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By F. W. Jessen, C. C. Patton

Adsorbed films were formed on polished stainless steel specimens from dilute benzene solutions of two crude oil distillation residua. Although the two residua were extremely dissimilar in composition, contact angle measurements showed that the two films increased the wettability of the steel specimens to oil by equal amounts. Furthermore, the wettability of the films was essentially unaffected by the desorption techniques used. Paraffin deposits were formed from heptane-wax solutions on the same stainless steel specimens. These deposits definitely adhered to the surface. Presence of an adsorbed crude oil film on the metal surface increased its free surface energy and resulted in increased deposition of paraffin. The addition to the heptane - wax solution of small amounts of the same distillation residua that were used to form the adsorbed films resulted in decreased cohesive strength in the deposits formed, which resulted in decreased deposition. The presence of a crude oil fraction both in the solution and as a preadsorbed film eliminated the adherence of a deposit of any kind. A mechanism of deposition is proposed which explains the results obtained. INTRODUCTION The natural formation of any predominantly organic accumulation in oilwell tubing, surface flow lines or other production and storage facilities is called a paraffin deposit. These deposits restrict the production of crude oil, causing a substantial increase in production costs because of decreased flow capacity, expense for periodic deposit removal and unproductive downtime. The conditions under which such deposits form, their physical characteristics and the nature and severity of the problem created are extremely varied. Over the past several years, much progress has been made in developing and utilizing methods to remove accumulated paraffin deposition. However, like so many other problems, the basic stumbling block appears to be a lack of understanding of the fundamental mechanism involved in the formation of such deposits. Crude petroleum is known to contain considerable quantities of polar, surface active substances which Doddl has shown to be present at the oil-water interface. Denekas, Mattax and Davis2 observed that the wettability of reservoir rocks was drastically altered by exposure to crude oil fractions; and Zisman, et a1.3 showed that the nature of the compounds adsorbed on a surface would determine its wettability characteristics. Cole and Jessen4 and Ehrig5showed that surface wettability can have a profound effect on the magnitude of paraffin deposition, and Parks6 demonstrated chat the presence of certain adsorbed films on a metal surface would reduce the adherence of paraffin to that surface. Zisman7 has since advanced the theory that the conditions for adhesion are the same as for wetting. Therefore, it was felt that there was adequate evidence to support the supposition that adsorption of compounds from a crude oil might play an important part in paraffin deposition. ADSORPTION-WETTABILITY EXPERIMENTS Initial experiments were conducted to determine the effects of adsorption from solution of crude oil residua on the wettability of a polished stainless steel surface. Distillation residua with initial atmospheric boiling points of 700F were used in preference to the whole crudes in order to concentrate on the molecular weight range of interest, and to eliminate the possibility of composition change due to evaporation of the light ends. Also, these high boiling materials would be expected to be adsorbed from the whole oil in preference to similar compounds of lower molecular weight.

Jan 1, 1966

By Robert G. Nisle

The classic theory of pressure build-up in shut-in oil wells as developed by Horner and van Everdingen is based on two-dimensional radial symmetry in the well-reservoir system. Such symmetry does not exist in the case of a well which parfiially penetrates the producing formation. As a result of this lack of symmetry the use of the classic theory in such cases become questionable. In this paper the mathematical theory has been extended to include the case of partially penetrating wells. Numerical solutions illustrating the up-dication of the equations are presented. The effect of partial penetration on pressure build-up is shown by a comparison of synthetic pressure build-up curves derived from the numerical solution of the equation for partially penetrating wells for various degrees of penetration. It is shown that partial penetration is detectable from the characteristic shape of the pressure build-up curve and that formation productivity may be calculated from the pressure buildup data in a manner identical to that described by the classic theory. INTRO DUCTION The use of pressure build-up data on shut-in oil wells is a well-established technique for the measurement of reservoir productivity. The work of Homer' and van Everdingen' is well known. Since the publication of their pioneering work, others"' have elaborated and extended the technique. These authors have dealt exclusively with the case of wells that completely penetrate he producing formation. Two-dimensional radial symmetry is achieved, thereby, and the problem is greatly simplified. This ideal situation is seldom encountered in practice. But, in spite of this, the technique is often employed anyway. The question, therefore, arises: how much confidence can be placed in the results of such calculations when the data are taken on wells that only partially penetrate the producing formation? It is the purpose of this work to answer this question. Only the single-phase fluid case will be considered. van Everdigen' has presented a rigorous solution of the two-dimensional case, but because of mathematical complexity, this solution has not proved to be particularly useful. Horner' utilized Kelvin's point source solution in two dimensions and showed that it is a sufficiently good approximation for oil reservoir studies. The geometry of the well and the producing formation is illustrated in Fig. l. Geometrically the formation may be described as an infinite slab. The infinite slab is defined as the solid (the porous medium in this case) bounded by two parallel planes. Thus, the slab extends to very great distances in both the positive and negative directions of two of the coordinate axes, but is finite in

