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By J. W. Hickman, E. A. Gulbransen

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By AIME AIME

Maurer's review summarizes quite thoroughly the various theoretical developments and experimental findings that contribute to the knowledge of rock mechanics in drilling. This discussion supplements Maurer's paper by including generalities that either have been incompletely treated in his review, or formulated from new considerations by the discussant and from hitherto unpublished experimental data. These generalities are associated with the observation that all mechanical methods of rock drilling essentially comprise a sequence of indexed, concentrated loadings on the bottom of the hole being drilled.

Jan 1, 1967

There are no data available of shipments until 1858, and then estimated, when railroad service became available. By reason of the iron made in the county, and the large amounts of salt, the tonnage used locally was quite large, and until 1860 these are estimated from the probable salt and iron production. After 1859 the tonnages shipped by rail are partly estimated from the total shipments of the Allegheny Valley Railroad from four counties. It is believed that the totals are below, rather than above, what the actual production was. While considerably larger for the same years than figures given by the Secretary of Internal Affairs and census reports, these data were always too low in those days, partly because of lack of facilities for gathering them, but more largely because of the strong prejudice existing in those days against furnishing such data to any governmental agencies.

Jan 1, 1942

By Gerhard Derge, Harold Markus

The first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from 1.12† volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. Experimental Data Cations.—The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.1 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 10-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

By Harold Markus, Gerhard Derge

The first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from 1.12† volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. Experimental Data Cations.—The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.1 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 10-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

By Harold Markus, Gerhard Derge

THE first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from I.I2[t] volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. EXPERIMENTAL DATA Cations.-The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.2 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 0 7-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

By J. M. Seeman, R. A. Dodd

If some solution-quenched supersaturated aluminum solid solutions, e.g.., Al(Cu), are plastically deformed at room temperature and then aged at 200oC, the hardness may first decrease before increasing in the usual manner ' A similar transient softening is observed, even in the absence of plastic deformation, when a thin foil or small-diameter wire Al(Cu) specimen is rapidly quenched from the solution-treatment temperature and then aged.' Also, some solution-quenched and neutron-irradiated alloys undergo an initial hardness decrease during subsequent aging.3 The usual explanation of the transient softening in the above examples involves the effect of vacancies introduced by plastic deformation, rapid quenching, and neutron irradiation, respectively However, the mechanism of softening is not unequivo-cably established. In the first-noted case, Gane and parkins' observed that the softening was approximately proportional to the difference in the atomic diameters of solute and solvent, and it was argued that, if a large relative difference in atomic diameter promoted vacancy-assisted room-temperature solute diffusion to dislocations, dislocation climb occurring during subsequent aging at 200°C could cause transient softening. Some substantiation of this theory was offered by the additional observation that discontinuous yielding of solution-quenched polycrystalline Al(Cu) tensile specimens was suppressed by interrupting the test for a short aging treatment at 200°C. Of course, reversion (resolution of GPI) at 200°C would also cause softening, and Sil-cock4 expressed the opinion that the softening in the case of Al(Cu) must be partly associated with reversion. Also, Hirsch5 commented on the possibility that, if jogs cause hardening, an anneal at 200°C should straighten the jogged dislocations and result in softening. However, parkins' has re-expressed his belief that these mechanisms are not entirely consistent with the observed serrated stress-strain curves. Experimental. New data has now been obtained for Al(Cu), Al(Ge), Al(Mg), and Al(Zn) primary solid-solution alloys. These alloys were prepared from metals exceeding 99.99 pct purity, and specimens 4 by 4 in. diam were solution-treated, quenched, deformed 10 pct in compression at room temperature, and aged at 200'C in a cottonseed oil bath for various times. Generally, these operations could not be carried out in rapid succession, so the alloys were stored in a freezer between treatments to minimize aging. The variation in hardness with aging time, Figs. 1 to 4, was determined by microhardness testing with a 3.0-kg load. At least five readings were averaged to obtain each data point, and all measurements were taken about the center circumference of each cylinder (region of maximum deformation). Each specimen was used to obtain only one data point, i.e., specimens were not replaced in the aging bath after measurements were made. In

