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By R. Haynes

ON the basis of compositional changes of a phase observed in a eutectoid Cu-Al alloy1 it has been suggested that mechanisms for the decomposition of the ß phase proposed by earlier workers2-5 were incorrect. These data are reinterpreted in conjunction with lattice parameter data obtained on an alloy containing 12.2 pet Al, whose isothermal transformations have been reported elsewhere.5 The a Lattice Parameters of a 12.2 Pet A1-Cu Alloy—~iffraction patterns of completely transformed specimens were obtained in a back reflection camera using copper Ka radiation. Lattice parameters of

Jan 1, 1959

By A. S. Michaels, R. S. Timmins

A study of the effect upon oil recovery from an un-consolidated porous medium of chromatographic transport of selected reverse-wetting additives during water displacement is described. Flow tests were performed on hydrocarbon oil-saturated sand columns (containing connate water) into which small volumes of short-chain aliphatic amine solutions were introduced during water flooding. Concurrently, meusurements of oil-silica contact angles, oil-water interfacial tensions and oil-water distribution coefficients were measured us a function of additive concentration. Certain treatments were found to cause a slight reduction in oil recovery, while others produced a significant increase (up to 50 per cent of the normtzl irreducible rninimum oil saturation). Recovery eficiency was correlated most satisfactorily with the maximum degree of reverse wetting produced during additive transport; conditions which resulted in only mild oil wettability of the sand reduced recovery, while those favoring strong oil wetting increased recovery. A mechanism of reverse-wetting additive action during chromatographic transport is developed which ascribes the results to transient changes in oil-solid contact angle during flow, with consequent release of oil trapped by capillary forces. Implications of these observations with regard to improved waterflood efficiencies are discussed. INTRODUCTION The need for finding improved methods of oil production is amply illustrated by the large volume of oil considered economically unrecoverable by existing production practice. Water flooding has long been an excellent method of secondary recovery. However, even in those areas of a formation which are well swept by a water flood, 20 per cent or more of the oil remains trapped within the formation and is not recovered. This trapping of oil within the pores of the rock structure results primarily from interfacial forces. If these interfacial forces were altered, it is possible that the trapped oil could be released and recovered. The addition of surface-active agents to a water flood to alter the interfacial properties of the oil-water-solid system has received considerable attention as a method of increasing oil recovery. Studies of surfactant treatment have yielded varied and, in some cases, apparently conflicting results. Increased oil recovery using surface-active agents has been reported by a number of investigators. Others have found that use of surfactants in a water flood either has no effect upon oil recovery or decreases it. Since surface-active agents tend to alter the formation wettability and oil-water interfacial tension simultaneously, several investigators have tried to determine the role these two factors play in oil recovery. Data have been presented which indicate that the most desirable condition for the solid surface is strongly water-wet. Other results indicate that, although breakthrough recovery may be less, the greatest ultimate recovery is obtained when neutral wettability prevails.", " The desirability of low interfacial tension seems to depend upon the wettability of the formation. Reports of higher recoveries, when the interfacial tension is high in a water-wet system and low in an oil-wet system, are at odds with reports of increased recovery in water-wet systems when surfactants which decrease the interfacial tension are added to the water flood. A review of previous work studying the effects of using surface-active agents in a water flood shows that these agents produce widely different effects and that opinions as to the role of the various interfacial properties are diverse. The consensus, however, is that the interfacial properties are quite important in the displacement of oil from a porous medium by water. Even in those investigations where appreciable increases in oil recovery resulted from treatment with a surface-active agent, economic considerations generally made practical application of the treatment unattractive because surfactants tend to be adsorbed within the formation. This adsorption would necessitate using large quantities of surfactant if all of the flood water were treated to contain a given surfactant concentration, even if this concentration were quite low. Preston and Calhoun suggested that the principles of chromatography could be applied to the use of surface-active agents as a means of increasing oil recovery. A small volume of surface-active material is injec-

By Paul D. Merica, O. B. J. Fraser

PROBABLY the first metallic objects used by man were nickel alloys. In search for flints suitable for the fashioning of their rude tools, our paleolithic ancestors, some 25,000 years ago, quite likely may have come upon some of those heavy, metallic fragments that we now know as meteorites, which consist of an alloy of nickel and iron containing usually from 5 to 15 pct of nickel. Whether paleolithic man ever did discover and use meteoritic fragments, his sketchy records do not actually disclose. We do know, however, that such fragments have been found and used by peoples, particularly the North American Eskimos, for weapons and implements in just the same manner as stones, and prior to any knowledge by those peoples of the reduction of metals from ores. Meteoritic showers were recorded frequently in earliest times and the meteorites often were found and fashioned into useful objects. The ancient Arabic and other myths of "invincible swords fallen from heaven" seem thus to have had a very definite basis in fact, and such weapons, of meteoritic material, have actually been re- covered from archeological excavations. It thus seems probable that meteoric nickel-iron was found and used long before iron was recovered by smelting iron ores (perhaps about 1200 B.C.) and probably even before there was knowledge and use of bronze and gold. Although many centuries were to pass before nickel was first isolated, in 1751, from Swedish ores and recognized as an elemental