By Ivor Hawkes

A wide variety of borehole gages have been developed for measuring rock stress. They all operate on the principle that stress changes around a borehole result in deformation that can be measured by the gage and interpreted in terms of the stress change either by calculation or calibration. In general terms, gages that comply with the borehole deformations are referred to as “deformation meters” and those that restrain the deformations by reason of their rigidity are referred to as “stress meters.” The main advantages claimed for stress meters are: their “stress” sensitivity is much less dependent on the rock modulus than that of deformation meters, and they are clamped firmly in the borehole. The use of each of the borehole gages developed for stress determinations in rock in the main has been confined to the laboratory responsible for its development. To be generally accepted a gage must meet the following specifications : 1) Gages to be left in place to measure stress changes must be relatively cheap, and if possible recoverable, so that large numbers can be used to obtain an overall picture of the changing conditions. This, of course, is not necessarily the case for recoverable gages designed for absolute rock stress measurements where usually only one or two gages are involved. 2) For use in the adverse environmental conditions encountered underground, it is essential that gages be robust, stable, and unaffected by high humidity, corrosive water, or dust. 3) Highly qualified technicians are rarely employed specifically for rock mechanics studies in mines or on civil engineering sites and there- fore gages designed for measuring stress changes must be easy to set and

Jan 1, 1972

By R. Simon

The sources of energy dissipation for concentrated loadings on rock are considered in an attempt to account for the experimentally measured magnitude of the work required to break out a unit volume of rock from the free surface of an essentially semi-infinite medium. It is concluded that most of this work probably represents the elastic strain energy developed by the loading in a much larger volume of rock beneath the loaded region than the volume of the rock fragment broken out to the side of the loaded region. This strain energy is largely dissipated in the form of stress waves generated by the high rate of unloading produced by the propagating cracks. The energies associated with the formation of the new surfaces of the cracks and with the stress waves generated directly by the loading process are computed to be negligibly small. Possibilities for improving the utilization of energy to drill rod. subject to the geometrical limitations imposed by down-hole operation, are discussed. It is pointed out that any such possible improvements would probably have to be differential ones, since each rock configuration of more favorabIe loading geometry that can be created down the hole is accompanied by a complementary configuration of less favorable loading geometry. INTRODUCTION Dislodging each cubic inch of rock from the bottom of the hole by the action of a bit requires the expenditure of an amount of energy that varies from approximately 5,000 in.-lb to approximately 100,000 in.-lb, depending on the hardness of the rock, or, more technically, upon its fragmentation strength.1 In this paper we will discuss (I) why the energy expended in drilling is so large, (2) what happens to this energy upon completion of the drilling process, and (3) what are the possibilities for reducing the magnitude of the energy required to drill rock. DETERMINATION OF ROCK DRILLING ENERGY The volume of rock removed per unit time from the bottom of a hole of diameter D is evidently (7/4)D2R, where R is the rate of penetration of the bit. If P is the rate at which work is done by the bit on the rock at the bottom of the hole, the energy required to break out a unit volume of rock is given by: Ev =(4/p) P/D2R............(i) For rotary drilling, of either the rolling-cone or drag-bit varicty, P = 2pLN, where L is the torque resistance to rotation at the bottom of the hole and N is the rate of rotation of the bit. L is essentially the same as the torque measured at the rotary table only when drilling in shallow holes. The energies expended in rotating the drill string against the frictional resistance of the walls of the hole and and against the viscous drag of the drilling fluid are extraneous to the subject under consideration, although these may be much greater in magnitude than E, when drilling in a deep hole. For percussion drilling, P = fE where f is the percussion frequency and E is the work done on the rock per impact. The latter quantity can be both computed and measured for a percussion drilling machine. 2 (Under satisfactory drilling conditions, defined in terms of ranges of numerical values of certain dimensionless parameters, E is only 30 to 50 per cent less than the impact energy of the striker.2) Alternatively, E, may be measured directly by dropping chisels shaped like bit edges, backed by rigid weights, onto the surfaces of laboratory rock samples of effectively semi-infinite extent. Under these circumstances, essentially all of the impact energy is converted to work done on the rock, and the relationships among volume of rock broken out, chisel shape, impact energy and indexing distances can be obtained.3 The values of the energy required to break out a unit volume of rock under favorable circumstances are substantially in agreement for rotary drilling, percussion drilling and drop testing at atmospheric pressure. The energy per unit volume is a quantity of the order of magnitude of roughly twice the com-pressive strength of the rock as measured by a uniaxial loading test. The phrase "order of magnitude" in this paper means from about 1/3 as much to 3 times as much; i.e., the energy per unit volume may range from roughly the same up to several times