Jan 1, 1968

By G. H. Cady, L. C. McCabe, D. R. Mitchell

While running certain float-and-sink tests, unit coal calorific values were determined for gravity fractions of a series of Illinois coals from several districts in the southern part of the state. When these values were plotted against specific gravity what appear to be characteristic curves of somewhat different shape were obtained for each district represented. This in itself seems noteworthy. The shape of the curves seems to indicate that the lightest fraction of the coal, which inspection shows to be largely vitrain, suffers the least deterioration in storage. It was also observed that on dilution curves established with dry ash and B.t.u. values the fractions of 1.35, 1.40 and 1.50 sp. gr., which constitute the greater weight per cent of a given coal sample, fall more frequently on a straight dilution line than do the lighter or heavier fractions of the same sample. In most instances there is a marked steepening between the 1.35 and the fraction of lighter gravity. In general the curve increases in steepness between the fractions of 1.50 and 1.70 specific gravity. The variations in the unit coal-specific gravity curves as well as those observed in dilution curves which appear to be pertinent to this problem are: (I) variation in coal substance with change in specific gravity, (2) variation in kind and quantity of mineral matter with the specific gravity of the fraction, (3) factors of analytical procedure which tend to introduce error in analysis, particularly in high-ash and high-sulfur fractions. DISCUSSION (A. C. Callen presiding) E. Stansfield, ? Edmonton, A1ta.-—The necessity of avoiding oxidation in grinding and in drying should be emphasized. My assumptions as to pure coal coincide with t,he author's but most of my curves are nearly straight lines. The low sulfur content

Jan 1, 1934

By S. Stutz

Three years ago, at the Philadelphia meeting, in February, 1881, the author had the pleasure of presenting to the Institute a paper on coal-washing machinery.* Since that time many new machines, with important improvements and labor-saving apparatus, have been introduced, the construction and description of which may be of interest to some of the members of the Institute. By referring to the above-mentioned paper, and more especially to Plate IV., representing a vertical section of a coal-washer, it will be noticed that the bottom of the plunger-box B is made level or horizontal, and supports a spring-buffer F for the purpose of limiting the down-stroke of the plunger P and receiving the impacts of the latter. Althongh the construction of the box, in view of these impacts, received from the start the proper attention (the bottom of the chamber 3 being made of three thicknesses of 3-inch planks, resting on 6-inch sqnare columns), yet, through careless working of the machinery, without the necessary water in the box, it proved in several instances not strong enough, and had to be changed. To prevent such interruptions in future, it became necessary to devise some means for relieving the machine from the impacts of the plunger altogether. This has been accomplished by the arrangement shown upon Plate I. of this paper, representing a new waesher; and not only has the difficulty been overcome, but also sorne other advantages have been obtained, as will be seen further on. The compartments +, A' of the separator-box have been set upon heavy cast-iron brackets B, leaving sufficient space below the bottom for the buffer F and the sediment-valve K. By means of the plunger-rod 6 passing through the stuffing-box s to the outside, and provided at its lower end with a shoe a, the impacts of the plunger are now transmitted from the buffer F directly to the foundation. At the same time a better guide for the plunger P in its up and down movement has been obtained. The plunger of the former machine had only the guide I and the yoke Y, whereas the new machine has an additional guide in the stuffing-box s, thus preventing wear and friction of the plunger against the lining of the box. Further-

Jan 1, 1884

By Clyde Williams

IF you would allow me some liberties, I would restate the title of this talk as "Scientific Research, Our Greatest Resource," because that title would represent more clearly a present-day conception of the metals and minerals situation. It is a subject worthy of careful consideration. Canada and the United States are so similar and interdependent in their national economies that, in the following discussion, examples of conditions in the United States may be interpreted to apply to Canada as well. Moreover, it is a striking fact that the per capita value of mineral production in Canada and the United States in 1940 was almost the same. Therefore, in the consideration of this subject, I have made no attempt to differentiate between the two countries. Consumption of the world's mineral resources in the last few decades. and particularly during World War II, has been so enormous as to require some form of magic to ensure the continued progress of civilization in the face of a diminishing supply of these resources which are so critically essential. As C. K. Leith pointed out, in 1941, indus-