Jan 1, 1953

By J. Handin

Triaxial compression tests with independently applied external confining pressures and internal pore pressures show that the ultimate compressive strengths of representative oil well cements are nearly linear functions of effective pressure — the difference between external and internal pressures on the jacketed cylindrical specimens (to 15,000 psi). The strengths are little affected by the test temperature to 350F (not to be confused with the curing temperature). At an effective pressure of 15,000 psi, strengths are in the rage of 30,000 to 50,000 psi, comparable to those of sedimentary rocks under similar conditions. The cements become very ductile even under low effective pressures; permanent shortenings of 30 per cent or more are attainable without rupture. INTRODUCTION Since the pioneering work of Richart, Brandtzaeg and Brown1 on the failure of cement under combined compressive stresses, it has been recognized that ultimate compressive strength is greatly enhanced by the application of confining pressure. More recently, Mc Henry2 showed that the strength of concrete was a linear function of the effective pressure (the difference between the external confining pressure on a jacketed specimen and the internal fluid pore pressure), at least for a range of 0 to 1,500 psi. The effect of temperature had not been investigated, and no previous systematic triaxial compression testing of naterials used for oilwell cementing seems to have been done. The present work was suggested by the late J. hi. Bugbee3 who stated that "consideration of the common application of high-pressure hydraulic fracturing to the initial completion or recompletion of wells, and the large pressure drawdowns in some producing wells, particularly those in abnormally high-pressure gas-condensate reservoirs, raises the question of what is a suitable cement strength for various completions. The intuitive belief exists that cement strength need be no greater than formation strength. Tests should, however, be conducted at downhole conditions." The ultimate compressive strengths of rocks penetrated by the borehole must rise several fold with increasing depth.4 This marked enhancement of strength is due to the influence of the effective pressure, the total weight per unit area of the overburden less the hydrostatic pore pressure. (The effect of temperature due to the geothermal gradients is relatively small for depths to 30,000 ft.) .A significant comparison of the strengths of rocks and cements at downhole conditions requires knowledge of the confined compressive strengths of cements as well. EXPERIMENTAL PROCEDURES The theory and technique of triaxial compression testing are fully discussed in earlier reports.4-6 Briefly, cylindrical specimens 1-in. long and 0.5-in. in diameter are jacketed in thin copper tubes of negligible strength, placed in the test chamber and subjected to an external confining pressure of kerosene and loaded axially by the piston at a strain rate of 1 per cent per minute. Pore pressures of water (or kerosene) are applied independently through the hollow piston and are maintained constant during the shortening of the specimen, Tests at sensibly 0 pore pressure are arranged so that any free water in the cement can escape to the atmosphere. (If egress of water were denied, pore pressure would rapidly attain the value of the external confining pressure because of reduction of pore space.) The test chamber can be heated for high-temperature experiments. Unless otherwise noted, the cement samples were air dried for about a week. Recorded during a test are pore and confining pressures, shortening and axial differential force (total force less the product of the confining pressure and the area of the piston). True stress-strain curves are constructed by dividing the measured differential force by the actual cross-sectional area of the specimen at a given

