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By A. U. Seybolt

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By Grimes, J. A.

EXTENSIVE discovery 'and rapid exploitation of orebodies within the past half century have attracted many able geologists to the mining industry and furnished them a wealth of data from which to develop theories concerning ore genesis. By tosting and elimillating theories which are not sufficiently sup- ported by fact, or which are based on inaccurate observation of field data, the trend of geological opinion has . moved strongly in certain directions until, at the present time, large numbers of geologists subscribe to a broad concept of .ore genesis that I would summarize as below:

Jan 1, 1928

By N. Mungan

Formation damage, i.e.. reduclion in permeability, has been generally attribuled to clay minerals which expand or disperse upon contact with water that is less saline than the connate water. Luboratory, studies show that penneahility reduction can also occur in formalions containing only nonexpandable clays such as illite or kaolinite, and can be caused also by changes in pH. Furthermore, pH changes can damage even formations that are essentially free of clays. It is suggested that permeability reduction is due to the small passages being blocked by particles, which may be dispersed clays, cemenlion material or other fine parricles. These particles are dislodged by dispersion of clays due to changes in salinity or by dissolution of calcareous cement by acids, or of silicaceous cement by alkaline solutions. In working with reservoir cores, it was found that extracted cores damaged more easily and extensively than nonextracted cores. The extent of damage depended also on tenlperatltre. INTRODUCTION Permeability is an important property of porous media and has been the subject of many studies by engineers and geologists. Many of these studies are conccrned with formation damage, i.e., reduction in permeability, resulting from exposure of oil-producing formations to water substantially less saline than the connate water. This effect causes understandable concern since during drilling, completion and production phases formations are often exposed to fresh water. The damage resulting from contact with relatively fresh water has been attributed to expansion and dispersion oF clay minerals. During laboratory investigation of the use of NaOH as a wettability reversal agent to increase oil recovery from oil-wet reservoirs, several cores used in the displacement studies suffered loss in permeability. Despite the traditional usage of NaOH for conditioning aqueous mud systems, the role of the caustic filtrate in wellbore damage seems to have been overlooked. Browning2 as recently reported on the effects of NaOH in dispersing clay minerals but he was concerned only with complications that may arise in drilling massive shale beds. The following study was made to examine the role of pH and salinity changes in core damage. Where cores from reservoirs were used, tests were performed with extracted and nonextracted cores both at room and reser- voir temperatures, since it was felt that the test environment and core condition may affect the results. Because of its limited coverage and exploratory nature, this study is not intended to provide answers to field formation damage problems. It is hoped that it will encourage research into new aspects of the permeability reduction problems, particularly those allied to new recovery and production processes. PROCEDURE In all permeability tests, fluids were pumped through the cores at a constant volumetric rate. Only deaerated fluids and reagent grade chemicals were used. The fluids were passed through two ultrafine filters before injection to remove any entrained particles. The cores, with the exception of the unconsolidated cores, were mounted in Hassler holders. Water was used to transmit pressure to the sleeve. The inlet endpiece had two entry ports which permitted scavenging one fluid with another to avoid any mixing in the small holdup volume. The cores were flushed with CO2 gas, evacuated for 5 to 6 hours and saturated with the first liquid at a pressure of 1,000 psi for 24 hours to eliminate any free gas from the cores. Pressure differences up to 20 psi were measured by transducers, calibrated in inches of water and continuously recorded. For greater pressure drops, gauges were used. All reservoir cores were cleaned with a light refined mineral oil, then with heptane, and finally dried with CO2. Compatibility tests showed that no precipitates formed when mineral oil and the crudes were mixed. Some cores were extracted in Dean-Stark-type solvent extractors using xylene and trichloroethane and dried in a vacuum oven at 450F. Each test consisted of a sequence of water, test solution, and again water flow. RESULTS AND DISCUSSION STUDIES IN BEREA CORES Salinity Contrast Berea cores 2-in. in diameter and 12-in. long were cut from sandstone quarried in Cleveland, Ohio. The clay minerals were identified by X-ray diffraction to be chlorite, kaolinite, illite and incerlayered illite. Flow of fresh water or 30,000 ppm brinc does not cause any permeability reduction (Fig. 1). However, after injection of brine the core is readily damaged by fresh water. Damage starts almost instantly as the fresh water injection is begun, and at a cumulative injection of 1.2 PV fresh water, the permeability has dropped from 190 to 0.9 md. Upon continued injection, the effluent contains clay minerals dislodged from the core. The final core per-

