration of collector which is required to produce a water-repellent surface upon the mineral is determined among other things by the rate of collector diffusion through an impeding film of more or less stagnant fluid. Its thickness depends upon the intensity of agitation. In the first part of this study a method is developed for determining the thickness of the fluid film upon a polished surface of synthetic chalcocite. The film thickness is then determined as precisely as possible under three readily reproducible condi-tions of agitation intensity. These determinations serve as a quantitative evaluation of agitation. In Part 2 it is demonstrated that in solutions of lime at PH 10.5 and in the absence of air or dissolved oxygen the concentration of collector required to develop water-repellency upon the surface in any given time is a function of the fluid film thickness, and that after about 10 min the relation becomes linear. This points to the possibility that the collector ions may be involved in a diffusional process through the fluid film. In Part 3 it is shown that where air is present more collector is required to produce water-repellency than for the case in which air is excluded. Next, it is shown that for the latter case the most minute amount of sodium sulphide suffices to preclude development of water-repellency. Both oxygen and sulphide are in a sense, therefore, depres- sants for chalcocite in a lime solution at PH 10.5. When oxygen and sulphide are present simultaneously there is a region of minimum critical collector concentration for water-repellency which is very markedly lower than the concentration where oxygen alone or where sulphide alone is present. Moreover, this minimum appears to be identical with the collector concentration which is required where sulphide and oxygen are both excluded. This would appear to indicate that in certain ranges of concentration of oxygen and sulphide, each cancels the effect of the other. The range of concentration of solution for this effect in solutions saturated with oxygen is a function of the agitation intensity. Thus we are led to believe that a chemical reaction involving sulphide and oxygen occurs at the surface of the chalcocite. Part 4 of this study is a further development of this idea and some of its consequences from an electrochemical standpoint, while in Part 5 the disappearance of sulphide from pulps of several minerals is noted with an indication that both dissolved oxygen and the mineral are necessary, the reaction being catalytic or pseudocatalytic. Part 1. Determination of Fluid Film Thickness The Fluid Film Concept: The hindrance to the diffusion of collector to the surface of the chalcocite is a barrier of stagnant fluid in the vicinity of the surface. It is the same barrier that limits the rate of transfer of heat, the rate of solution of dissolving crystals, or any of the other rates pertaining to chemical engineering unit operations in which the film resistance to diffusion plays a principal role.' Fluid films are present upon the surface to an extent which varies with the geometry and intensity of agitation. They result from the fact that in the region within the fluid near a surface, motion is entirely parallel to it. From the standpoint of transfer to or away from the interface the effect is as though the fluid were stagnant. Outside of the film, movement of the fluid may be streamline or turbu-

Jan 1, 1951