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By E. M. Kalar, I. Iwasaki, J. D. Zetterstrom

Several methods of removing fatty acid coatings from iron ore flotation concentrates were tested both on a Mesabi oxidized iron ore and on a magnetic taconite concentrate, and their effects on the duplex flotation process and on pelletizing were compared. Either acid or alkali alone could not remove the coatings, but a combination of such reagents as lime and quebracho, calcium chloride and pyrophosphate, or sulfuric acid and an organic acid (oxalic, malonic, or citric acid) was quite effective. The use of activated carbon was found to be particularly promising. The removal of fatty acid coatings from iron ores is of much practical interest when a pelletizing process is being considered for a concentrate floated with a fatty acid collector or when a duplex flotation process is being considered for upgrading an oxidized iron ore. A duplex flotation process is a fatty acid flotation of iron minerals followed by an amine flotation of the siliceous gangue from the rougher iron concentrate. Such a process is being used in the Florida phosphate fields.' Although in northern Michigan mills fatty acid flotation concentrates have been pelletized successfully, at other locations fatty acid coatings on iron flotation concentrates have proved so undesirable in the agglomeration operation that other methods of concentration had to be sought.' Since fatty acid coatings cannot be removed as readily with a simple acid or alkali treatment from iron oxide surfaces as from Florida phosphates, a combination of reagents, such as lime and quebracho,3 lime and alkali phosphate,4 or sulfuric acid and oxalic acid,' has been proposed. It was also thought that activated carbon might be effective in removing fatty acid coatings due to its high adsorptive capacity. Activated carbon, with its enormous surface per unit of volume, is well known for its exceptional efficiency in removing organic pollutants from industrial effluents. This article presents the practical aspects of the above methods when they are applied to the duplex flotation process and to the pelletizing of iron flotation concentrates. The article also includes a preliminary investigation of the common parameters involved in the depressant activity of the reagents. EXPERIMENTAL WORK Initially, the experimental work was directed towards the optimization of each method for the removal of hydrophobic coatings from iron oxide surfaces floated with fatty acids. Subsequently, the methods thus optimized were tested in the duplex flotation process with an oxidized iron ore and in the pelletizing process with a magnetic taconite concentrate. Preliminary Flotation Tests: Although the three types of chemical treatment reported in the literature were briefly investigated for the purpose of comparison, major emphasis was placed during the preliminary flotation tests on the use of activated carbon because it was thought to have certain advantages over the chemical methods. LIME AND QUEBRACHO - To obtain a flotation concentrate for optimizing the lime and quebracho method of fatty acid removal, the magnetic taconite concentrate was used. The concentrate had a size consist of 90% passing 325 mesh and analyzed 64.5% iron. After a few preliminary tests the fatty acid flotation procedure with the magnetic taconite concentrate was standardized as follows. A 1200-g sample of the magnetic concentrate was pulped in a Fagergren laboratoy flotation cell to 40% solids, conditioned with 0.5 lb of soda ash per ton for 2 min, and then further conditioned with 1.0 lb of Acintol FA-2 per ton for 2 min. After 5 min of flotation, recovery was nearly complete, averaging 98.6% of the weight and 98.7% of the iron. The cell product, which amounted to 1.4% by weight and analyzed 63.2% iron, consisted mainly of relatively coarse middling particles. Since the repro-ducibility of the flotation concentrates produced by this procedure was vey high, the same procedure was used to prepare fatty acid concentrates for each of the six tests of the lime and quebracho method. To test the removal of the fatty acid from the magnetite surfaces by the lime and quebracho method, a fatty acid froth product was returned to the flotation cell, repulped by 30 sec of agitation, and then con-

Jan 1, 1968

By W. Kauenhowen

The production of petroleum in Germany during 1932 totaled about 1,608,558 bbl., a slight increase over the 1, 602,517 bbl. produced in 1931. A decline, as shown in Table 1, occurred chiefly in the Volkenroda (Thuringia) field. The total production of the other fields (salt domes), however. reached a new record, about 21 per cent above 1931. Table 1.—Oil Production of Germany by Fields and Oil Provinces, 1928-1932 (Barrels of 42 Gallons)" Salt Dome Province __________________________________________________|_________________________________________________________________________________________________________________________ 1928 274,323 322,742 679 46,319 644,021 644,315 1929 310,891 337,582 10,535 67,578 719,901 720,069 1930 586,404 427,539 100,716 72,485 1,186,969 29,806 1,220,296 1931 506,548 403,634 213,549 116,088 1,242,598 360,885 1,602,517 1932 769,405 366,982 230 979 130,711 1,498,077 110,481 1,608,558 " Official figures published in Germany are given in metric tons. For the above conversion into barrels a factor of 1 metric ton equaling 7 barrels has been used. Includes a very small production from Hcide, Holstein. c Includes a very small production from Tegernsee, Bavaria, and Bruchsal, Baden. Nienhagen-Hanigsen Field In 1932 the Nienhagen-Hanigsen yielded about 51 per cent of the production from the four German salt dome fields. During 1932 the productive area was again extended, chiefly towards the northwest in the so-called north district, to which the present drilling activity is confined almost entirely. Since the discovery of the north district in 1928, about 45 wells have been drilled in it, of which only two were