Jan 1, 1966

By A. G. Guy

Thermodynamic activity rather than chemical composition is basic to the analysis of diffusion. This is the essential conclusion reached by Darken1-3 and by Birchenall and Mehl.4 If so, it is reasonable to expect that diffusion calculations should be carried out using activities. This paper will illustrate a method of employing activities in analyzing interstitial diffusion. For interstitial diffusion (of carbon in iron and probably generally) the diffusion of the solvent atoms, volume changes, and other such complexities not explicitly provided for in the usual diffusion equations cause a negligible error of the order of 1 pct. Therefore it is relatively easy to test the validity of an analysis based on activities in the instance of interstitial diffusion. The mathematical treatment of the more complex substitutional diffusion could be simplified once the adequacy of the activity method had been established for substitutional diffusion. Thus the present work has the purpose not only of providing a superior analysis of interstitial diffusion but also of indicating a possible approach to the more important question of an adequate treatment of substitutional diffusion. Development of the Diffusion Equation Although activities are convenient quantities to determine experimentally, they are derived from the more fundamental fugacities.9 Possible confusion in using activities can be avoided by basing equations involving their use on the relationship, dP = -D1d/ax dt [I] where, dP = the number of grams of solute crossing one cm2 in the time dt sec. D, = the diffusion constant for use with fugacities; it is assumed to be constant at a given temperature, and has units of secs. f = the fugacity of the solute in the solid solution; the units are those of pressure, dynes per cm2. x = the distance in cm. Eq 1 can be considered to be the basic form of the first Fick Law for one-dimensional diffusion. In order to convert Eq 1 into an equation involving activities, a choice of a standard or reference fugacity, f°, must be made: then. a = f [2] where a is the activity corresponding to the fugacity f. However, the value of a is also determined by the relation, a = a\c [3] where a is the activity coefficient and c is the concentration. For a given value of a (such as a = 1) it is evident that the units used for expressing concentration will affect the numerical value of a corresponding to a given amount of carbon dissolved in y-iron. Since weight per cent concentration is so widely used, this unit will be adopted as the standard in this paper. When the value off given by Eq 2 is substituted in Eq 1, the first Fick Law becomes, dP= -D,f°dl [4] Since D,f° is constant (at a given temperature), the second form of Fick's Law can be obtained in the usual manner, -dt D'f° dx [5] where c' is the concentration in g per cm3. In terms of weight per cent concentration, c, Eq 5 becomes, dc _ 100 d2a Tt = T /f w [6] where p is the density of the solid solution and will be assumed to be constant. In order to simplify Eq6, it is necessary to consider the standard state, f°. Standard states are chosen for convenience. There appears to be one especially convenient choice for the analysis of interstitial diffusion. If the activity coefficient, a, is set equal to unity at infinite dilution of the solute, 100 then — 100D1fl° is approximately equal P to the usual diffusion constant in dilute solutions. This is true since the activity, a, in Eq 6 can be replaced by the concentration, c, with little error in an infinitely dilute solution.* Here f1° is the standard fugacity necessary to achieve this standard state. It is proposed that a diffusion constant Da' be defined, Da1=100/pD1f1° [7] where A is the metal whose diffusion is * The second derivative of a is equal to the second derivative of c in dilute solution only if -da/dr- is. zero. Although theory does not require this condition, in the systems C in Fe, and Zn in Cu, dc is in fact found to be essentially zero.

Jan 1, 1950

By Howard S. Bryant

FROM the viewpoint of the oil producer, the oil refiner, the oil marketer, and the investor, in oil securities, a brief picture of the crude oil supply and demand in the present critical season of the year will be timely and interesting. Although crude oil production has been in a comparatively poor statistical position this year, increased sales and sustained refinery and crude oil prices have allowed increased profits for many oil companies. The large amount of crude oil going into storage during the present period of peak consumption, just previous to the major yearly fall decline in consumption, has caused oil producers to make plans to leave the oil in the ground for the present in several of the areas of large flush production. The present moment is looked on as the turning point in the current year.

Jan 1, 1929

By John N. Hobstetter

IT is widely believed that the nucleation of phase transformations in solid metals is accomplished by some type of local atomic fluctuations in the parent phase which arise from spontaneous diffusion in the metal or alloy system. Under appropriate conditions, these fluctuations are believed to be stable in the sense that the free energy of the entire system is lowered if the fluctuations, or nuclei, grow,' Under other conditions they are thought to be unstable in the sense that the free energy is lowered if they redissolve. The criterion for stability is usually taken as the size of the fluctuation. This view has been rationalized by Becker1 in terms of the free energy released by the volume of the nucleus and the free energy associated with the formation of a new surface surrounding the nucleus. The qualitative result of this reasoning is shown in Fig I where the changes in free energy for the surface and volume effects are plotted together with their sum against the radius of the nucleus. There is evidently always a critical size r. beyond which the release of free energy which is proportional to the volume always dominates the increase of free energy which is proportional to the surface area. Borelius2 has also attempted to rationalize the stability criterion for binary alloys, but in terms of the internal concentration of the fluctuations. He has found that, if surface energies are entirely ignored, the fluctuation must still reach a critical concentration if it is to become stable and avoid subsequent dilution. Although the Borelius theory fails to predict many observed nucleation phenomena such as the vanishing of the nucleation rate at the critical temperature, the major premise must certainly be valid. In this paper a reconciliation of the Becker and Borelius views is made by means of a search for nuclei which are at once stable with respect to both size and internal concentration, The increase in free energy per mole accompanying the formation of a nucleus which is just stable, ?fe, is independent of the path whereby the nucleus is brought into being. It is thus appropriate to seek critical nuclear attributes without reference to the fluctuation mechanism. The rate of nucleation, however, cannot be treated without a detailed understanding of the exact fluctuation process which produces stable nuclei. In this and succeeding papers the purpose will be to find the size, shape and internal concentration of the stable nucleus which is formed with a minimum increase in free energy in a wide variety of systems. THE NATURE OF THE NUCLEUS It is necessary to have rather detailed knowledge of the nature of a nucleus if ?Fe is to be computed. Fortunately, enough facts are known or suspected about the nucleus to make possible a detailed analysis. X ray diffraction studies have shown3