Jan 1, 1966

By F. J. Fayers, R. L. Perrine

For many years the problem of increasing ultimate recovery of oil from a reservoir has been a subject of interest to the oil industry. At present, a standard secondary recovery technique is to flood the reservoir with water once natural forces of the system are depleted. The permeability characteristics of the rock, together with interfacial forces which exist between the two fluids and the porous material. allow only part of the oil in the rock formation to be recovered by the water-flooding process. Laboratory experiments have shown that when detergents are added to the flooding water, the flow properties of oil in a porous rock arc improved. This improvement results in greater oil recovery. Even though higher recoveries are obtained using detergents, the extra cost associated with the method may make it economically unsatisfactory. To establish economic feasibility requires experimental laboratory measurement of fluid and rock properties together with a calculational procedure to predict field results. Pilot tests in the field may also be required. This paper presents a mathematical procedure for predicting detergent flood behavior. A number of reasonable simplifying assumptions are made to obtain a tractable system of equations. The resulting method may be regarded as a generalization of Buckley-Lev-crett' theory to solve simultaneously for water saturation and detergent concentration profiles. Consequently this type of calculation can be used in much the same manner as Buckley-Leverett theory is used to evaluate a water flood. The mathematical method employed is the so-called method of characteristics for solving hyperbolic partial differential equations. This application of the method is instructive because several other problems in reservoir analysis may be analyzed in a similar manner. FLUID FLOW EQUATIONS The flow behavior of oil and water without detergent through porous reservoir rock is usually expressed by Darcy's law and a continuity equation for each phase. If gravitational forces are neglected, vrg = kr (s)µr v p rg.........(1) vrg = kr (s)µr v p rg.........(1) ? pa va = F ?/?t (sd) where v is the volumetric flux, k represents permeability, S is saturation, and P the pressure. Fluid viscosity is denoted by 11, p is the density, 4 is porosity, and I the time. The subscripts w and o refer to water and oil. The capillary forces in the system lead to a difference in pressure between phases. This may be expressed by the relation: Pm -P0 =Pc(S).........(5) The capillary pressure? P,, is determined experimentally as a function of saturation. DETERGENT BALANCE EQUATION Addition of detergent to the water phase affects the flow properties of the system. Capillary pressure and relative permeability become functions of detergent concentration, c, as well as fluid saturation. That is: P--P (S,c) and k,,,.- - -- k,,,. At low oil saturation values, the presence of detergent reduces capillary pressure and reduces the relative permeability ratio. Detergents are surface-active and adsorb on rock surfaces. The quantity adsorbed, a, will depend on the concentration c of detergent solution and may also depend on the saturation; thus, a = a(S,c). In this analysis we have assumed that the detergents used are water soluble but not oil soluble, and their movement is therefore restricted to the water phase. The dispersion of detergent in water is neglected by comparison with transfer by flow within the system. Detergent movement is determined by the water flux and adsorption: ? cv m = -F ?/?t (cs + a) We will assume that the quantity of detergent in solution is too small to significantly change water density or viscosity. When the permeability and capillary pres-

By Eugene N. Cameron

Graphite is the hexagonal form of crystal-line carbon. It is found in nature locally as tabular crystals but occurs mostly as disseminated flakes, foliated, platy, or fibrous masses, or microcrystalline compact to earthy material. Graphite is characterized by its gray to black color, metallic luster, black streak, perfect basal cleavage, softness (H = 1-2) and unctuous feel. It is sectile and flexible and has a specific gravity of 2.1 to 2.3. It is an excellent conductor of heat and electricity and is inert to ordinary chemical reagents. It melts at a temperature of about 3500°C and vaporizes at a temperature of about 4500°C. In the presence of oxygen it oxidizes to CO2 in the temperature range 600° to 700°C, but it is stable at ordinary temperature and markedly resistant to chemical weathering. Although some natural graphite is nearly 100 pct pure carbon, most contains mechanical impurities of various kinds; quartz, biotite, muscovite, pyrite, iron oxides, and feldspars are the most common. Commercial graphite products have a wide range of graphite content, but the better grades contain 80 pct graphite or more. Both natural and manufactured (artificial) graphite are used in industry. Natural graphite products are divided into two broad categories based on grain size. Graphite composed of visible crystals is called "crystalline" graphite, whereas graphite so fine-grained that it is not visibly crystalline is termed "amorphous." The distinction is arbitrary, for all natural graphite is crystalline, and all gradations between the two commercial categories are known. Within the two categories the terminology used in industry is confusing and not entirely consistent. Crystalline graphite comes from two principal types of sources. The first consists of rocks containing disseminated flakes of graphite. This source yields the "flake graphite" of industry. The second comprises vein deposits of graphite, of which those in Ceylon are the most important and furnish the Ceylon graphite of industry. Amorphous graphite comes from any of a variety of sources, including some of those that yield crystalline graphite. Manufactured graphite is made by electric furnace processes, mostly from petroleum coke. Occurrence and Distribution of Graphite Deposits GENERAL Graphite is widely distributed in nature, occurring in igneous, sedimentary, and metamorphic rocks, and even in nickel-iron meteorites. Graphite deposits of economic interest, however, occur mostly in metamorphic terranes. Five principal geologic types of deposits are recognized: 1. Deposits consisting of flake graphite disseminated in metamorphosed siliceous sediments. 2. Deposits consisting of flake graphite disseminated in marbles. 3. Deposits formed by thermal or dynamothermal metamorphism of coal or other highly carbonaceous sediments. 4. Vein deposits of the Ceylon type. 5. Contact metasomatic or hydrothermal deposits in marble. DEPOSITS IN METAMORPHOSED SILICEOUS SEDIMENTS Deposits consisting of flake graphite disseminated in metamorphosed siliceous sedi-