Jan 1, 1947

By G. Thomas, O. Johari

MEIERAN and Richman' have proposed a method for the determination of electron-diffraction patterns from twinned bcc crystals. It is the purpose of this note to present a general method capable of predicting the positions of all reflections from both matrix and twin regions for all possible orientations of cubic crystals. The method has been verified for twinning in explosively deformed copper, and is found to be a very useful tool when used in conjunction with stereographic projection, and dark-field electron microscopy. Let an isometric crystal be twinned in any (hkl) plane. The twinning can be considered either as a reflection in the twin plane or as a 180-deg rotation about the twin axis. In reciprocal space, the 180-deg rotation about the twin axis would place a given point p, q, Y to a new position P, Q,R, such that both will be equally inclined to the twin axis. This is represented in Fig. 1. If the coordinates of three such pairs of points are determined, the matrix of the transformation can be obtained.' It is also seen that such pairs would satisfy another condition, i.e., the vector [p,q,r] plus the vector [P,Q,R] will yield a multiple of hkl, i.e., the indices of the twin plane, because in isometric systems the axis [hkl] is perpendicular to the plane (hkl). This can be simplified by taking the points along the three axes. If a point h2 + k2 + 12, 0, 0 is taken along the x axis, it is seen that its new indices should be so as to yield a sum 2h2, 2hk, 2hl,i.e., 2h(h,k,1). (Also the points h2 - k2 - 12, 2hk, 2h1, and h2 + k2 + 12, 0, 0 are equidistant from the origin and both points make equal angles with the twin axis, i.e., cos-' h/dh2 + k2 + l2.) Similar operations for the points yield respectively, after the 180-deg rotation about the twin axis. Following the method due to Buerger,' the matrix of the transformation is obtained as follows: Using this matrix the indices of any other point in reciprocal space can be determined. This matrix is much simplified for (111) twinning commonly encountered in fcc metals, since are each equal to —1; hence

Jan 1, 1964

By TRUMAN S. FULLER

THE GREAT INTEREST in decomposition and trans- formation, so evident in the study of alloys during the last two years, was reflected in the many papers on this subject, presented at the first session of the Institute of Metals, Tuesday morning. Dr. F. A. Thomson, of Montana State School of Mines, presented the first paper by C. Wilson, H. F. Silliman, and E. C. Little, "Rate of Precipitation of Nickel Silicide and Cobalt Silicide in the Hardenable Copper-nickel-silicon and Copper- cobalt-silicon Alloys." Dr. R. F. Mehl, in discussing this paper, stated that the title was somewhat deceptive, as it indicated that the rate of precipitation is determined; the method used is a measurement of electrical conductivity and hardness, neither of which is suitable for a quantitative measurement of rates of reaction or precipitation in the solid state. Hardness is also uncertain because it depends so much upon particle size. Of the various methods proposed for the study of rate of reaction and precipitation the evaluation of volume of reaction produced from the area of photomicrograph is the best.

Jan 1, 1933

Discussion of the paper of George C. Stone, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 82, October, 1913, pp. 2401 to 2402. D. S. JACOBUS,* New York, N. Y.:-The engineers of the country are waking up to the possibilities of waste-heat boilers. As the cost of fuel increases, and as more attention is given to economies, it is evident that a great deal may lie gained by utilizing heat that has ordinarily been wasted. The art in the manufacture of' waste-heat boilers has. advanced so that it will now pay to install them under certain conditions where it would not have paid to install boilers constructed in accordance with older methods. In using boilers where the gases are at a comparatively low temperature, a great deal depends on the method of baffling the boiler in securing good results. The Babcock & Wilcox Co. has made a careful investigation of the laws of heat transfer and has applied the same to waste-heat boilers, which have been carefully tested under operating conditions, with the result that we now know what to expect with different arrangements of baffles and heating surfaces. The old idea of installing waste-heat boilers was to provide an arrangement where the draft loss would be a minimum, and little or no attention was paid to the effect of different systems of baffling on the steaming capacity of the boiler. In some instances, to secure a minimum draft loss no baffles were placed in the boilers. After making a most careful study of the subject it developed that this practice was bad, and that to obtain the best commercial economy, in place of endeavoring to obtain a minimum draft loss, an arrangement should be used that would lead to the maximum amount of heat transmission with a comparatively high draft loss. In nearly every case the amount of resistance of the gases fussing through the boiler involves the use of an induced-draft ,fan, but the additional capacity developed by the boiler over that which could be secured with the older designs, through arranging the heating surface properly and using proper baffles, much more than pays for the increase in the steam required to drive the fan.