Jan 1, 1948

By JESSE L. MAURY

DEVELOPMENT of new gold mines in Canada since the price of that metal was increased in 1932 and 1933 has been of interest and importance to many of us. The day-by-day story has given an impression of aggressive effort and enough good luck so that the spirit of enterprise has been encouraged. It is the purpose of this article to report the results of a statistical appraisal which give emphatic numerical confirmation to this impression, together with certain side lights on the costs of development and equipment of new mines. The data presented have been taken from all readily available published sources up to the close of 1938 and are representative of that year. A. B. Bower did a large part .of the spadework and Weston Thomas offered many helpful suggestions.

Jan 1, 1939

By J. B. Morrow

BITUMINOUS COAL production for 1937 up to Nov. 27, was 400,000,000 ions, an increase of 3.43 per cent over the comparative period in 1936. The in- crease in consumption, however, was not so great as the increase in production. Stocks of coal, mostly in the hands of consumers, on Nov. 1 were 57,000,000 tons, compared to 44,400,000 tons at the same periods in 1936. The prospects were that both production and consumption for December, 1937, would be lower than for the corresponding month of 1936. , Anthracite production for the period ending Nov. 20 was 43,900,000 tons, com- pared to 48,500,000 tons for the corresponding period in 1936, or a decrease of 9.5 per cent. Production of mechanically loaded coal in. 1936 was approximately 57,000,000 tons, an increase of 17.5 per cent over

Jan 1, 1938

By G. Sachs, S. I. Liu

Introduction In a previous investigation on the effects of repeated strains of large magnitude on the aluminum alloy 24 ST, it was found that the reduction in ductility by straining in tension was partially restored by a subsequent compression.&apos; As illustrated by the dashed line in Fig I,$ the ductility (e~) retained after prestraining in tension by a certain amount (el) and measured in a subsequent tension test is represented by a straight line sloping down under 4s°. If a compression of the same magnitude as the first tension is inserted (€2 = — €1) between prestraining and final testing in tension, such a "balanced" tension-compression cycle yields a ductility considerably higher than that present after prestraining in tension only. The results of these tests can be correlated with those of an investigation on the effects of prestraining in compression.~ As also shown in Fig I, the ductility in subsequent tensile tests decreased with com- pression, at a rate considerably slower than that after prestraining in tension. The above discussed testing conditions can be considered as special cases of a general straining cycle, consisting of first, straining in tension by an amount el, subsequently straining in compression by an amount e2, and finally determining the retained &apos;ductility, e,, in a tensile test. Prestraining in tension is then represented by el > o and e2 = o. Prestraining in compression is given by e~ = o and e~ < o. Balanced cyclic straining is defined by the condition el > o and cz = — 61. In order to obtain further information on the effects of straining cycles consisting of tension and subsequent compression, further tests were made, varying both the tension strain, el, and the compression strain, e2, within extreme limits; el varied between 0.06 and 0.28 and e2 between — 0.008 and —0.h approximately. Apparently, such tests have not been previously performed. They revealed phenomena which have not been recognized to date, The results of the investigation are herewith reported, without attempting to correlate them with internal processes within the metal structure. However, in order to assist in an analysis of this type, the results have been represented in various manners. In addition, further test data on the effects of prestraining by compression were provided by using specimens of various contours (notched specimens) in the sub-