Jan 1, 1960

By G. L. Oldright

THE economic manufacture of sulfuric acid by the ordinary chamber process usually involves production on a large scale and a plant that is costly to construct. The nature of sulfuric acid makes it costly to transport any great distance. For these reasons, the metallurgist has not found it feasible, at times, to beneficiate ores amenable to leaching, and a. need exists for a local process that will produce acid cheaply on a small or large scale. To leach ores containing residual sulfides, an oxidizer, such as ferric sulfate, is needed in solution. Precipitation with scrap iron is one of the cheapest methods of removing some metals from solution, giving a plant of low first cost and supplying a source of cheap ferrous sulfate. The other ingredient needed for the process is SO2 roaster gas; the addition of which, as, described below, will give both ferric sulfate and sulfuric acid. Where roaster gas is a waste or obnoxious, product, the expense. for materials is still further lessened. The use of ferric sulfate and sulfuric acid as a solvent lends itself, well to the utilization of scrap iron as a precipitant, and the stages of the process fit in well together as an economic whole.

Jan 8, 1925

By R. S. Cartwright

Two types of automatic drilling controls, the Halliburton and the Hild, are now available and are coming into more or less general use in deep drilling. The primary function of both is to maintain a safe limit of torque on the drill pipe, this being accomplished by automatically controlling the weight or pressure on the cutting tool. Neither type will necessarily increase drilling speed, but by permitting advantage to be taken of "breaks" in the hole higher average cutting speed may be maintained. The control is essentially a safety device, and should be considered as such. It is not the purpose of this paper to discuss the merits of drilling controls, although the advantages over manual feed at the brake drum are obvious, but rather to point out some of the limitations. The Halliburton Control The Halliburton control is designed to operate during drilling through the agency of the draw works. Automatic and constant control. of the torque on the bit is governed by clutches on the control itself, and the line shaft to drum shaft drives on the draw works. In operations other than drilling the control is simply a jackshaft between prime mover and draw works. It is, of course, adaptable to any type of power. Because control of the torque on the bit is dependent upon the various ratios or clutch combinations available on the Halliburton control and the draw works, it follows that there are certain limitations in points of control. Table 1 shows the possible ratios which can be obtained with the control and a popular type of three-speed draw works, it being assumed that the highest possible gear combination-the combination which when engaged will suspend the least amount of weight-has a value of 1.00.

Jan 1, 1928

By Joel H. Watkins

The terms kaolin, china clay, ball clay, and paper clay are more or less loosely and interchangeably applied to a large class of white-burning clays. These clays are made up chiefly of hydrous amorphous (colloidal) aluminum silicates with variable amounts of free silica and other impurities in small quantities. Occasionally also the term kaolinite is wrongly applied to a white-burning clay, for kaolinite is a mineral of definite chemical composition and definite crystalline form which occurs but sparingly in nature. It is not the purpose of this paper, however, to define or classify clays, or to enter into a discussion of the chemistry of clays. It is rather a general description of the occurrence and methods of mining of a kindred group of clays, and a discussion of their future economic aspect. In the Southern Appalachian States, the mining of white-burning clays has in recent years become an important industry. Although these clays are of several distinct types, which occur in as many localities under different geologic conditions, they are for the most part primarily of the same origin. They are essentially the same in elementary constituents, and are largely consumed in the game industrial arts. From the standpoint of a mining engineer, therefore, and for convenience in comparison and correlation, it should be interesting to discuss them under one heading. Kinds of Clay The most important types of clay which are now being actively mined in the Southern Appalachian States and with which this paper is particularly concerned are the North Carolina, Virginia, and Georgia kaolins or china clays (residual); the South Carolina and Georgia kaolins or paper clays (sedimentary); and the Florida and Tennessee plastic kaolins or ball clays (sedimentary). Other varieties which are interesting but which are as yet of little importance are the pocket deposits of white clay in Augusta County, Virginia, the bauxitic kaolins of Tennessee,

Jan 1, 1915

By C. F. Nagel

THIS paper is written primarily for those who are familiar with the processes mentioned but who desire a further insight into some of the fundamental principles. It does not give a complete description of the various practices employed in the working of aluminum and its alloys, but presents a few illustrations of the essential respects in which aluminum differs from other common metals, and emphasizes the controlling factors of the processes under consideration. HEAT TREATING Certain aluminum alloys are capable of having their mechanical properties greatly altered by a heat-treatment process. The degree of this improvement may be illustrated by some typical properties of duralumin (Table 1). It is essential that the material be in the wrought condition in order to obtain maximum heat-treatment effects. [ ] In the case of duralumin, the process consists of heating the metal to a prescribed temperature and then quenching it. Immediately after quenching, the material is relatively soft though not as soft as in the annealed state. If allowed to stand at room temperature, the material changes, increasing in hardness and strength without loss of elongation, but at the expense of the plasticity. This action is very rapid at first, gradually diminishing in intensity and to all practical purposes being completed in about four days. This process of hardening is termed