Jan 1, 1933

By C. G. Dunn, F. W. Daniels

IN recent publications1-5 the existence and behavior of subgrain boundaries in high-purity metals has been clearly brought to light. Lacombe and Beaujardl by means of special etching methods disclosed in polycrystalline sheets of aluminum the existence of substructures differing in orientation by small amounts (about 1/4"). Boundaries of these structures at relatively high temperatures had the remarkable property' of moving about while the ordinary boundaries remained stationary. Cahn2 also observed substructures in bent and annealed single crystals of aluminum, zinc, magnesium, and rock salt. The position of subboundaries could be explained in terms of a dislocation mechanism of polygonization in which dislocations move into lines at right angles to the bent glide planes thereby relieving elastic stresses in these planes. Guinier and Tennevin8,6 disclosed the further interesting feature that polygonized structures coarsened significantly upon prolonged annealing. Somewhat similar subgrain phenomena have been observed in silicon iron of commercial purity. Although some evidence for the development of macro-mosaic structures in silicon iron already has been reported by one of the authors6,7 under the phenom-enological term "crystal recovery," much better evidence recently has been obtained due to improved etching techniques. In addition, phenomena regarding structural changes have been uncovered. The present investigation is divided into three parts: (1) The phenomenon of Laue spot sharpening on annealing cold-rolled crystals, (2) the phenomena of polygonization and subgrain coarsening The material used in the present investigation was high-grade commercial silicon iron sheet of nominal composition, 3.3 pct Si, 0.004 C, 0.011 P, 0.010 S, 0.04 Mn, 0.01 Al, 0.04 Cu, 0.01 Sn. Large single crystals of this material Were prepared for cold-rolling or bending as scheduled. Cold-rolling of 12 pct was carried out on a laboratory 8-in, diam rolling mill. The bending deformations were performed by pressing the crystals between a solid Fig. 2—lllustrative foue patterns to show Laue spot sharpening. a (Left)—Specimen as cold rolled, b (right)—After 48 hr at 1400°C. round bar and a mating half cylinder, both heavily greased. Individual specimens were cut from the deformed crystals, and the cut edges were deeply etched prior to annealing. Laue photographs were made using 40-kv tungsten radiation. The technique used to disclose the various subboundaries was an electropolish and electroetch in a bath of chrome-acetic acid.' The anodic polishing done at 22 v was immediately followed by etching at a reduced voltage, which was dependent upon the nature of the subboundaries. Phenomenon of Laue Spot Sharpening on Annealing Cold-Rolled Crystals Fig. 1 gives the initial and final orientations of the specimens cold-rolled 12 pct. Each specimen was annealed at a temperature and for a time which caused significant structural changes as evidenced by alterations in Laue patterns. Representative Laue patterns and micrographs showing the essential changes are given in Figs. 2, 3, and 4. The essential points to be derived from these illustrations follow: 1. Annealing at 950°C clearly develops a substructure with the orientation of the cold-rolled specimen. 2. The subboundaries formed obviously separate regions of nearly the same orientation. Some of the subboundaries appear as a sequence of dots similar to those observed in aluminum by Lacombe and Beaujard,' but whether this is due to extremely small differences in orientation is not known at present. 3. The substructure coarsens upon prolonged annealing. 4. Prolonged annealing also causes a decrease in orientation spread according to Laue spot sharpening'

Jan 1, 1952

Greater automation of facilities is probably the best hope of the mining industry in its efforts to surmount continually rising labor costs. Underground mining, with its inherently low unit labor output, is especially vulnerable to rising costs, and here maximum automation is becoming increasingly important. One area of such operations that has been receiving a great deal of investigation is that of ore haulage and hoisting, two steps that often account for 10-35% of underground operating costs. Innovations and experimentation by mining firms and manufacturers over the past few years have resulted in larger, faster and more efficient tramming and hoisting equipment, but the White Pine Copper Co., at its operation in the Upper Peninsula of Michigan, is preparing to start up an entirely new concept in haulage later this summer. Known as the Dashaveyor System, it consists of individually powered modules (cars) that run on tracks inside a rectangular tube or on an open trackway at predetermined speeds up to 50 mph. At White Pine the Dashaveyor will be used to carry ore (crushed underground to -10 in.) from the mine to the concentrator. Dr. James Boyd, president of Copper Range Co., which is a 25% shareholder in The Dashaveyor Co., has indicated that if the Dashaveyor meets the expectations for surface operation, it will also be used underground for ore transport in place of the several miles of conveyor belts currently in use (Business Week, July 29, 1967).