Jan 1, 1949

By J. N. Hobstetter

It is widely believed that the nucleation of phase transformations in solid metals is accomplished by some type of local atomic fluctuations in the parent phase which arise from spoutaneous difiusion in the metal or alloy system. Under appropriate conditions, these fluctuations are believed to be stable in the sense that the free energy of the entire system is lowered if the fluctuations, or nuclei, grow. Under other conditions they are thought to be unstable in the sense that the free energy is lowered if they redissolve. The criterion for stability is usually taken as the size of the fluctuation. This view has been rationalized by Beckerl in terms of the free energy released by the volume of the nucleus and the free energy associated with the formation of a new surface surrounding the nucleus. The qualitative result of this reasoning is shown in Fig I where the changes in free energy for the surface and volume effects are plotted together with their sum against the radius of the nucleus. There is evidently always a critical size r, beyond which the release of free energy which is proportional to the volume always dominates the increase of free energy which is proportional to the surface area. Borelius2 has also attempted to rationalize the stability criterion for binary alloys, but in terms of the internal concentration of the fluctuations. He has found that, if surface energies are entirely ignored, the fluctuation must still reach a critical concentration if it is to become stable and avoid subsequent dilution. Although the Borelius theory fails to predict many observed nucleation phenomena such as the vanishing of the nucleation rate at the critical temperature, the major premise must certainly be valid. In this paper a reconciliation of the Becker and Borelius views is made by means of a search for nuclei which are at once stable with respect to both size and internal concentration. The increase in free energy per mole accompanying the formation of a nucleus which is just stable, AF., is independent of the path whereby the nucleus is brought into being. It is thus appropriate to seek critical nuclear attributes without reference to the fluctuation mechanism. The rate of nucleation, however, cannot be treated without a detailed understanding of the exact fluctuation process which produces stable nuclei. In this and succeeding papers the purpose will be to find the size, shape and internal concentration of the stable nucleus which is formed with a minimum increase in free energy in a wide variety of systems. The Nature of the Nucleus It is necessary ti have rather detailed knowledge of the nature of a nucleus if AF, is to be computed. Fortunately, enough facts are known or suspected about the nucleus to make possible a detailed analysis. X ray diffraction studies have shown

Jan 1, 1949

By W. S. Cavender

The Round Mountain mining district, Nye County, Ne- vada, was discovered in 1906 on claims owned by Lewis D. Gordon. Initial mining operations uncovered gold veins of spectacular richness, and within a few days of discovery, Gordon sold his controlling interest for some $87,000. From this sale emerged the Round Mountain Mining Co., predecessor of Nevada Porphyry Gold Mines, Inc., the latter destined to become the major property owner in the area. Vein mining in the district continued sporadically into the early 1930s, yielding 9.3 Mg (330,000 oz) of gold plus substantial silver credits from approximately 626 kt (690,000 st) of ore. In addition to the lode deposits, the early miners recognized the placer potential in the alluvial fan material accumulated around the west and north sides of Round Mountain itself. Intermittent placer operations were carried out for a number of years, and in the 1940s and 1950s, Round Mountain Gold Dredging Co. worked the placers under a lease from Nevada Porphyry Gold Mines. The last placer operation terminated in 1959 when it, like some of its predecessors, proved uneconomic. Total placer production for the district is estimated at 3657 km (4 million yd) of gravel containing 59 Mg (210,000 oz) of gold and possibly 2.0 to 2.3 Mg (70,000 to 80,000 oz) of silver. Round Mountain is a small hill situated on the east flank of the Toquima Range in central Nevada. The hill is com- posed of relatively flat-lying Tertiary rhyolitic ash flow tuffs, which overlie Paleozoic metasediments and Cretaceous granites. Throughout the surrounding Round Mountain mining district, most of the known gold ores occur in the tuffs, although the metasediments and granites are also mineralized. Mineralization is structurally controlled, principally by a series of northwest-trending shears and shattered zones. Vein, stockwork, and disseminated ores occur, usually containing simple quartz-pyrite-gold mineral assemblages. The gold itself is electrum, having a silver content of 30% to 40%. In September, 1967, Elwood Dietrich, a prospector and mine promoter, obtained a purchase option on the 4452 ha (1 1,000 acres) of mineral rights held at Round Mountain by Nevada Porphyry Gold Mines. The original option had a buy-out price of $1 million and was established through Dietrich&apos;s friendship with officers of Nevada Porphyry. In April, 1968, Dietrich conveyed his option to Ordrich Gold Reserves Co., a partnership created by a group of west coast investors, mostly employees of the airline industry. There- after, Ordrich invested considerable funds in trying to test and develop the property, but soon recognized the need to seek financial and technical support from the mining industry. In December, 1968, Dietrich contacted Wayne Cavender, then Regional Geologist, Southwest, for Copper Range Exploration Company (CRX) in Tucson, Arizona, and made a data presentation. Shortly thereafter, Cavender was appointed Manager of Exploration and Chief Geologist for Copper Range Co. (parent company of CRX), New York City, and he asked C. Phillips Purdy, CRX Regional Geologist, Northwest, to make an initial property examination. Purdy&apos;s one-week field study took place in March, 1969, and resulted in a recommendation that CRX pursue its investigation of the property. The presence of low-grade gold mineralization in both the alluvial gravels and in the bedrock was verifiable, but the placer was deemed to have the greater immediate economic mining potential. At that time, gold was in the $1.41/g ($40 per oz) price range. Working from Purdy&apos;s information, Cavender decided to attempt acquisition of the property, and the first in a long series of negotiations was initiated with Ordrich. Basically, CRX felt that the placer had a promising potential for several reasons, including (I) past operators had recovered free gold but not the gold contained in the pebble fraction of the gravels; (2) past operations appeared to have been ineffectively designed or managed and not costefficient; and (3) the price of gold appeared to be poised for an upward move. Negotiations with Ordrich were prolonged and difficult, with CRX competing against several ma* mining companies, but finally an agreement was reached, effective June I, 1970. Gold was then back to $35. It is believed that, in