Jan 1, 1928

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 commentators 1.2.1 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

THE paper on "Specific Efficiency of the Blast Furnace" by Richard Franchot, which was pub-lished in the September issue of MINING AND METALLURGY, was presented for discussion at the Pitts-burgh meeting. The session opened with a discussion among S. P. Kinney, Mr. Franchot, and J. N. Reese as to the methods and results in sampling for cyanides in the blast furnace. This is covered in detail in writ-ten discussion below. T. T. Read objected to the use of the term specific efficiency as likely to be confusing. The blast furnace has to perform the function of reducing Fe, 03 to Fe as well as that of fusing the metal and, since the reduc-tion of Fe, 0? involves a CO equilibrium, it seems mis-leading to calculate efficiency on the basis of burning the , all carbon to CO? since it is not possible. Mr. Franchot replied that he used the term in the sense defined by Richards in his "Metallurgical Calculations;" but a subsequent search failed to reveal the term in Richards, who says (page 245, 1st edition): The practical conclusion is that a blast furnace generates in itself not much over 40 per cent of the calorific power of the fuel used, and rejects nearly 60 per cent; by using part of the waste gases to heat the blast, however, some of this rejected heat, to an amount representing net 5 to 10 per cent of the calorific power of the fuel used, is returned to and injected bodily into the furnace, thus rendering available for the purpose of running the furnace about 50 per cent of the calorific power of the fuel as a maximum. The efficiency with which the furnace applies this 50 per cent usefully to the objects of the reducing and smelting is another question for investigation.

Jan 2, 1927

By H. Biloni, G. F. Bolling

The microsegregation in tin specimens containing 0.2, 0.5. or 1 wt pct Pb has been studied m detail. The specimens were grown from the melt in a controlled fashion and exhibited a well-developed cellular substructure. In general, a severe microsegre-gation can be observed in all the photomicrographs presented. Some observations of special interest are: the distribution of a second phase, the presence of a eutectic in several forms, the evidence for dif- THE Smialowski or cellular substructure which forms during solidification has been extensively studied during the past decade.'* Many of the im- *Most references to the cellular substructure except for the last 2 years are reviewed by Winegard.' portant characteristics of this substructure, such as its occurrence and variability with growth conditions, its association with the phenomenon of constitutional supercooling, and its effect on dislocation production and mobility, have received quantitative fusion of solute in the solid, and the enhancement of segregation at a dislocation subboundary network ("striations"). On the basis of the metallographic observations, it can be deduced that the segregation observed is representative of the solute segregation produced during crystal growth. Some deductions are also made about the interplay of the two substructures, cells and striations, and about the mode of cellular growth. investigation both experimentally and theoretically. However, the concentration profile of the solute segregated during crystal growth has not been examined in detail. Tin crystals grown from melts containing various concentrations of lead have been most extensively studied. In a recent investigation of Sn-Pb alloys, Kramer et a1.2 were able to measure the effective solute distribution coefficient, k,, at the most advanced points of the solid-liquid interface, over a large range of growth conditions, finding it to approach the value of k,, the equilibrium distribution coefficient. As will be shown, this must lead to drastic segregation. Another recent study of several Sn-Pb alloys was made by Plaskett and winegard3 who investigated the variation of growth conditions

Jan 1, 1963

By E. S. Davenport

WHEN annealed carbon, or low-alloy, steels are suitably heated the ferrite (alpha iron solid solution) and the carbide, of which they are composed, react together to form a single solid solution of carbon (and other elements) in gamma iron (austenite). This reaction may begin only at a certain minimum temperature called the eutectoid temperature. The first ferrite and carbide thus to react together do so in definite proportions known as the eutectoid composition. With further heating the original constituent that is present in excess is dissolved in the austenite until exhausted. Whether the excess constituent be ferrite (hypoeutectoid steels) or carbide (hypereutectoid steels) the procedure is much the same, and upon slow cooling the homogeneous austenite expels the excess of either (proeutectoid ferrite or carbide) until the eutectoid composition is reached. Thus the reaction upon heating is strictly reversed upon cooling and accordingly an equilibrium diagram of this process may be constructed. Such an equilibrium diagram concerns itself only with the tempera¬tures involved and with the proportions and compositions of the phases developed under conditions that suffice to permit equilibrium. Specifically it has no concern for the type or mode of distribution of these constituents nor with any extra-equilibrium conditions such as undercooling, which is almost universally encountered in metals. Actually, however, of great importance is the sluggishness toward equilibration caused by the not inconsiderable time involved in diffusion. Thus instead of the theoretical transformation point AE, we find for a certain rate of heating or cooling the use of the designations Ar and Ac (transformation temperature found on cooling and upon heating). These figures obviously have no particular meaning except as measured and expressed for a definite heating or cooling rate, and represent the apparent temperature displacement caused by an inadequate time allowance. In this paper are presented the results of a study of the time required for' the transformation of austenite to ferrite and carbide at a variety of temperatures and also of the time required for the reaction austenite ?martensite at the temperatures at which this reaction occurs instead of