Jan 12, 1913

By D. N. Witman

ONE of the special uses to which the electric furnace has been put recently is the melting of an alloy of nickel and cast iron for the production of electrical-resistance grids. The metal sections of these grids, Fig. 1, are quite uniform for each pattern, but there is, among the various patterns, a variety of thicknesses. The cross sections vary from 1/2 by 3/16 in. to as small as 1/8 by 1/8 in. The electrical resistance f a perfect casting lies within 10 per cent. above or below the fixed listed resistance for each pattern. Good molding is essential to success in the making of these grids, for with absolutely correct metal, a variation of 0.01 in. in width and thickness of section on some of the patterns may mean as much as 12 or 14 per cent. variation in resistance. The service for which these castings are intended demands that the metal, even in the smallest castings, be very soft, showing an open, gray, highly graphitic structure in order that they may be resistant to shock, and stand up well under rough usage. The metal used for this purpose is a gray iron alloyed with 4 to 5 per cent. of nickel, which element, when the composition of the alloy is correct, imparts toughness and pliability to the metal and helps to overcome the tendency of metal to run white and become brittle because of the rapid cooling action of the sand mold. When cold, these castings can be twisted into various shapes, taking a permanent set without breaking. The alloy has approximately double the electrical resistance of ordinary cast iron. The metal specification is as follows: PER CENT. Silicon 2.40 to 2.60 Sulfur Under 0.05 Phosphorus Under 0.08 Manganese Under 0.40 Total carbon 3.60 to 4.00 Nickel 4.00 to 5.00 Copper 0.50 to 0.70

Jan 8, 1921

E. T. Dumble, Houston, Texas (communication to the Secretary) : During the field-season of 1890 I had occasion to examine some of the salines of eastern Texas. As the result of my stridy of them I came to the conclusion that, together with the oil of Hardin county (since extended to Beaumont by the work of Capt. Lucas) and the rock-salt and gypsum-deposits of the coast country, extending southward to the Rio Grande, these were simply a continuation of similar deposits in Louisiana described by Hilgard, Hopkins, and others; and I recommended the sinking of wells wberever they were found.

Jan 1, 1902

By D. I. Bardos, F. X. Spiegel, R. K. Malik, Paul A. Beck

Study of the occurrence of elongated ß-Mn phase fields and of their direction of extension in fifteen ternary systems indicates that the ß-,mn phases formed by manganese with other transition elements and with either silicon, germanium, or tin may be considered as electron phases. In these phases the alloying behavior of silicon on the one hand and of germanium and tin on the other shows a significant difference . Formally all observations can be satisfactorily described by attributing to germanium and tin an apparent electron concentration of nine electrons per atom. This behavior may be interpreted by assuming that germanium and tin exclude itinerant electvons because of a strong repulsive potential arising fromthe requirement that their wave junctions be orthogonal to those of- the closed d shells of these atoms. The absence of a d shell in silicon allows this atom to admit itinerant d electrons. The following new ternary phases of unknown structure were identified by means of their X-vay difjraction patterns: (Mn,Co,Si)I , (Mn,Co ,Si)Y, (Mn.Co,Si)Q , (Mn ,Ni ,Si)W , and (Mn, Ti ,Si)A. The X-ray data suggest that these phases have large unit cells and that to some extent they may he related structurally to the 0 phase. The a phase and certain other phases formed by transition elements are characterized by their preferred occurrence at a constant electron concentration. AS a result, these "electron phases" have relation to electron concentration. The tendency of the B phase to form elongated phase fields in ternary systems along the directions of constant electron concentration has been previously demonstrated. The occurrence of an elongated 0-Mn phase field in the ternary system Mn-Co-Si was schematically indicated by Cherkashin et al.l0 The present study includes fifteen ternary systems, each containing in addition to manganese a second transition element from the group Ti, V, Cr, Fe, Co, Ni and one of the nontransition elements silicon, germanium, or tin. In each system the boundaries of the B-Mn phase were determined in the 900°, 950°, or 1000°C isothermal section, the temperature being dictated on the one hand by the requirement of sufficient rates of diffusion to approach equilibrium conditions in reasonably short annealing periods and on the other hand by the need to avoid as much as possible the partial melting of alloys during annealing.