Jan 1, 1985

By AIME AIME

The following financial report of the Treasurer of the United Engineering Society is published for the information of members NEW YORK, February 15, 190S. To the Board of&apos; Trustees, United Engineering Society I beg to submit herewith the report of the Treasurer as of December 31, 1907. Your attention is called to the fact that the resources and liabilities, receipts and disbursements statements cover all the financial transactions of the United Engineering Society from its organization up to December 31, 1907. The income and expenses of operating the building during the whole operating period from December 1 to December 31, 1907, somewhat in excess of twelve months, are given. Included in the expenses, amounting in all to $52,647.11, will be found an item entitled "Building Equipment (construction account)." The expenditures under this item were not made for the operating expenses of the building, they represent a construction account, properly speaking, covering expenditures for furnishings and equipment of the building. The Founders&apos; Agreement specifically provides for this class of expenditure under the provision that the Founder Societies shall each be liable for a charge not to exceed $200,000 of principal, which shall include the land and building completed and ready for occupancy, together with the " furnishings, equipment and personal property therein." Certain details of equipment are yet to be supplied, and it. is proposed in the near future to call upon the Founder Societies for an assessment on their respective land and building funds to cover this item of building equipment. Such action would enable the item of $10,039.85 to be transferred to the income account and reduce correspondingly the assessment

Mar 1, 1908

By Charles Will Wright

MINERAL production in almost all European countries suffered a sharp setback because of the war. Plants were damaged, transportation facilities disrupted, and labor dispersed and demoralized. Since the war, due to lack of confidence and economic stability, there has been little incentive to rebuild and expand the mineral industries even though a big demand at high prices exists for mineral products. Most mining and metallurgical companies in Europe hesitate to invest their capital because of the tendency towards nationalizing industry, high taxes, and low output of labor, as well as the deficiency of mine supplies and equipment within their countries. In short, they do not have faith in the future, and for these same reasons and fears most of the mining companies in America will not risk capital investment in Europe. In Europe, including the United Kingdom, free enterprise has been losing ground and as a result the foundation of their economic welfare is being undermined. American mining interests willing to take the initiative could help in counteracting this influence if a way were found for them to co-operate with the European producer without too great a risk.

Jan 1, 1948

By Å. Sterten, R. Tunold, J. Brun, K. Dalatun

The subjects of this study are two corrosion phenomena familiar to operators of aluminum plants employing Soderberg anodes of the vertical type, namely the sul-fide scale formation observed at the steel contact spikes and the corrosion wear observed at the lower edge of the gas collecting skirts. The causes of these corrosion phenomena are discussed on the basis of observations from practice and measurements on commercial cells as well as on laboratory experiments. It is concluded that the anode spike corrosion is mainly due to the attack by sulfur compounds contained in the anodically evolved gases and that this attack is greatly promoted by cracks and pores in the anode carbon embedding the lower spike ends. The corrosion of the gas collecting skirt is mainly attributed to anodic dissolution of the iron during occasional contacts with the melt. ANODE SPIKE CORROSION The visible result of this corrosion is the formation of a brittle loosely adherent scale on the lower ends of the mild steel spikes maintaining the electric contact to the carbon anode, Fig. 1. The thickness of the scale usually varies from 0.5 to 3 mm, but in some cases scale of about 10 mm thickness has been observed by the writers. During the spike pulling, usually repeated every 3 weeks, part of the scale often loosens and remains in the anode carbon, resulting in contamination of the aluminum with iron. This corrosion has been attributed to reaction of the iron with gaseous sulfur compounds originating from the anode paste materials.&apos;-4 This paste usually consists of 70 pct precalcined petroleum coke with 1.2 to 1.4 pct S and 30 pct coal tar pitch containing 0.5 to 0.7 pct S. During operation the gasification of the anode materials takes place in two ways: First, gases are evolved by the gradual baking of the anode paste added on top of the anode. Due to the sealing effected by the upper semifluid zone of the paste, these gases, containing sulfur compounds from the pitch, are forced downward through pores and cracks in the rigid anode carbon. At the temperatures of the zone of the lower ends of the spikes, 700" to 900°C, the original components of the baking gas must undergo decomposition, similar to that taking place with the production of coal gas, resulting in a gas mixture consisting mainly of H2 and CH4 with small percentages of H2S as the main sulfur compound.5 Second, the anodic reaction results in a mixture of C02 and CO, the total quantity of which is about 15 times that of the baking gas. These anode gases must carry the entire sulfur content of the carbon gasified by the anodic reaction. Henry and Holliday6 have shown that COS is the main sulfurous component of the anode gases from Soderberg cells. Soderberg anodes usually exhibit a network of vertical cracks, frequently traversing from one spike to the next one and to the outside of the block and widening downward to the working face of the anode. In addition the anode carbon, particularly that below the spike ends, is rather porous, as indicated in Fig. 1. It therefore seems probable that the anode gases also may partly penetrate to the spike ends. As the anode is partly immersed in the melt, the static pressure of this must forward this penetration. I) SPIKE SCALE COMPOSITION A great number of freshly extracted spikes from industrial plants were inspected and samples of the scale collected for examination. Before analyzing the samples a thin iron oxide layer, formed by air oxidation of the outside of the red hot scale immediately after spike pulling, was removed. On the average the Fe/S ratio found by these analyses corresponded to I the composition FeSl. oo7. X-ray powder patterns showed no oxide and otherwise agreed with those found by Haraldsen7 for iron sulfide with 50.00 at. Pct