By F. B. Plummer

GEOLOGICAL engineering as applied to oil fields, or production geology as some prefer to designate the profession, is designed to fill in the border line between pure geology and pure petroleum engineering. Therefore the production geologist may, and frequently does, reach out to grasp much in both professions. Where once the oil geologist was content to pick samples out of a mud ditch and try to identify oil formations from the color or appearance of flakes of rock bailed out of a well, now he has to deal with graphic electrical logs obtained by intricate and highly technical electrical apparatus and to make exact determinations to the fraction of an inch of the depth and thickness of an oil sand 2 miles below the surface.

Jan 1, 1944

By D. Hanson

Fox most of their practical applications metals are required to with-stand stresses of appreciable magnitude: indeed, it is because they possess the quality of resisting stress without becoming permanently deformed that they find such extensive use in the service of man. Metals and alloys must, in service, usually behave as elastic substances-or nearly so. It is not difficult to satisfy this condition at ordinary temperatures. Iron and its alloys, especially the steels, are at normal temperatures excellent elastic bodies, capable of satisfying most of the mechanical requirements of the engineer: where electrical, chemical or other properties are impor-tant, which cannot be met by steels, it is usually possible to find a non-ferrous alloy such as nickel, copper or aluminum, which will prove satisfactory. When the metals or alloys are not inherently sufficiently elastic, cold-working or heat-treatment may develop elastic properties to a sufficient extent for practical needs. By means of relatively simple, rapid tests we can measure such properties as elastic modulus, limit of proportionality and proof stress, upon which design can be based with confidence. The case of the soft metals, such as lead and tin, is well known to be exceptional. They possess no definite limit of elasticity, and the value of proof stress or tensile strength depends to a great extent on the speed with which the test is carried out. Design here must be based on other considerations than a well-established theory of the proportionality of stress and strain. It is now generally recognized that steels and non-ferrous alloys possess at temperatures not greatly exceeding that of the atmosphere, characteristics quite different from those existing at ordinary temperatures, and that they assume qualities similar to those of the soft metals. Not only have they no limit of elasticity, but the proof stress and the ultimate stress depend on the time of application of the load. Flow under load may persist for long periods of time, possibly indefinitely, and the determination of a true maximum stress becomes a matter of great difficulty.

Jan 1, 1939

By J. C. Uy, T. E. Davidson, A. P. Lee

The effects of hydrostatic pressures to 26 kbars on the micro structure of poly crystalline Cd, Zn, Bi, Sn, Zr, Mg, Cu, and Fe were examined. Pressure-induced microscopic plastic flow in the form of boundary migration, slip, multiple slip, or twinning has been observed either singly or in combination in cadmium, zinc, bismuth, and tin. No deformation was observed in zirconium, magnesium, copper, and iron. The occurrence of such deformation, in terms of its intensity and initiation pressure, relates directly to the degree of anisotropy in the linear compressibility. Pressure cycling does not significantly affect the residual tensile properties of a zinc alloy which exhibits pressure-induced deformation similar to that of Pure zinc. CLASSICAL elastic theory predicts that a superim-posed hydrostatic pressure will not induce shear stresses in an ideal material. Thus, in the case of homogeneous and isotropic materials plastic flow will not occur as a result of pressure exposure, regardless of the magnitude of the pressure, unless some form of phase transformation or permanent density change takes place. However, real materials, such as metals, often vary considerably from the condition of homogeneity and isotropy. For this reason, Vu and johannin' examined and observed hydrostatic pressure-induced microscopic deformation in polycrystalline cadmium and, zinc, but not in aluminum, to pressures of 9 kbars and indicated that its occurrence is related to anisotropy in the linear compressibility. In addition, Davidson and omaan' have reported pressure-induced deformation in polycrystalline bismuth below the 1-11 transformation pressure. It becomes apparent then that under certain conditions hydrostatic pressure can induce localized internal shear stresses in some metals of sufficient magnitude to cause plastic flow. In this work, eight pure single-phase metals of different lattice structures and degrees of elastic anisotropy were examined after pressure exposures of up to 26 kbars in order to establish the conditions under which such deformation occurs and the type of deformation as a function of pressure. The effects of pressure cycling on the mechanical proper-