Jan 7, 1968

By O. D. Gaither

This paper is an analytical study of the flow of fluids through small vertical conduits. Small conduits are defined as 11/4-in. nominal diameter tubing size and smaller, and approximately twice this area for annular conduits (i.e., 1- X 21/2-in. annulus and smaller). Experimental data are presented for the 1-X2-in. and 11/4- X 2%-in. annuli, and the I-in. and 11/4-in. tubing, since these represent the small conduit sizes and configurations generally encountered in oilfield applications. Data have been gathered for these conduits for single-phase water, single-phase gas and two-phase water-gas mixtures, with particular emphasis on high gas-liquid ratios. Water rates in excess of 2,000 BID and gas rates in excess of 2.5 MMcf/D, and two-phase flow ratios in between these two, represent the scope of the data gathered. Existing equations have been applied to predict flowing pressures and compared with experimental data. New correlations have been developed. INTRODUCTION The increased economic pressure on the domestic oil industry in the United States has constantly required the use of new techniques and equipment designed to reduce the cost of finding and producing oil and gas. Since tangible items are most readily apparent in economic analysis, the advent of lower-cost well completions was inevitable. One of the methods used to reduce costs which has received widespread attention is the slim-hole completion technique where tubing is used as the well casing and in which small conduits are used for tubing if necessary. Small conduits, defined by Kirkpatrick1 as "11/4-in. diameter nominal tubing and smaller for tubing flow and less than twice the 11/4-in. diameter nominal tubing internal flow area for annulus flow", have also found widespread usage as siphon strings for de-watering gas wells and as "kill" strings in deep high-pressure oil and gas wells. The growing use of small-diameter tubing has resulted in an increased need for development of improved methods to measure or predict flowing bottom-hole pressures since the physical dimensions generally preclude the use of subsurface-recording pressure gauges. Even in the cases where small bombs are available, the relatively high velocities encountered at nominal flow rates make it necessary to use excessive weight bars or special hold-down devices. Attempts to use recognized correlations to accurately predict flowing or gas-lift performance in wells equipped with small conduits have been generally unsuccessful. Insufficient field data were available to allow the development of a correlation on this basis, and an experimental approach was applied in an attempt to obtain a workable relation. The experimental approach used to obtain the data presented in this paper was actually a compromise between a field installation and a laboratory study. A test well 1,000 ft in length was used to obtain flow data on single-phase liquid, single-phase gas and two-phase water-gas flowing mixtures. Liquid rates up to 2,200 B/D and gas rates up to 3 MMcf/D were used in the single-phase flow studies. Two-phase flow rates from 100 to 600 B/D with gas-liquid ratios from 500 to 8,000 cu ft/bbl were recorded. Experimental data were obtained for single- and two-phase flow through 1-in and 11/4-in. nominal tubing, and through the annuli between 1- and 2-in. and 11/4- and 2%-in. nominal tubing strings. Experimental results for the two-phase flow are compared to the Poettmann-Carpenter correlation2 which is widely used as a comparative standard for development of multiphase flow predictions in flowing and gas-lift wells. Correlations developed by Tek,3 Baxendell and Thomas" were also investigated. The experimental data recorded herein fell in between the two flow regimes as defined by Ros," and this correlation also failed to yield satisfactory results. The fact that existing correlations failed to confirm the experimental data led to the need for development of a new correlation. Although a two-phase flow study was the primary objective of this investigation, data were also recorded for single-phase flow of water and gas, and constants were developed relating to pipe roughness and equivalent diameters for annular flow. These single-phase studies assisted materially in the development of certain of the two-phase flow results. Considerable previous work has been published which presented relationship of surface measurements to bottom-hole condition. The works of Buthod and Whiteley,6 Jones,' Poettmannb and the Texas Railroad Commission" are classic examples of the successful use of mathematical relationships which allow acceptable predictions of subsurface pressures, when gas is the flowing fluid. Darcy and others have derived relationships which may be used with minor modifications to predict subsurface flowing conditions in injection and water-supply wells. As previously stated, the application of the single-phase flow relationships

By K. Heindlhofer

ESTIMATES of the "plasticity" of a metal are commonly deduced from three types of test-tensile, torsion and impact. The several results have been more or less at variance, though this disparity has attracted little notice, largely perhaps because they have been expressed in different terms. The discrepancy between the results of the three tests becomes obvious when each is made at a series of low temperatures, for the temperature range within which the "plasticity" of iron largely disappears proves to be very different in the three types of test. The rather abrupt disappearance of "plasticity" of iron within a narrow temperature range cannot be due to any physicochemical change (such as a precipitation) taking place in the material at that time, because the original plasticity is immediately regained when the temperature of the material is brought above the sensitive range. Accordingly this differ-ence in behavior shows that the "plasticity" of a metal depends upon the mode of action of the stresses which produce the deformation, and there-fore upon the method of test. Analysis of the stresses leads to the conclusion that the observed plasticity of a metal is determined by the relation between its resistance to rupture by separation and its resistance to shear (slip), on the one hand, and between the effective normal and shearing stresses on the other; and that the relation between the two resistances does not in general remain constant with change of temperature, and may somehow be altered to some extent by the previous treatment of the specimen. This suggests the view that the results of none of the usual mechanical tests are directly comparable even for a single metal tested at a series of tem-peratures, or for a series of metals at one temperature, because the propor-tion of the total resistance of the metal to the test contributed by the