Jan 1, 1930

By C. L. Dake

Discussion of the paper of. C. L. DAKE, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 103, July, 1915, pp. 1429 to 1436. A. C. LAWSON, Berkeley, Cal.-It appears that our bog-iron ores are due in a large measure to the activity of certain iron bacteria, and a paper dealing with this subject that makes no reference to that particular agency strikes me as rather curious. C. L. DANE, Rolla, Mo.-Mr. Lawson's criticism that this paper makes no reference to the activity, of iron bacteria is scarcely true. On p. 1430 I stated: "Certain bacteria precipitate iron by building the hydrated oxide into their body cells," and again, "There are many other means by which, under special conditions, iron may be precipitated in nature. Oxidation, evaporation of CO2, and iron bacteria have been held to be the most important." Thus the activity of bacteria receives as extended mention as the action of any other agency in precipitation of iron. The paper makes no pretense of covering exhaustively the origin of bog ores, but, as its original title suggested, refers to Some Principles Controlling the Formation and Distribution of Bog Iron Ores. Mr. Lawson seems to have entirely missed the main thesis of the paper, which attempts to establish some relation between glaciation and abundance of bog ores now forming. Unfortunately, I have no immediate access to the literature of the subject, but my best recollection is that the data regarding iron bacteria throw no light whatever on the cause of bog ores being so much in ore abundant within the limits of the glaciated regions, and being reported much less frequently from the tropics. This lack of data is suggested in the following (p. 1434): "It has already been shown that bacteria aid in the precipitation of iron. Whether tropical conditions increase or decrease the activity of such bacteria is unknown."

Jan 12, 1915

By K. M. Kolobova, E. Z. Kurmayev, A. Z. Menshikov, S. A. Nemnonov, V. A. Trapeznikov

The present work represents a review of our intestigations into the X-ray spectra of solids, which have been carried out by us along two lines of upproach: 1) St@ of the electronic structure of high -rnelting compounds of transition metals; 2) stzddy of the interatomic binding forces by the fine structure of absorption spectra under varying temperature and concentration conditions. With this in mind, int>estigations hare been made into the emission and absorption spectra of the K-series of atoms of transition elements in alloys and compounds. In the problem concerned with the electronic structure of high-melting compounds of transition metals, considerable importance is attached to the question of ascertaining the role played by 3d4sp electrons of metal and 2p electrons of metalloid in the formation of chemical bonds and of giving, on the strength of this data, an explanation of the properties which seem to be contradictory at first sight: good conductivity inherent in metals and high brittleness and high-melting characteristics typical of covalent compounds. Over the last few decades this question has attracted the attention of many investigators whose studies were devoted to this type of compound. Many works, both of theoretical1-3 and experimental4- l5 nature , have contributed much to the elucidation of the physical character of the phenomenon referred to. Alongside the investigations in the field of electric resistance, Hall effect, paramagnetic susceptibility, electronic heat capacity, and the temperature of transformation into a superconducting state, we should particularly emphasize the studies on X-ray spectra, which have played a significant role in the development of the zonal theory for high-melting compounds. This fact has become highly evident after the theoretical calculation of the energy spectrum has been made and the density of states curve in Tic, TiN, and Ti0 has been plotted by Ern and Switendick3 who used the method of augmented plane waves. Correlation of the results of the theoretical calculation of the band structure in the compounds listed above with the data obtained by X-ray spectroscopy studies showed that X-ray spectra can be a source of valuable information on the electronic structure of high-melting compounds within a wide range of ener- gies. It is well known that X-ray emission spectra basically give a direct picture of the occupied excited states above the Fermi level of a solid (valence band, conduction band) and that the absorption spectra (region of initial absorption) give a similar picture of states corresponding to the unoccupied levels near the Fermi surface. Full information on the density distribution of electronic states by energies can be obtained by combining the emission and absorption spectra. Such an opportunity arises from investigation