Jan 1, 1965

By J. D. A. Morrow

TO my mind the National Bituminous Coal Act so far has proved one of the unhappiest experiences that has ever befallen the bituminous coal operators of the United States. Viewed in the light of its ugly consequences everyone should recognize this measure for what it is -a weird thing as unreal as a page from "Alice in Wonderland." Indeed it might be another stanza to the tale of the Walrus and the Carpenter, with the coal operators in the role of the unfortunate oysters who were taken on that memorable ramble. It is time that coal producers open their eyes, jerk themselves out of any lingering hypnotic optimism about the price-fixing provisions of this law, demand the repeal of these corroding clauses, and then set about remedying as best they can the disastrous effects of this retromingent scheme to regulate the coal business.

Jan 1, 1939

By Bauer, Alan

In considering blasting it is necessary to consider the drilling and explosives since one is generally concerned with the total cost of muck of a certain size in the pit or through the crusher. To get a current idea of the drilling situation in open pit mines plotted in Fig. 1 are the drilling costs per ton of material vs. hole diameter for rotary drill holes in large limestone, iron ore and taconite operations. The exception is the 2-in. diam hole which was drilled with a percussion drill in limestone.

Jan 1, 1968

By L. Russell Van Wert

DURING an investigation in which the solubility relations of the phases in Muntz metal (60 per cent. copper, 40 per cent. zinc) were under study, certain phenomena that had no immediate connection with the main problem were observed, which were thought sufficiently interesting to study further. Because of lack of time, only a preliminary survey was made of two of these; namely, the cleavage structure developed under certain conditions in a 60:40 brass and abnormal grain growth in this alloy. CLEAVAGE STRUCTURE IN HEAT-TREATED MUNTZ METAL Carpenter noted many years ago that cold-working a brass of the Muntz metal type, which had been quenched previously from within the beta field, results in a partial breakdown of the supersaturated beta solution and the precipitation of the solute (the alpha solution) in the cleavage planes of the beta grains. This manner of rejection of a solute from a metastable solid solution is not peculiar to this particular alloy, for among others, it occurs in the cold-working of certain austenitic steels; for example, the austenitic nickel steels. In these ferrous alloys, cold deformation produces a partial decomposition of the austenite, with the formation of martensitic "needles" and zigzags in the austenitic poly-hedra. It is interesting to note that while the two solid solutions-austenite and quenched Muntz metal- are metastable and in their mode of decomposition behave quite alike when deformed in the cold, the metastability of each results from a different cause; viz., that of the austenite from the fact that it is a supercooled solution (its solvent, gamma iron, at ordinary temperatures is below its normal stable range) whereas the metastability of the quenched Muntz metal is the result of supersaturation.

Jan 1, 1929

By U. N. Bhrany, N. Arbiter

Over the last one hundred years the problem of assessing the efficiency of energy consumption in producing rock breakage has been studied by many investigators from a variety of viewpoints. Their contributions fall into three main categories: (1) those characterized by a priori assumptions of a relation between the energy required for fracture and the degree of fragmentation produced (e.g. Rittinged(l), Kick(2) Bond(3)); (2) those studying simple systems with controlled energy applications (Gross(4)?(5) ); (3) those treating operating data to develop practical relative measures of efficiency (Coghill(6), Taggart(7)). Closely involved in the efficiency problem is the characterization of size distributions produced by comminution. Unless an experimental size distribution can be approximated by a distribution function and its constants, it becomes difficult if not impossible to develop quantitative energy-particle size relationships. While many such functions have been proposed, none are both completely adequate and convenient. The simpler fonns usually describe only a part of the sizing data, while those which apply to a greater extent are cumbersome(8). The thesis underlying the study here reported can be stated as follows: Size reduction in a tumbling mill subjects ore particles to a relatively constant fracture-producing environment. The intensity of the forces is determined by such factors as the mass of the breaking bodies (rods, balls, rock), and the speed and dimensions of the shell. For a particular ore the extent of size reduction will depend both on the intensity and on the duration of exposure. The latter is the residence time in a batch mill, or is determined by the effective volume and the flow rate in a continuous mill. Size reduction can thus be regarded as a rate process in which the weight of material in size intervals varies as a function of grinding time. Although both the rates of disappearance of coarser sizes and