Jan 1, 1934

By R. A. Wolfe, H. W. Paxton

Self-diffilsion coefficients for cr51 and Fe55 in 12 pct Cr-Fe and 17 pct Cr-Fe for Fe55 in chromium, and for Cr51 in vanadium have been measured. The results are compared with other values for the Fe-Cr system, and with the various theories of diffusion in hcc metals. Some empirical correlations are discussed between Do and Q in hcc systems, or, expressed differently, the constancy of ?G*/T solidus for seveval bcc metals and alloys is noted. It appears very probable that a vacancy mechanism is operative in bcc metals, hut this cannot he stated with certainty. THE great bulk of work on diffusion in metals, both experimental and theoretical, was for many years concentrated on those with close-packed and, in particular, fcc lattices.1,2 There appears to be little doubt that the mechanism of diffusion in these solids is vacancy migration, leading to mass transfer and in substitutional solid solutions to a Kirken-dall effect.3,4 For bcc metals, the picture is much less clear. The Kirkendall effect certainly occurs in several alloys.5-10 However, attempts to understand the factors contributing to the pre-exponential in the usual expression for the diffusion coefficient D =D, exp {-Q/RT) by extension of ideas useful in close-packed lattices have not always been successful. Zener,11 Leclaire,12 and Pound, Paxton, and Bitlerl3 have suggested that various forms of ring diffusion may be important in some bcc metals. For close-packed metals, Do is usually about 1 sq cm per sec and Q - 35Tm kcal per mole (Tm = melting temperature in OK). The theory of Pound et al. suggests for ring diffusion that Do may be about 10-4 and Q, although difficult to calculate with any precision, would be significantly less than 35 T,. The experimental results on self and solute diffusion in ? uranium14,15 and ß zirconium,10 and for solutes in 0 titanium,17 and possibly for self-diffu- sion in chromium below about 0.75 T,," gave some credence to this theory. However, not all bcc materials display low values of DO and Q, and the exceptions were not predicted by any theory. Furthermore, it has recently become apparent that, in bcc materials, log D is not always linear with T-l if a sufficiently wide range of temperature is studied.16,18 This variation may be such that Q may increase18,19 or decrease20 with increasing temperature. The present work was undertaken in an attempt to provide further diffusion data on bcc metals, and to try to understand the factors which contribute to differences in behavior between the various elements. For part of this work, the Fe-Cr system was chosen since it is of considerable technological importance, and data on 12 pct Cr and 17 pct Cr alloys appeared well worthwhile to supplement that existing for the remainder of the stern.18,22 The diffusion of Fe55 in chromium was studied as an example of a more or less "normal" tracer element in a possibly abnormal host lattice. Finally, no data were available for vanadium, the neighbor of chromium in the periodic table, because of lack of a suitable isotope so cr55 was used as a tracer in a few preliminary experiments. For convenience, we shall refer to elements whose Do and Q are low compared to those predicted by Zener's theory as "anomalous". PROCEDURE This investigation determined self-diffusion rates by means of radioactive tracers and the integral-activity method first utilized by Gruzin.23 In this method a thin layer of radioisotope of the diffusing element is plated or coated onto a planar surface of the diffusion sample, which is then given an isothermal-diffusion annealing treatment. The determination of an activity-penetration curve involves measuring the residual activity of the specimen after each successive layer or section has been removed parallel to the original planar surface. The method used here is essentially the same as that used by Gondolf18 and Kunitake.21 Two radioactive tracers, cr51 and Fe55, were used in this investigation. Diffusion coefficients were determined for the diffusion of one or both of these tracers in four different materials, viz., Fe-12 wt pct Cr alloy, Fe-17 wt pct Cr alloy, chromium, and vanadium. The diffusion samples had nominal dimensions of 1.5 cm diameter and 0.5 cm thickness. The grain size was several millimeters for the Fe-Cr alloys and at least 1 mm for the chromium and vanadium samples. Accurately planar surfaces

Jan 1, 1964

PLANS are underway for the annual meeting of AIME, to be held in New York, February 17 to 21. The technical program includes meetings of all divisions of all three branches, Mining, Metals, and Petroleum. The bulk of the technical sessions will be held at the Statler Hotel, and the annual banquet will be held at the Waldorf-Astoria, Wednesday evening, February 20. The technical program of the Mining Branch activities is included in this issue. While it is not complete in every detail, it shows general interest groupings as well as subjects to be discussed. The program for each division is shown separately to facilitate following the activities of these special interest groups. Then, after a full scale and possibly somewhat strenuous technical meeting, a post-meeting feature will appeal to many of the members. A restful cruise to Bermuda and Nassau is offered at special rates to AIME members and friends. The schedule is a 3:00 pm departure from New York on the Queen of Bermuda on Saturday, February 23; arrival at Bermuda at 7:00 am Monday, February 25; arrival at Nassau at noon, Wednesday, February 27; and the trip ending again in New York at 9:00 am, Saturday, March 1. Rates begin at $202.10 per person, with higher rates depending upon accomodations desired. The base rate includes outside room with private bath and all meals, as well as Federal, Bermuda and Nassau taxes. Reservations for the trip should be made immediately through Leon V. Arnold, 36 Washington Square West, New York 11, who is in charge of arrangements.

Jan 1, 1952

By Amitava Gangulee

A recent investigation has shown that solid solution hardening is almost absent in the quasibinary system SnTe-pbTe.1 The lack of solid solution hardening was attributed to the small difference of only about 3 pct between the atomic sizes of lead and tin, and to the fact that the formation of these solid solutions involved changes only in the sublattice occupied by the lead and tin atoms. The investigation reported here is concerned with the quasibinary system PbSe-PbTe which, similar to the SnTe-PbTe system, forms a continuous series of solid solutions2 and has the same NaC1-type (Bl) structure. The size difference between the selenium and tellurium atoms, however, is slightly larger than 7 pct. No indication of any ordering of the lead and tin atoms at. selected compositions had been found in the system SnTe-PbTe, which had been explained by the weak second-nearest-neighbor interactions between lead and tin atoms.' The possible occurrence of an ordering transition in the system PbSe-PbTe was also investigated in the present work. Polycrystalline specinlens of PbSel-1-xTex (x = 0, 0.20, 0.25, 0.33, 0.50, 0.67, 0.75, 0.80, and 1.0) were prepared by melting appropriate amounts of 99.999 pct pure Pb, Se, and Te j.n evacuated and sealed Vycor capsules. The capsules were quenched in water. The solidified ingots were homogenized at 800°C for 14 days. Chemical analysis of the homogenized ingots showed that the deviations from the stoichiometric compositions were less than 0.1 at. pct for each component. Part of each ingot was ground to pass through a 75 g sieve and pressed into 25.4 mm by 12.7 by 2 mm briquettes. Duplicate sets of specimens, each containing at least one briquette and part of the ingot of each composition, were sealed in evacuated Vycor capsules. Both sets were annealed at 500°C for 7 days; one set was quenced in ice-water and the other was cooled to room temperature over a period of 14 days.