Jan 1, 1970

By Sidney Diamond, Charles Wert

The anelastic behavior of Ni-C alloys of nominal 0.5 wt pct C has been determined over a wide temperature range. The most prominent damping effect, that due to the presence of C-C pairs, was measured both above and below the Curie temperature. The effect on diffusion of the C-C pairs by magnetic spin ordering is deduced to be very small. The diffusion coefficient for C-C pairs in nickel is given by the expression ThE solid-state diffusion of both interstitial and sub-stitutional solutes in ferromagnetic solvents has been the subject of a number of investigations. Measurements of the self-diffusion of iron,"' the diffusion of nickel1,4 gold,"1 and cobalt4 into iron, the diffusion of vanadium in an Fe-V alloy,' and the diffusion of cobalt and nickel in Co-Ni alloys9 show an unusual behavior. In both the ferromagnetic and paramagnetic regions, far removed from the Curie temperature, the diffusion coefficient, D, obeys an Arrhenius relation. However, in the ferromagnetic region D is markedly lower than would be expected from an extrapolation of D from the paramagnetic region; this results in an increase in the activation energy in the ferromagnetic region. The cause of this effect for self- and substitutional diffusion is uncertain. Since substitutional diffusion is presumed to proceed by the vacancy mechanism, it has been variously suggested that the increase in activation energy below the Curie temperature is due to one of the following causes: 1) an increase in the energy of formation of a vacancy because of local demagnetization around the vacancy,2,3 2) a decrease in vacancy mobility in the ferromagnetic state,' or 3) an effect on the entropy of motion of a vacancy in the ferromagnetic state.5 Quite another explanation for the observed effect has been proposed by Borg.7 The diffusion coefficient is a function of the elastic constants of a metal. Since the temperature dependence of the elastic constants often changes at the Curie temperature, the temperature dependence of D might be expected to undergo a universal change in the vicinity of the Curie temperature. The magnitude of the change in D would, of course, depend on the magnitude of the change in the elastic constants. One might attempt to differentiate between vacancy effects and elastic effects by making measurements on interstitial alloys, in which vacancy effects play no role. Some measurements of this type have been made; this paper reports additional observations. Measurements of the diffusion of carbon in a Fe by a tracer technique8 and of the diffusion of carbon in a Co and in Co-Fe alloys by a decarburization method9 reveal a small effect, if any, on D of the magnetic change at the Curie temperature. If the effect of spin ordering is only to alter the parameters controlling formation or mobility of a vacancy, interstitial diffusion should indeed remain unchanged through the magnetic transition, as these measurements imply.

Jan 1, 1968

By E. V. Daveler

THE milling plant of the Alaska-Gastineau Mining Co. is located at the town of Thane, Alaska, on Gastineau Channel, 4 mi. south of Juneau and directly across the channel from the Ready Bullion mine of the Treadwell mines on Douglas Island. Previous to the organization of the Alaska-Gastineau Mining Co., in 1912, the milling was done at the stamp mill of the Alaska Perseverance Co. located at the mine in Silver Bow Basin. But the contemplated increase in production made it necessary to locate the mill on Gastineau Channel, as not enough water was available at the mine during the winter months, nor was there room for taking care of the large tonnage of tailings that would ultimately be discarded from the mill. CHARACTER OF ORE The gold and silver values occur in quartz lenses associated with pyrrhotite, galena, arsenical pyrites, and zinc blende. These lenses occur in large bodies of slate, schist, and metagabbro, which also carry some valuable metallic contents. With the essential low cost of mining, it was necessary to mine large bodies of low-grade material containing the high-grade streaks. Of the minerals, pyrrhotite, the magnetic sulfide of iron, is predominant, and galena is the next sulfide present in quantity. The gold occurs free and coarse and associated with the iron sulfide in its finer state. The silver occurs with the lead or is alloyed with the gold. A chemical analysis of the ore shows Silver 0.10 oz. Magnesia 0.4 per cent. Silica 59.7 per cent. Sulfur 1.2 per cent. Iron 5.2 per cent. Lead 0.1 per cent. Alumina 21.4 per cent. Zinc 0.2 per cent. Lime 5.0 per cent.