Jan 1, 1961

By A. L. Sweetser

EXPERIENCE has shown how difficult it is to obtain information regarding laboratory-tests in connection with the chlorination-process for the extraction of gold from its ores, and I therefore present the following method, somewhat in detail, for the benefit of those who may desire to pursue research work in this field. The ore chosen was a partly-decomposed porphyry, extremely siliceous and comparatively soft, and of an average value per ton of from $25 to $26 in gold and $0.68 in silver. The chemical analysis gave : Fe2O3, 3.35; FeS, 1.5; MnO2, 0.75; ZnCO3, 4; Al2O3, 3.20; H2O, 0.7; SiO2 and insol., 83.50 per cent. The ore, first crushed to pass a 5-mesh screen, was coned and quartered until a 45-lb. sample was obtained. Samples for assay and analysis, taken from this lot by means of riffles, were crushed to pass a 100-mesh screen. The original sample was divided into 10-lb. lots, of which one was crushed to pass a 10-mesh screen; another through a 12-; the third through a 20-, .and the last through a 30-mesh screen. Because of the production of an excessive quantity of fine material it was deemed inexpedient to crush finer than 30-mesh size-a decision the wisdom of which is proved by the data in Table I., showing the increasing ratio of slimes, in proportion as the ore is crushed finer. In order to determine the percentage of fines in the sizes of mesh selected, a weighed sample of ore was taken from each mesh, and a sample from the 10-mesh lot was passed successively through 20-, 40- and 100-mesh screens, and the percentage remaining on each screen determined. This process was repeated with the 12-, 20- and 30-mesh lots, with the results given in Table I.

Sep 1, 1907

By J. D. Doherty

That America's great coal deposits eventually will be our principal source of liquid as well as solid fuels is generally accepted. Moreover, the day when synthetic oil from coal will begin to supplement our petroleum supplies does not appear to be far off. The American petroleum industry has not spared effort or expenditure in its attempt to keep pace with the demand for oil, and recent production has exceeded expectations. However, the rapidly rising demand for liquid fuels plus the increasing difficulty of finding and developing the new oil needed even to maintain present production rates make it highly unlikely that oil from domestic wells can fully meet future oil requirements. Therefore, it appears that one or more of the following courses must be followed: 1. Curtail oil consumption. 2. Increase imports. 3. Develop new sources such as synthetic liquid fuels.

Jan 1, 1949

By R. R. Joseph, K. A. Gschneidner

The solid solubility of magnesium in the close-packed modifications of lanthanum, cerium, praseodymium, neodymium, gadolinium, dysprosium, and lutetium was determined from approximately 250°C to the eutectoid temperature by the X-ray parametric technique. The maximum solubility at the eutectoid temperature was found to be 9.4 at. pet in La, 8.2 in Ce, 9.2 in Pr, 8.2 in Nd, 14.1 in Gd, 13.5 in Dy, and 11.5 in Lu. The solubility when compared at a homologous temperature was found to increase in a smooth manner with decreasing size factor from lanthanum to lutetium. It was found that the apparent atomic radius of magnesium when dissolved in the lanthanide solvent was constant and could be accounted for by consideration of several models dealing with departures from Vegard's law. The eutectoid temperatures for the lanthanide-rich La-Mg, Ce-Mg, and Nd-Mg systems were found to be 544", 505°, and 551°c, respectively. A study of the solid solubility of magnesium in the lanthanide metals was initiated because the valency and electron egativity difference are essentially constant and favorable for solid-solution formation, and thus one could examine the effect of size on terminal solid solutions. The size factors based on metal radii range from 14.6 pet for lanthanum to 7.5 pet for lutetium. Since the electronegativity difference is small, 0.06 unit or less, application of the Hume-~othery' and Darken and Gurry2 criteria for solid-solution formation indicates that the solubility of magnesium would be expected to be small for lanthanum (between 5 and 10 at. pet) and to increase as we proceed along the lanthanide series. A search of the literature revealed no data on the solubility of magnesium in the lanthanide metals except for the solubility of magnesium in cerium at 450oCA typical phase diagram for the lanthanide-rich end of the lanthanide-magnesium phase diagram is shown in Fig. 1. EXPERIMENTAL PROCEDURES Preparation of Alloys. The lanthanide metals used in the preparation of alloys for this investigation were prepared from the corresponding fluoride by metallothermic reduction techniques previously described by Daane.4 The chemical analyses of the metals used are listed in Table I.