Jan 1, 1970

By Kenneth Cottingham

The year 1941 brought a considerable increase in drilling activity in Ohio. In 1940, the total of wells completed was 1228, whereas in 1941 it was 1561, or an increase of approximately 27 per cent. Of the 1561 wells, 333 were oil wells, 701 gas wells and 527 dry holes. The completions for the past five years are shown in Table I; the number of productive oil or gas wells for the year 1941, arranged by producing formations, are given in Table 2; the number of wells, oil, gas or dry, completed in each county in 1941, in Table 3, and wells by sands in Table 4. The production of oil increased by about 500,000 bbl. in 1941, nearly all of the increase being in Pennsylvania grade. In 1940, the total production was 3,052,000 bbl. from 25,500 wells. In 1941 the total production was 3,547,534 bbl. from 24,801 wells. The increase in production is chiefly due to the Clinton pool in Clayton township, Perry County, which is briefly men- tioned later in this review. The number of oil wells, by grades of oil, and the total quantities produced are shown in Table ;. Annual oil production for five years is listed in Table 6. The average prices paid for crude in 1941 were slightly higher than in 1940 These 1941 prices, with dates of change, are shown in Table 7. The maximum production of natural gas in Ohio was in the year 1915, when the total was just under 80 billion cu. ft. The maximum consumption occurred in the year 1916, and was approximately 169 billion cu. ft. For the past several years, Ohio has ranged from eighth to eleventh, in order of gas production for the different states, being in tenth place in 1940. In the matter of consumption, however, Ohio remains in fifth place. Preliminary figures for 1940 indicate that production of natural gas increased II per

Jan 1, 1942

By Kenneth Cottingham

The year 1941 brought a considerable increase in drilling activity in Ohio. In 1940, the total of wells completed was 1228, whereas in 1941 it was 1561, or an increase of approximately 27 per cent. Of the 1561 wells, 333 were oil wells, 701 gas wells and 527 dry holes. The completions for the past five years are shown in Table I; the number of productive oil or gas wells for the year 1941, arranged by producing formations, are given in Table 2; the number of wells, oil, gas or dry, completed in each county in 1941, in Table 3, and wells by sands in Table 4. The production of oil increased by about 500,000 bbl. in 1941, nearly all of the increase being in Pennsylvania grade. In 1940, the total production was 3,052,000 bbl. from 25,500 wells. In 1941 the total production was 3,547,534 bbl. from 24,801 wells. The increase in production is chiefly due to the Clinton pool in Clayton township, Perry County, which is briefly men- tioned later in this review. The number of oil wells, by grades of oil, and the total quantities produced are shown in Table ;. Annual oil production for five years is listed in Table 6. The average prices paid for crude in 1941 were slightly higher than in 1940 These 1941 prices, with dates of change, are shown in Table 7. The maximum production of natural gas in Ohio was in the year 1915, when the total was just under 80 billion cu. ft. The maximum consumption occurred in the year 1916, and was approximately 169 billion cu. ft. For the past several years, Ohio has ranged from eighth to eleventh, in order of gas production for the different states, being in tenth place in 1940. In the matter of consumption, however, Ohio remains in fifth place. Preliminary figures for 1940 indicate that production of natural gas increased II per

Jan 1, 1942

By R. L. Slobod, H. A. Blum

A semiquantitative method for measuring the wettability of reservoir rocks has been developed. These data are needed for reservoir analysis and for interpretation of laboratory displacement studies. The wettability of a core sample is measured by the contact angle for the system oil-water-solid. These contact angles are calculated from the displacement pressure (threshold pressure) obtained by use of the centrifuge, using first oil-water and second air-oil in the same core sample. This method is based on the assumption that the air-oil and oil-water interfaces occupy similar positions in the porous medium when desaturation of the wetting phase is initiated. The assumption is also made that the Contact angle for the air-oil-solid system which is close to zero in value does not change appreciably even when the contact angle for the oil-water-solid system experiences marked changes. "Apparent contact angles'' for five different solids ranging from 31" to 82" have been determined, and changes irr the "apparent contact angle" of a given sample with laboratory use from 33" to 53' {lave been observed. INTRODUCTION Reservoir rocks vary in their wettability, 1,2,3,4 some being preferentially water wet while other are apparently preferentially oil wet. The degree of wettability, in theory, is measured quantitatively by the contact angle for the system solid-oil-water, hut in 1)practice this quantity is extremely difficult to determine." The need for obtaining some measure of this quantity has become obvious in recent years as a result of both laboratory. and field observations. Several reservoir.: such as the Bradford Sand in Pennsylvania and the Wilcox' at Oklahoma City are reported to be oil wet. If these report:: correctly reflect the true nature of the surface of the rock in the ground, then these reservoirs probably will not perform as predicted on the basis of a water wet rock. In the laboratory many core samples have been Observed to be oil wet. These samples, while perhaps not correctly representing the reservoir, have markedly different properties from water wet rock. The location of the phases is different (oil is in contact with rock instead of water), and other quantities such as the connate water, the capillary pressure curve; residual oil. relative permeabilities. and the recovery of oil by water flooding are markedly affected by the value of the contact -4 A further complication observed in the laboratory is the chang-ing of the wettability of a rock specimen with use. such changes mean that repeat runs on the same core are not the duplicate tests desired, but represent new experiments on a more oil wet material. The changes in surface characteristics are sometimes so rapid that by the time an experiment requiring several days is completed, the results may not be representative of the core as originally described, The, rock material itself (Silica. carbonates. etc.), whell Clean and uncontaminated, is water wet. There seems b( : little evidence of the presence of oil wet minerals such as heavy metal sulfides. The oil wetness of reservoir samples, therefore, is believed to be caused by the accumulation of an adsorbed film in which the polar group of a large organic. molecule is adsorbed on the surface leaving the organic or hydrocarbon part of the molecule projecting out from the solid. Such a surface is much more readily wet 17" oil than by water. These considerations indicate the need for a method which will provide some measure of tile wettalbility (Contact(angle if possible) for reservoir rock ..samples) The method should be capable of (1.1 distinguishing between tile wettalility of dif. ferent formation,.. (2) detecting (change. ill wettalbility of a core with use. and (3) measuring the changes in Wettability which may be accomplished with cleaning operations. such as the use of sodium silicate for increasing water wrettalbility." A preliminary report on such a method is preseted below. not with the idea that this procedure alone will Solve the wettabil-ity problem. but rather that it may provide encouragement to