Jan 1, 1967

By V. B. Kurfman

Grain refinement of Mg-Al melts by carbonaceous additions has been attributed to nucleation by aluminum carbide. The effects of process and alloy variables are interpreted and predicted in terms of the dispersion and chemistry of this phase. The grain coarsening action of Be, Zr, Ti, R.E., chlorination, temperature extremes, and prolonged holding times is described. Measures necessary to insure an adequate dispersion of the catalyst are discussed. CARBON inoculation treatments have become fairly well known and used for grain refinement of magnesium alloys containing Al. Although there is general agreement that a nucleation process occurs, the process is not understood and the inoculants are used in a rather empirical fashion. The treatment is applied to the class of alloys containing 3 to 10 pct Al, i.e., AZ31A to AM100A. Typical methods involve melting, alloying, and adjusting the temperature to 1400° to 1450°F. Then 0.01 to 0.5 pct C as CaC2, C6C16, or lampblack is added by any convenient means, and the melt poured within 10 to 30 min. Investigators generally have been impressed by an assumed similarity of this refinement process to superheat grain refinement, which depends on heating approximately the same alloys to a temperature in the range of 1550" to 1650°F, then pouring promptly after the melt is cooled to the pouring temperature. Various predictions have been made that carbon refinement would replace superheating in commercial practice due to reduced process costs, but this replacement has not fully taken place because of production difficulties and conflicting observations. Davis, Eastwood, and DeHaven1 agree with Nelson2 and wood3 in suggesting that an excess of inoculant may be harmful. Wood however says that overtreat-ment is not a problem in production use of hexa-chlorobenzene inoculation, and Hultgren and Mitchell4 claim no evidence of harm from excess additions. Various grain coarsening reactions are known to occur, including the possibility of overtreatment mentioned above. Trace amounts of Be,2 Zr, and Ti may prevent refinement by either a carbon treatment or a superheat. Occasionally treatment with cl25 may cause coarsening, although the Battelle refinement process' uses a CC14-C12 blend. Grain coarsening also tends to occur on holding at temperatures below 1350°to 1400°F, especially after a superheat treatment, and for this reason Nelson2 stresses the desirability of a refinement method useful at lower temperatures for open pot melting practice. Since a carbon treatment can be made to work at temperatures below 1400°F, it seems desirable to investigate the mechanism of the refinement and the mechanisms of the coarsening reactions in order to establish control conditions for use in commercial production. The identity of the nucleating phase must first be established and then the factors affecting its chemistry and physical dispersion must be determined. THE IDENTITY OF THE NUCLEATING PHASE Davis, Eastwood, and DeHaven suggested that the nucleating phase in this system is Al4c3,1 but Mahoney, Tarr, and LeGrand8 disagree, largely because they found no evidence of the compound in alloys after carbon treatment and because there is no indication that aluminum carbide should be unstable over the temperature range used in the superheat treatment. This latter objection is based on the assumption that both the carbon treatment and the superheat treatment introduce the same nuclei. Electron diffraction studies have been made to identify the nucleating phase. Samples of grain refined A292 have been selectively etched SO that clean surfaces are obtained and so that secondary phases are in relief. Electron diffraction patterns from these surfaces have established that the carbon treatment of A292 introduces into the metal a large number of small, plate-like particles with a structure very similar to Al4C3. In most cases, the plate-like nature of the particles prevented positive identification but in the cases where the identification could be made the particles proved to be AIN A14C3. However, enough variation in lattice constants was observed so that all compositions from pure A14C3 to the 50:50 solid solution A1N.Al4C3 were probably present.14 In A14C3 and especially AlN.Al4C3 the A1 atoms occur in layers within which they have the same hexagonal symmetry and spacing as the Mg atoms in a single basal plane of a magnesium crystal. The solid solution spacing lies between the 3.16 of AIN and the 3.3? for Al4C3, in satisfactory agree-