Jan 1, 1965

By R. W. Drier

THE conductivity of copper wire is of prime importance to the electrical industry and consequently to the copper refiner and wire manufacturer. Annealed copper wire has a higher conductivity than hard-drawn wire, but, on the other hand, its tensile strength is lower. In an attempt to explain the reasons for these changes in property or at least to study the conditions existing in these two types of copper wire, the experiments described here were carried on in the Department of Metallurgy of the Michigan College of Mining and Technology. This is only a partial and preliminary report on some of the work done to date on a research program of which the object is an intensive study of copper. It is offered with the hope that, though it is not an exposition of the most rigorous of conclusions, the general trend of inferences which may be drawn will be of value and interest.

Jan 1, 1929

By Howard A. Meyerhoff

AS a source of mineral wealth, the larger islands of the West Indies have never had an enviable reputation. The Spaniards took possession of them in the sixteenth century hopeful that they would yield gold; but it was not long before they knew the rather rigid limitations of Antillean gold production and were seeking-and finding ---richer deposits of the precious metals in Mexico and on the west coast of South America. Although a great deal of wealth changed hands in the West Indian islands in subsequent years, the fact may be laid to the abundance of pirates and privateers and not to the richness of local ore bodies.

Jan 1, 1941

By Lucien Eaton

THE use of filling in mines is less common in the United States than it is in Europe, where in some places it is required by law. In most cases the filling is placed by hand, and the material used for this purpose is the waste from development and that sorted from the ore in the stopes. When these sources provide an insufficient supply, additional rock must be quarried on surface or mined underground, or some other material :st be used. In different parts of the world sand, clay, gravel, culm, nulated slag, mill tailings, and even ashes, have been used as filling material in place of or in conjunction with rock. Of all the materials used for filling the best is probably clean sand. Gravel, finely crushed rock, granulated slag and coarse mill tailings are almost as good, and the methods used for placing and confining sand will apply equally well to any of these. The advantages of sand are its comparatively slight compressibility and the ease, economy and convenience with which it may be placed. On account of the voids, which necessarily occur in fills made of coarse waste, such fills will compress 10 to 25 per cent before they develop their full strength, whereas clean sand seldom compresses more than 5 per cent. Sand is especially desirable when practically complete filling is required, and sand derived from mill tailings, especially when not thoroughly cleaned, has been remarkably effective in sealing off and extinguishing mine fires. When natural sand is available on surface, or when it can be obtained from the mill tailings or tailings dump, the cost of using this material for fill will probably be considerably less than that of rock. In this paper it is not proposed to discuss all methods of filling, butt to describe some of the methods used for placing sand fill and to make a brief comparison of their merits.