Jan 1, 1970

By T. G. Richardson, F. M. Perkins

In the recent paper of Richardson and Perkins entitled "A Laboratory Investigation of the Effect of Rate on Recovery of Oil by Water Flooding,"&apos; the authors found very little appzrent effect on oil recovery of having free gas saturation present prior to water flooding in unconsolidated sands. We agree that the effect in this particular system was small but do not feel that the data presented should be regarded as disproving work of others which has shown an appreciable effect. The authors do not make such a claim, but neither do they advance an explanation of the difference. In our experience the following factors must be carefully considered when studying the relation between residual oil saturation after water flooding and initial free gas saturation: (1) the magnitude of the inherent residual oil saturation, i.e., the residual oil saturation with no free gas; (2) the increase in oil-water viscosity ratio with pressure lowering if the gas saturation is obtained by solution gas drive; and (3) the oil shrinkage which occurs with pressure lowering and gas evolution. The system studied by Richardson and Perkins gave residual oil saturations as low as 20 per cent without free gas present, and one should perhaps not expect much further lowering. As an illustration of the magnitude of the effect when the residual oil saturation is inherently higher we submit the accompanying figure. These data were obtained on an unconsolidated sand under elevated pressure in a system similar to the one described by Richardson and Perkins. Gas saturation was established by gas drive before water flooding. The viscosity ratio was 600:1 under the conditions of the displacement. Here the gas was extremely effective in reducing residual oil saturation. This fact was also indicated by Kyte, et al.2 Their plots of residual oil saturation vs initial gas saturation show trends of greater free gas effect with higher oil viscosities. The pressure-dependent effects were not discussed by Richardson and Perkins. They should be separated from the free gas effect if the objective of the study is a correlation of residual oil saturation vs initial free gas saturation. The increase in oil viscosity when gas is released from solution tends to increase residual oil saturation. This effect is rather small in the viscosity range of kerosene. A Buckley-Leverett calculation, assuming an increase in viscosity ratio from 1.2 to 1.8, indicates an increase in residual oil saturation of about 1 per cent of pore volume. Thus, one would expect this system, if operated at constant viscosity ratio, to show a slightly greater free gas effect. As Dyes- as shown, oil shrinkage can offset the beneficial effect of free gas on waterflood oil recovery, if the gas saturation is established by depletion. Since

Jan 1, 1958

By A. U. Seybolt

A FEW copper-zinc-base alloys meet die-casting requirements reason- ably well, although improvements are desired. Aluminum bronzes, high-tinbronzes and some copper-nickel-zinc alloys can be die-cast, accordingto Herb,1 but seldom are because of such factors as higher melting ranges and greater cost than certain of the brasses. Fox2 has summarized the copper-base die-casting alloys that were in commercial use in 1937 and has given the effects of different alloying constituents. Table 1 gives some of the properties of these alloys as reported by Fox. TABLE 1. Commercial Die-casting Brasses a Constituent Yellow Brass Low-silicon High-siliconb Brass Brass Nickel Silver Composition, Per Cent Cu 57-59 63-65 80 -81.5 42.0 Zn 40-42 33-35 13.5-16.0 41.0 Sn 0.5-1.5 Si 0.75-1.25 3.75-4.25 Pb 1.0 Ni 16.0 Properties Tensile, lb. per sq. in.. 55,000-60,000 65,000-70,000 85,000-95,000 85,000-95,000 Yield, lb. per sq. in.d.. 30,000-35,000 35,000-40,000 65,000-70,000 65,000-72,000 Elong., per cent in 2 in . 15-20 20-30 8-12 10-20 Brinell hardness 120-130 120-130 160-180 160 Specific gravity 8.47 8.50 8.15 8.45 Properties reported by Fox.2 b Trade name of Brastil, Doehler Die Casting Co., similar to Webert Alloy, 3,4 American Brass Co., and Tombasil Alloy,5 Ajax Metal Co. c Trade name Tinicosil, Titan Metal Manufacturing Co. Melting point (liquidus) of the yellow brass is given by Herb&apos; as 1650° F., of the high-silicon Brastil (with 4.5 to 5 per cent Si) as 1600° F., and of the nickel silver as 1675° F. d Criterion not stated.