Jan 1, 1952

By L. Thomassen, N. Spooner, J. M. Thomas

NI-CR and some Ni-Cr-Fc alloys, when used as electrical resistance heating elements in reducing atmospheres, at times suffer rapid breakdowns due to so-called "green rot." These reducing atmospheres are most frequently used in bright annealing and heat-treating furnaces which are kept for long periods of time at 1500' to 1800°F. The green rot is a preferential oxidation of the chromium in the alloy to such an extent that the remaining metal frequently becomes ferromagnetic. The Curie point (magnetic transition point) at room temperature for a pure Ni-Cr alloy is known to be at about 7 pct Cr.¹ This represents a severe loss in chromium for one popular grade of resistance alloy, which is nominally 80 pct Ni-20 pct Cr. The formation of oxides along the grain boundaries makes the ribbon brittle and gives the fracture a green, earthy appearance—hence the name. The authors have studied this phenomenon, simulating the industrial conditions by heating resistance ribbons in various reducing atmospheres, such as moist hydrogen or the atmosphere specified in the ASTM test.² This atmosphere contains 16 pct H2, 10 pct CO, 4 pct C02, 1 pct CH1, 1.5 to 2.5 pct H2O, balance N2. Little success was had in producing severe corrosion with the commercial 80 pct Ni-20 pct Cr alloys. It had been noticed, however, that 90 pct Ni-10 pct Cr alloy wires deteriorated very rapidly when placed in the bottom of narrow thermocouple protection tubes. The bottoms of the tubes with the wires were heated in air. This took place both in porcelain tubes and in Inconel* tubes either with the cold end open or loosely stoppered with asbestos. On examination the wires showed microstructures which would be classified as green-rot corrosion. Subsequent investigations with various alloy wires confirmed the observation that corrosion occurred in some wires, including 80 pct Ni-20 pct Cr alloys, much more rapidly in such tubes than had occurred previously in test atmospheres mentioned above. When 90 pct Ni-10 pct Cr alloys are oxidized with an abundant air supply, the oxide coat consists of both nickel and chromium oxides. In this case thermodynamic equilibrium between the oxides is not established. However, when oxidized 90 pct Ni-10 pct Cr alloy specimens were heated to 1500" to 1800°F inside small diameter tubes, the oxide coat transformed to a bright metallic outer layer of nickel or nickel-rich alloy, beneath which appeared a green oxide, followed by intergranularly attacked metal. The obvious explanation is that in the narrow tubes, thermodynamic equilibrium is being established according to the equation NiO + Cr (in alloy) ? Ni + Cr2O3 This reaction is favored due to the fact that the oxygen pressure over nickel oxide is more than 10"' times the oxygen pressure over the green chromium oxide. The initial oxygen in the tubes is depleted very rapidly by oxidation of the wire and of the tube, if it is metallic. A confirmation of the occurrence of the reaction, reduction of NiO by the chromium in the alloy, was obtained by putting oxidized nickel foil into an evacuated quartz tube along with a piece of bright 90 pct Ni-10 pct Cr alloy ribbon, and heating the tube at 1820°F for a number of hours. The nickel oxide on the foil was completely reduced to pure nickel, leaving a bright foil. The 90 pct Ni-10 pct Cr alloy became strongly magnetic and showed the typical green-rot structure. Weights of the samples before and after testing showed the weight loss of the foil to approximately equal the weight gain of the ribbon. Evidently the bottom of long, narrow protection tubes, stoppered or not, may under certain conditions act just as the sealed quartz tubes in respect to being a confined space in which oxygen is not freely replenished. This condition of oxygen depletion can be prevented by introducing a small amount of air into the bottom of the tube. Many conditions becloud the green-rot phenomenon, such as carburization, sulphidization, and the presence of other corrosive agents. However, these experiments have shown that the basic reaction is a case of internal oxidation which can occur simply by adjusting the oxygen pressure to a low enough level so that the atmosphere will leave the nickel intact and oxidize the chromium. The action of the other agents in commercial atmospheres can then be taken up as individual cases. From these and numerous other tests completed to date or still in progress, it is believed that a more critical evaluation of electrical resistance alloys for their resistance to green-rot corrosion can be made. A much better understanding of the mechanism for this type of corrosion should also result. A more complete report on these experiments will be published later. In the May 1953 issue: TP 35213 Discussion: Solubility of Carbon and Oxygen in Molybdenum by W. E. Few and G. K. Manning, discussion by N. A. Gokcen: p. 747, first column, the fifth, sixth, and seventh lines should be the first, second, and third lines, followed by the present first, second, third, fourth, eighth, ninth, and tenth lines.