Jan 1, 1932

By D. W. Levinson, L. E. Tanner

DURING the course of an investigation of the zirconium-iron-tin system the zirconium-iron system was reexamined up to 55 pct* Fe. The alloys pre- visible melting3 and X-ray diffraction studies were made of samples of the alloys. The ferromagnetic properties of ZrFe2were determined by Professor P. W. Selwood* using a modified Faraday balance.4 The zirconium-rich portion of the phase diagram is presented in Fig. 1 and compared with the work of Hayes et al.1 The maximum solubility of iron in ß is somewhat decreased while the eutectic temperature is raised. There seemed to be no change in the eutectic composition of 16 pct Fe. Since the base material was so low in iron content, it was possible to establish the maximum solubility in a between 0.017 and 0.025 pct Fe at the eutectoid temperature. The observation of fine ZrFe, particles in the micro structure of a specimen of 0.012 pct Fe alloy quenched from 700°C indicated that the solubility drops below this composition at 700° C and lower. Further study was made of the intermediate phase ZrFe2. wallbaum5 identified the compound initially as ZrFe2 with a C 15 (MgCu2) structure, placing it at 55 pct Fe stoichiometrically. Hayes et al.1 believed they found the phase at about 47.2 pct Fe and called it Zr2Fe3 but reverted to ZrFe, in the discussion of their paper.6 Jordan and Duwez7 confirmed Wallbaum's work as well as finding the same single-phase structure to about 62.3 pct Fe or Zr0-61 Fe2-18. In order to establish the ternary phase relations in the zirconium-iron-tin systema the exact position of this phase had to be known. This was accomplished by X-ray diffraction, visible melting, and metallographic techniques. Elliott8 obtained a single-phase ZrFe2 X-ray diffraction pattern from an alloy of about 55 pct Fe. This was confirmed in the present study with an alloy of 54.81 pct Fe. However, extra lines (attributable to a or ß zirconium) were found in diffraction patterns of the 47.42 and 49.83 pct Fe alloys. The melting characteristics of these same alloys were studied by suspending 47.42, 49.83, and 54.81 pct

Jan 1, 1960

By E. B. Thornhill

Discussion of the paper of E. B. THORNHILL, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 104, August, 1915, pp. 1653 to 1670. D. B. HUNTLEY, Oakland, Cal.-About 15 years ago it chanced to be my lot to cyanide some mill tailings, assaying about $5 per toll in gold and, a few cents in silver. It was in southern Idaho, a. desert region where costs are nearly as large as in central Nevada. We knew that we had a lot of tailings that had been amalgamated and contained about 1 lb. of quicksilver per ton. We knew that we would dissolve some of the quicksilver when we cyanided them with say 0.25 per cent. cyanide solution. We figured (optimistically) that the cyanide would dissolve all of the quicksilver, and we thought to capture all of that, 1 lb. per ton; and we figured out profits as partly gold, partly silver, and partly quicksilver from the recovery in working those tailings. Actually, however, we did this: We had a battery of three large, old-fashioned silver-mill retorts. We retorted our zinc-dust precipitate, recovering about ¼ lb. of quicksilver per ton treated. That was only a loss of 75 per cent. of what we originally had, but still it was profitable by virtue of the conditions. I mention it partly to call attention to the crude old way of doing it, and partly to call attention to how chemical methods for recovering quicksilver have developed in the last 15 years.

Jan 12, 1915

By N. A. Gjostein

The real and apparent dependence of the surface self-diffusion coefficient, Ds, of gold on crystallo-graphic orientation has been investigated by isolated scratch smoothing and grain boundary grooving experiments. No systematic variation of Ds with orientation was found along the [100] zone. In view of the experimental scatter in these results, however, only aniso-tropy ratios, p, greater than -1.3 would be detectable. Anomalously low values of Ds were found on the [0ll] and [110] zones when the diffusion direction lies along (the scratch or grain boundary groove is perpendicular to) these zones. By comparing these results with a previous y plot study of gold, it is hypothesized that this is not an intrinsic diffusivity effect, but rather it results from a decreased driving force for mass transfer at orientations where the y-plot curvature is negative and appreciable in magnitude relative to y. The characteristics of this type of anisotropy do not appear sEVERAL investigations1-7 have dealt with the anisotropy of the surface self-diffusion coefficient, Ds, of metals as measured by the decay of single or multiple to be in agreement with the hypothesis of fast diffusion along ledges in the surface structure. In certain cases the Fourier method of determining Ds, described in Paper I of this series9 was compared with the second moment analysis in order to determine whether or not the method of analysis affects the anisotropy ratio. While the type of analysis does influence the magnitude of the anisotropy ratio, this effect is not associated with the shape of the profile, but rather is connected with the iterative volume diffusion correction used in conjunction with the second moment analysis. It is further demonstrated that the volume diffusion correction can be too large by either method when the y-plot curvature effect is large. Certain orientations exhibit an unusual temperature dependence of Ds ; this is discussed in terms of the y-plot curvature effect and/or the influence of impurities on Ds . scratches in the surface. Depending on the system investigated, both large1"3'6'7 and small4'5 anisotropies in Ds have been found. Although adsorbed impurities undoubtedly play an important role in determining the magnitude of the anisotropy,8 there are other factors that can give rise to an apparent anisotropy in Ds, thus obscuring the true nature of an intrinsic anisotropy in

Jan 1, 1968