Jan 1, 1920

By E. T. Turkdogan, Klaus Schwerdtfeger, P. Grieveson

The rate of growth of "Fe4N" on a iron was measured by nitriding purified iron strips in flowing am -monia -hydrogen gas mixtures at 504" and 554°C. It is shown that a dense nitride layer is formed when a zone -refined iron is used in the experiments. With less pure iron, the nitride layer is found to be porous. Through theoretical treatment, the self-diffusivity of nitrogen is evaluated porn the parabolic rate constant, and found to be essentially independent of nitrogen actirlity, e.g., D* = 3.2 x l0-12 and 7.9x l0-12 sq cm per sec at 504" and 554?C. Some consideration is given to the mechanism of diffusion in the nitride phase. THERE is a great deal of background knowledge on the solubility and diffusivity of nitrogen in iron, and on the thermodynamics and crystallography of several phases in the Fe-N system. Although case-nitrided steels have many applications in practice, no work seems to have been done on the diffusivity of nitrogen in the iron nitride, ?', phase. The only work reported on the related subject of which the authors are aware is an investigation by Prenosil,1 who measured the growth rate of the e phase on iron by nitriding in ammonia-hydrogen gas mixtures. EXPERIMENTS Purified iron plates of approximate dimensions 1 by 0.5 by 0.03 cm were nitrided in flowing mixtures of ammonia and hydrogen, in a vertical furnace fitted with a gas-tight recrystallized alumina tube. After a specified time of reaction, the sample was cooled to room temperature by withdrawal to the water cooled top of the reaction tube. The furnace temperature was controlled electronically in the usual manner within *l°C; the temperature was measured using a calibrated Pt/Pt-10 pct Rh thermocouple. For each experiment the iron strip sample was cleaned with fine emery cloth and degreased with tri-chloroethylene prior to the experiment. The ammonia-hydrogen gas mixtures were prepared from anhydrous ammonia and purified hydrogen using constant pressure-head capillary flowmeters. The gas mixture flowed upward in the furnace with flow rate of 400 cc per min at stp. The composition of the gas mixture was checked by chemical analysis at regular intervals. In most cases, the compositions of the exit gas and metered input gas agreed within about 0.3 pct, indicating that cracking of ammonia did not pose a problem at the temperatures employed. Two series of experiments were carried out using two different types of purified iron samples. In the first series of experiments at 550°C, vacuum carbon deoxidized "Plastiron" was used. The main impurities present in this iron were, in ppm: 4043, 50-Cr, 20-Zr, 40-Mn, 20-P, 20-S, 20-C, 50-0, and 10-N. In these experiments the rate data were obtained by measuring the change in weight of the iron specimen suspended in the hot zone of the furnace by a platinum wire from a silica spring balance. The nitride layer formed in these experiments was found to be porous, particularly near the outer surface. In other experiments, high purity zone-refined iron (prepared in this laboratory) was used. The total impurity content of this iron was 30 ppm of which 20 ppm was Co + Ni, 4 ppm 0, other metallic impurities were less than 1 ppm. The zone-refined iron bar, -2.5 cm diam, was cold rolled to a thickness of about 0.03 cm and the specimens were prepared for the experiment as described earlier. After the nitriding experiment, the sample was copper plated electro-lytically and mounted in plastic for metallographic polishing. After polishing, the thickness of the ?' layer was measured using a metallographic microscope. The nitride layer formed on the zone-refined iron was essentially free of pores. RESULTS The different morphology of the nitride layers grown on "Plastiron" and zone-refined iron is shown in Fig. 1. Both samples were nitrided side by side for 55 hr. The holes in the less pure iron, Fig. l(a), are confined to a region about one half thickness from the outer surface. The dense layer grown on zone-refined iron, Fig. l(b), is thinner than the porous layer on the "Plastiron". The impurities in the iron are believed to be responsible for the formation of a porous nitride layer. The pore formation may be due to the high nitrogen pressures existing within the nitride layer, e.g., the equilibrium nitrogen pressure is 1.2 x l05 atm in the 38.6 pct NH3-61.4 pct H2 and 6.6 x l03 atm at the Fe-Fe4N interface at 554°C and 0.96 atm. It is possible that the oxide inclusions present in the electrolytic iron may facilitate the nuclea-tion of nitrogen gas bubbles within the nitride layer. Support for this reasoning is the fact that pores are only encountered in the outer range of the layer where nitrogen pressures are largest. The photomicrographs in Fig. 2 show the effect of reaction time on the thickness of the dense nitride layer formed on zone-refined iron. These sections are from samples nitrided in a stream of 29 pct NH3-71 pct H2 mixture at 554°C for 22, 70, and 255 hr. In all the sections examined the nitride-iron interface was noted to be rugged. These irregularities are be-

Jan 1, 1970

By J. A. Dresser

The controlling supply of asbestos for the world is obtained from southern Quebec, 150 miles or less north of the international boundary line between Canada and the United States, and about 75 miles south of the city of Quebec.

Jan 1, 1915