Jan 1, 1954

By Herbert Hoover

DURING the year, the' Institute has made the most remarkable growth in its history. Our actual increase in membership was 1816 and therefore was 80 per cent. larger than any previous year. Even without expectation of any abnormal growth, we should pass in the year 1921 the 10;000 mark. The causes of this increased growth are not far to seek.. They lie in the widening vision of the Institute's work, not only in its relation to' the profession but as an avenue of service to the nation as a whole. The Institute is today in the first rank of influence among public institutions in the country. During this year we have, for the first time in many years, had a ?deficit of some $3000 in our finances. The sum is not important, but it- does indicate the tendency of the times, and that is the high cost of living:' The increase in our expenses lay, to the largest degree, on the publishing side of the Institute's work. If we compare the year 1918, as a fairly repre¬sentative year, with that of 1920, we find that the costs of issuing the' Institute's publications, after deducting the income received from these publications, shows a .net increase of about $33,000. for the year. This has been to some degree due to the enlarged membership but to a large degree due to the cost of the paper and printing.

Jan 1, 1921

By R. Henry Norton

The State of Oregon, although admitted into the Union February 14, 1859, is to-day, so far as any practical knowledge of its mineral resources is concerned, almost terra incognita, as compared with the other Western States and Territories. This is partly to be accounted for by the class of emigrants who first settled in the country ; they seem to have been, as they still are, a pastoral community, to whom the terms " mines " 'and " mining " are synonymous with bankruptcy and disaster, and who discourage all attempts to develop the mineral resources of the State. This statement is emphasized by the fact that Oregon has no State Geolo-

Jan 1, 1891

By Nicholas J. Grant, Robert F. Wilde

TAYLOR and Floyd's"" work in establishing phase diagrams based on the elements Ni-Cr-Ti-A1 has led to an understanding of the precipitation hardening mechanism in alloys based on these elements. Nordheim and Grant4 concluded that in simple alloys, and where the aluminum to titanium atomic ratio was such that less than three out of five aluminum atoms were replaced by titanium, the precipitate on aging is the face-centered-cubic Ni 3A 1 phase, called They further found that increasing amounts of hexagonal ? phase, Ni3Ti, precipitated from these alloys when the titanium content exceeded the solid solubility of both matrix and Ni3A1. For alloys of Ni-Cr-Ti-Al, in which the titanium and aluminum contents each ranged from 0 to 4 wt pct, the titanium-rich was superior for strengthening to either pure ?' or 7. It was also noted that the combined titanium plus aluminum content (atomic pct) was a direct measure of the high temperature strength and overaging temperatures for these alloys.4 The present investigation was undertaken to extend existing data on precipitation hardening in the more complex commercial alloys containing higher titanium plus aluminum, and with significant quantities of cobalt, molybdenum, and carbon. Experimental Procedure Reforging of As-Received Bar Stock—The alloys were received as ground, forged bar stock. Chemical analyses and the as-received bar diameters are shown in Table I along with the ASTM grain size after the various treatments. All stock except the Waspaloy was reforged to % in. diam to gain material and to facilitate machining of stress-rupture specimens. Forging was carried out at 2100°F, and discontinued when the bar temperature fell to 1800°F. Heat Treatments—For experixental simplicity it was desirable to heat treat all of the alloys at, the

Jan 1, 1958

By K. S. Seljesater

Since the development of dispersion-hardenable lead-antimony alloys' in the laboratories of the Western Electric Co., Inc., studies have been made of the effect of various third constituents on these alloys.2 This paper covers a study of the effect of small amounts of arsenic. This element is important since it occurs as an impurity in many commercial antimonial leads and the results obtained are particularly interesting as indicating a class of addition agents which exert a stabilizing effect on dispersion-hardened alloys. Experimental In order to study the effect of increasing amounts of arsenic, a series of alloys were made up containing 1 per cent. antimony, and arsenic varying from 0. to 0.10 per cent., the balance Doe Run lead (99.997 per cent. lead). The alloys were cast into bars 1 1/2 in. wide by 3/4 in. thick and cold-rolled to about 1/8 in- thickness. Three samples of each composition were annealed 1 hr. at 225" C. and quenched in water. One set was aged at room temperature, one at 50" C., and the third at 100" C., the

Jan 1, 1929

By K. S. Seljesater

Since the development of dispersion-hardenable lead-antimony alloys' in the laboratories of the Western Electric Co., Inc., studies have been made of the effect of various third constituents on these alloys.2 This paper covers a study of the effect of small amounts of arsenic. This element is important since it occurs as an impurity in many commercial antimonial leads and the results obtained are particularly interesting as indicating a class of addition agents which exert a stabilizing effect on dispersion-hardened alloys. Experimental In order to study the effect of increasing amounts of arsenic, a series of alloys were made up containing 1 per cent. antimony, and arsenic varying from 0. to 0.10 per cent., the balance Doe Run lead (99.997 per cent. lead). The alloys were cast into bars 1 1/2 in. wide by 3/4 in. thick and cold-rolled to about 1/8 in- thickness. Three samples of each composition were annealed 1 hr. at 225" C. and quenched in water. One set was aged at room temperature, one at 50" C., and the third at 100" C., the