Jan 1, 1939

By Steve H. Carpenter, Henry E. Otto

The explosive welding of metals is dependent upon the production of a jetting action caused by the collapsing of one metal plate against another. Successful welds are generally accomplished if the yield strength of the metals is in the range of 10,000 to 90,000 psi and the sonic velocity of the metal is greater than the detonation velocity of the explosive if direct contact explosive is being used.&apos; Should the detonation velocity exceed the velocity of sound in the metal it may still be possible to obtain the jetting action and a good weld. However, in most cases where a high detonation velocity is used complications arise because of reflected shock waves which tear the bond apart as fast as it is put together.&apos; Explosive welding of lead presents several problems since its yield strength and sound velocity are very low. Various values have been published3-5 for the velocity of sound in lead ranging from 2000~ to 23004 m per sec. Most of the high-order explosives have detonation velocities on the order of 6000 to 8000 m per sec, which precludes their use. The dynamites have a lower detonation velocity of around 2800 m per sec which is still somewhat too high. Lower-order explosives such as ammonium nitrate (1070 m per sec) must be used to weld lead in the as-received condition if the explosives are used in direct contact. Rather than use low-order explo&apos;sives it was decided to alter the sonic velocity of the lead. The sonic velocity is directly related to the modulus of the material according to the following expression: Fig 1—Interface of explosive weld of lead to steel. Lead is on top As-polished Magnification 75 times as well as the yield strength. Bolling et al. 6 show that the shear modulus of lead single crystals increases from about 0.72 X1011 dynes per sq cm at 300°K to about 0.98 X1011 dynes per sq cm at 0°K, an increase of approximately 3 5 pct. This gives an increase in the sonic velocity of around 700 m per sec. Hence, the sonic velocity of lead at cryogenic temperatures is approximately equivalent to the detonation velocity of the low-order dynamites. We have obtained high-quality lead to steel explosive welds using a 40 pct dynamite in direct contact with the lead. Prior to detonation the lead was chilled with liquid nitrogen (78°K) to increase the strength and sonic velocity. Welds were made while the lead was cold. Specimen sizes were 3 by 6 in. A preset angle of 5 deg with a 0.10-in. standoff at the base was the geometrical setup used. The amount of explosive used for optimum welding of an 1/8 -in. -thick lead sheet to a steel plate was found to be 7 g per sq in. A PETN sheet explosive line wave generator was used to insure a linear detonation front through the dynamite. A photomicrograph of a lead-steel weld is shown in Fig. 1. The typical wave effect that constitutes a good explosive weld is present. When tested in shear, the weld failed in the lead, indicating that the bond is stronger than the lead base metal. Higher-order explosives were also tried without success. We believe this indicates the importance of matching the detonation velocity and the sonic velocity for successful explosive welding. Note Added in Proof. High quality explosive welds of lead to steel have recently been obtained at ambient temperature using a low velocity (1000 M per sec) free running dynamite. The weld interface obtained is comparable to Fig. 1. &apos;S. H. Carpenter, R. H. Wittman, and R. J. Carlson: Proceedings of the First International Conference of the Center for High Energy Forming, Syracuse University Press, syracu.se, N. Y., in press. &apos;A. HI Holtzman and G. R. Cowan: Welding Risearch. Council Bull., No. 104, April, 1965. &apos;Metals Handbook, 8 ed., p. 1062, Metals Park, Ohlo. &apos;J. M. Walsh, M. H. Rice, R. G. McQueen, and F. L. Yarger: Phys. Rev., 1957, vol. 108, pp. 196-216; &apos;L. V. Al&apos;tshuler, K. K. Krupnikov, B. N. Ledener, V. I. Zuchikhin,