Jan 1, 1962

H. H. Hill.—I believe that as petroleum engineers you are all more or less interested in geophysical prospecting. A large number of the papers that have been written on that subject are too detailed or too much involved to be of much value to a person who is not familiar with the subject, so I suggested to Mr. Fohs that he might bring us something that we could all understand. As I take it, we are interested in learning something about the different methods, the places where they have been used, their limitations and in general whether they have given satisfaction in locating oil deposits. F. J. Fohs, New York, N. Y.—I will briefly summarize some of the results as I Bee them from my practical contacts with them and my discussion of the subject with some of the more important rnen both in this country and Europe. Geophysical Methods 1. Seismographs: A. 1. Sonic refracting seismographs of Karcher, McCullom and Reiber. For rapid reconnaissance and also for detail—perhaps, the best type of instrument. 2. Mechanical refracting seismographs of the Weichert-Mintrop type. B. I. Sonic seismographs using reflected sound from contacts of sufficiently unlike beds where latter are thick enough, being used for detail of both salt domes and ordinary structures where a good reflecting key bed occurs. 2. Torsion Balances: Made in three sizes with greater portability and loss of but 20 per cent. in medium size and loss of 40 per cent. efficiency in smallest size. A. Used to best advantage in detailing salt domes, in noting anomalies of deep-seated structures of the Edgerly, La., type (but not always certain here and dependent on interpretation which involves both experience and the human equation to a large degree). R. Used to advantage in mapping faults where a lime or other denser bed occurs upthrown, and the topographic irregularities are not too involved. C. Of use where buried granite plugs and buried-hill structures occur as in the Western Texas fields. D. Believed of little use for other types of structure. 3. Magnetometers or Variometers: Now built horizontal and vertical with declinometer combined in one instrument. A. Practical in mapping granite or basic igneous rock plugs and intrusions, or of detritus therefrom. Adams has recently demonstrated definite results in mapping the well known Panhandle arch.

Jan 1, 1928

By W. H. Triplett

Silver-lead-zinc replacement deposits occur in limestones of the anticlinal Caja range at Providencia, near Avalos, Zacatecas, Mexico. The description deals with intrusives, outcrops, preferred horizons, changes from bedding to fracture, control in depth, and variations in abundance and ratios of minerals throughout a vertical range of 500 m. THE purpose of this paper is to record a few field observations and accumulated office data concerning outcrops, relation of ore occurrences to intrusive and host rock, and mineral zoning. Reasons for some of the phenomena are not clear to the author so the facts are given with the hope that other investigators may be able to furnish the explanations. The Avalos unit of the Compania Minera de Penoles, S. A., operates the Alicante, Bonanza, Providencia, Albarradon, San Eligio, Nazareno, Leona, Salaverna, and Santiago mines situated between Avalos railroad station and Concepcion del Oro on the Coahuila and Zacatecas railroad in the State of Zacatecas, Mexico. Some of these mines are within Penoles property while others are on mining claims leased from the Compania Nazareno y Catasillas, S. A., Mazapil Copper Co., and the American Smelting and Refining Co. The main office and camp are at Providencia, about 170 km southwest of Monterrey, N. L., so the silver-lead-zinc mines of the district are usually referred to as the Providencia mines. The Aranzazu, Catarroyo, and Cabrestante copper-gold mines are situated a few kilometers to the southeast on the same mountain range near Con- cepcion del Oro, the name by which the camp is known. It is operated by the Mazapil Copper Co. The main theme in the following pages is a description of the silver-lead-zinc ore occurrences of the district. Rock Formations Sedimentary Rocks: Many competent geologists have contributed generously to an ample fund of information concerning the sedimentary columns of northern Mexico. Among them are Carlos Burck-hardt, E. Bose, L. B. Kellum, and R. W. Imlay. Carlos Burckhardt, who covered a number of extensive areas in many parts of the Mexican Republic, devoted years to mapping the geology of the Caja, Zuloaga, and Santa Rosa mountain ranges around Mazapil, Concepcion del Oro, and San Pedro de Ocampo, Zacatecas. He did most of the original mapping which has been used as a basis and amplified by others. C. E. Burbridge and, more recently, John

Jan 1, 1953