Jan 1, 1929

By R. W. Brauchli

The author has made a statistical analysis of the relations between recovery and length of cores, diameters of cores and of drill pipe, and cost of coring under different contractual conditions. The data are presented in tabular form. The length of the core appears to play a minor part in the percentage recovered, with a tendency to lower percentages with increased core length; approximately 50 per cent of the length cored is normally recovered if the cores are more than 2 in. in diameter. The diarneter of the core has a more pronounced influence on the recovery; 1 3/8-in. cores average 29.1 per cent, 2 1/8 -in. core 53.4 per cent and 3 1/8-in. cores with 6 5/8-in. drill pipe 68.5 per cent. Where 31/8-in cores were taken with smaller diameter drill pipe, i. e., 4 1/2 - in. drill pipe in 8 1/4-in. hole, the recovery dropped to 49.8 per cent, indicating that the more rigid drill pipe favors good core recovery, a conclusion also borne out by the results obtained in using large drill pipe for smaller diame-ter cores. Surprisingly good recoveries were obtained from both the Johnson and Simpson sands; shale, limestone and dolomite each gave less then average recoveries. No serious fishing jobs resulted from coring operations. Attention is called to the need of a core drill which will make it possible to drill a full-sized hole while coring, and thus reduce the cost of cores. Data pertaining to core drilling should be consistently recorded, such as, diameter of drill pipe and collar, diameter of core, recovery, size of cutter heads, type of core-barrel, coring time, speeds of rotation and of pumps, weight on core-barrel, etc.

Jan 1, 1933

By T. H. Weldon, L. V. Whiton, R. R. McNaughton, J. H. Hargrave

Oxygen enriched air is being used quite extensively in the metallurgical plants of The Consolidated Mining and Smelting Co. of Canada, Limited, at Trail, B.C. The oxygen used for this purpose is a by-product from the Company's chemical plants located in the area. Most of the ore treated in the Trail metallurgical plants comes from Com-inco's Sullivan Mine at Kimberley, B.C. At Kimberley the ore is milled to produce lead and zinc concentrates which are shipped to Trail for further treatment to metal. One section of this paper deals with the use of oxygen enriched air in the suspension roasting of the zinc concentrates. In this process the concentrate is calcined for leaching preparatory to electrolytic recovery of the zinc. A second section of the paper describes the use of oxygen enriched air in operations at the lead smelter. There oxygen enriched air is used in the blast to the lead blast furnaces and in the slag fuming furnace which recovers the lead and zinc contained in lead blast furnace slag. The final section of the paper outlines the precautions necessary for the safe use of oxygen enriched air in any plant operation. The Use of Oxygen Enriched Air in the Suspension Zinc Roasters The suspension roasting of zinc concentrate developed at Trail, B.C., has been described in AIME Vol. 121, "The Electrolytic Zinc Plant of The Consolidated Mining and Smelting Company of Canada, Limited" by B. A. Stimmel, W. 11. Hannay and K. D. McBean. Since the publication of that paper, the use of oxygen enriched air in suspension roasting has been introduced as regular practice with marked advantage. The relative importance of a specific advantage may vary with changing conditions, but, in general, it may be stated that improved operation has been achieved at increased capacities. Suspension roasting is carried out at Trail in converted standard 25 ft diam Wedge roasters. The 2nd, 3rd, 4th and 5th roasting hearths have been removed and the drying hearth covered over. Drying of the concentrate is done on the drying hearth and the 1st roasting hearth. The dried concentrate, after any lump's have been broken up in a ball mill, is fed to a single burner located in the upper part of the combustion chamber. Oxygen is introduced at the burner fan along with the gases from drying, returned combustion gases from the waste heat boiler outlet and the required amount of new air. Up to 60 pct of the concentrate settles out on the 6th roasting hearth, the rest passilig out of the roaster. The product collected in the waste heat boiler is finished calcine, but the dust collected in the cyclones after the boilers is returned to the base of the combustion chamber where the sulphate is decomposed. Gases from the c'yclones go to a Cottrell precipitator. The discharges from the 7th roasting hearth and the waste heat boiler are combined with the Cottrell dust to give the finished calcine. Following small scale tests started in 1933, oxygen enriched air has been used continuously in the suspension roasting of zinc concentrate in Trail, beginning in 1937. A significant factor in promoting its use in this operation was the availability of by-product oxygen from the Company's near-by Chemical and Fertilizer Division. To-day it is standard practice at Trail to use oxygen enriched air for zinc concentrate roasting. The most important requirement in roasting a zinc concentrate for an electrolytic plant is that the zinc in the calcine should have maximum solubility. It is also desirable at Trail that the gas produced for the manufacture of suhhuric acid should have a ~naximum concentration of SO2 and that a substantial recovery of waste heat from the gas be achieved. High solubility of zinc requires that the sulphide sulphur and zinc ferrite in the calcine be kept low. These are both functions of temperature and time, with formation of zinc ferrite also dependent on contact between the iron and zinc particles. One of the inherent advantages of suspension roasting is that minimum time and contact are achieved. The limit on temperature is imposed by the fusion point of the concentrate and not by the need to control zinc ferrite formation. Operating temperatures are normally maintained within the limits of 1725" and 1850°F. A relatively low zinc sulphate in the calcine is required at Trail, and this results from discharging the calcine from the high sulphur dioxide atmosphere at a temperature above 1600°F.

Jan 1, 1950