Jan 1, 1968

By P. R. Sperry, P. A. Beck, J. Towers

Dahl and Pawlek1 found that electrolytic copper develops extremely coarse grains at 1000°C after about 90 pct reduction by rolling. This coarsening occurs only under conditions of penultimate grain size, deformation, and alloying which lead to the "cube" recrystallization texture.l,2,3,5 The peculiar angular shapes and straight grain boundaries of the coarse grains were noted by several investigator.1,4,5 On the other hand, coarsening in Fe-containing aluminum or in AI-Mn alloys8 does not depend on a "cube" (or any well developed) recrystallization texture. It is true that increasing deformation by rolling, and, therefore, an increasingly well developed re-crystallization texture, are associated with decreasing incubation periods of coarsening.6-7-8 Nevertheless, coarsening readily develops in aluminum even after only 30 pct reduction by rolling, where the recrystallization texture is very weak.6,8 Also, coarsening was observed by Jeffries9 many years ago in sintered thoriated tungsten, which presumably has no preferred orientation. In all these cases coarsening is associated with grain growth inhibition by a dispersed second phase.8,9 The annealing temperature has to be suficiently high to overcome the inhibition at a few locations. But if it is too high, growth starts at many points, and the resulting grain size becomes much smaller.9 Normally, the coarse grains are more or less equiaxed, and the boundaries have a typical ragged appearance.6.8 Cook and Macquarie4 demonstrated that, in addition to the texture-dependent coarsening previously found at 1000°C,l electrolytic tough pitch copper may also coarsen at 800°C after 50 pct reduction by cross rolling. The coarse grains formed under such conditions have rounded shapes and ragged boundaries, like those in aluminum. When the annealing temperature is higher, the tendency for their formation decreases. All these observations suggest that the coarsening at 800°C is associated with inhibition by a second phase. Actually, coarsening at 800°C after 50 pct reduction by cross rolling was observed only in tough pitch copper,4 which contains Cu2O particles. On the other hand, the texture-dependent 1000°C coarsening occurs in both tough pitch and oxygen-free copper;4 it does not appear to depend on the presence of a dispersed second phase. However, the interpretation of the 800°C coarsening in Cu after 50 pct rolling as an inhibition-dependent process, similar to the coarsening in A1-Mn alloys, is somewhat weakened by the fact that this coarsening was reported4 to occur only after cross rolling, and not after straight rolling. It was, therefore, decided to re-examine this question. A 1 in. diam electrolytic tough pitch copper rod, No. 2 hard drawn, was annealed for 20 min at 700°C, rolled to 0.5 in., annealed 10 min at 700°C, and straight rolled to 0.064 in. It was then given a penultimate anneal of 20 min at 500°C and it was cut into four sections, which were given final reductions by straight rolling as follows: A 30 pct reduction of area B 50 pct reduction of area C 70 pct reduction of area D 90 pct reduction of area Specimens cut from the four sections were finally annealed at 800°C in an oxidizing atmosphere. Strip A remained fine grained up to 10 hr, but the specimen annealed 12 hr consisted of only 2 large grains. Strip B had a few scattered large (1/2 to 3/4 mm) grains after 1 min, although the balance of the specimen consisted of fine grains of about 0.02 mm. After 5 min there were several 10 to 15 mm grains present, and after 1 hr strip B was completely coarsened. The coarse grains had the same characteristics (see Fig 1) as those obtained by Cook and Macquarie at 800°C after cross rolling. Strip C had several grains of 0.05 to 1 mm after 1 min, but it was still largely fine grained after 12 hr. After 48 hr it consisted entirely of grains of about 0.5 to 4 mm, with an extraordinarily large number of twin bands. Strip D remained com- pletely fine grained after 4 hr at 800°C. These results indicate that, in the deformation range of 30 to 70 pct reduction, the incubation period for coarsening as well as the rate of growth and the final size of the coarse grains decreases with increasing deformation. Similar

Jan 1, 1950

By James K. Richardson

Today, the enigma of the "missing man" in the metal mining industry equals, and frequently surpasses in objective importance, the problems of ore development, drilling, sampling, pumping, milling techniques, geophysical prospecting, or any one of a hundred highly technical subjects. Unfortunately, as engineers, we have confined our attentions, in the main, to the scientific phases of mineral technology, relegating our man power problems to the background. But what good has all our scientific study and preparation been if we can&apos;t get the ore mined, milled, or smelted? What has happened to our labor supply? Where is the good old miner who could timber, drill a round, lay track, or do any job underground?

Jan 1, 1949

IRON AND STEEL COMMITTEE ALBERT SAUVEUR, Chairman .A. A. STEVENSON, Vice-Chairman HERBERT M. BOYLSTON, Secretary, Abbot Bldg., Cambridge, Mass. Guilliaem Aertsen, Robert W. Hunt, .-E: Gybbon Spilsbury, John Birkinbine, J. E. Johnson, Jr., J. S. Unger, William H. Blauvelt, William Kelly, Felix A. Vogel, Charles A. Buck, Charles Kirchhoff, Leonard Waldo, James Gayley, Richard Moldenke, William R. Walker, Henry D. Hibbard, Joseph W. Richards, William R. Webster, Henry M. Howe, C. F. W. Rys, Frederick W. Wood. Manuscripts of the following papers on iron and steel for the February -meeting have been received and accepted: Albert Sauveur, Notes on Heating and Cooling Curves of Professor Carpenter&apos;s Electrolytic Iron. H. M. Howe and A. G. Levy, Notes; on the Plastic Deformation of Steel during Overstrain.

Jan 2, 1914