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Jan 1, 1940

By Rudolf Gahl

Some time ago the Detroit Copper Mining Co. had to decide the question whether it would pay to re-treat slime-tailings, and several machines were tested in order to ascertain the type of construction which would give the greatest saving. In previous tests on the ore of this company, several tables proved far inferior to the Frue vanner, and for this reason they did not receive any serious consideration. In the late tests, however, one table was found to surpass the vanner in the percentage of saving made. The Frue vanner used in these tests had been adjusted approximately to the slope which the slime-vanners in the concentrator of the Detroit Copper Co. had at that time, about 2 in. between the inside of the wooden posts, or 0.272 in. per ft. It had not been determined, however, if this slope was the most economical one for treating the slime-feed in the mill, or for re-treating the tailings from the slime-vanners, and I was instructed to ascertain by test-runs, under different conditions, the best adjustments for the work to be done. In order to determine if a change in the adjustments of the machines would improve the results, it seemed sufficient to continue running the tests between the vanner and the table before mentioned, keeping the feed and all other conditions the same, but varying the adjustments of the vanner from run to run. I employed a vanner-man of long experience to operate these machines, who expressed the opinion that a slope between 28 and 2.5 in. between the posts (0.323 and 0.340 in. per ft.) would give the best results. Some runs made this way gave a considerable improvement. While for a slope of 2 in. (0.272 in. per ft.) the saving had been only 40.5 per cent. of that of the table, it was 49.2 per cent. for 2.5 in. (0.340 in. per ft.) slope. A decrease of

Jan 1, 1910

By Harlowe Hardinge

The sound made by ball, pebble and rod mills has long been used by the operator as the "telltale" of their operation. The nature of this sound depends upon local conditions and the type of mill used. By experience an operator can tell whether the mill is running properly or not. Some operators are able to detect the difference in sound much better than others and get better results running the same mill under the same conditions. The automatic operation of a mill using sound as the fundamental means for maintaining control presents many problems. The satisfactory solution of these problems requires, for given operating conditions, a greater average output, with improved product for subsequent processing, than can be obtained by manual control. Relation of Sound to Useful Grinding Energy Experience has taught us that there is a difference in character as well as in intensity of sound between a mill grinding wet and one grinding dry, in open or closed circuit, to obtain a coarse or fine product, on the same material, to say nothing of the effect with a variety of different materials. Broadly speaking, a wet-grinding mill operates best at a lower sound level than the same mill grinding dry, with other conditions the same. Several reasons for this variation in sound intensity under these conditions can be advanced, but the important point is that there is a difference, based upon practical results. Since these reasons may be more or less involved, and may be subject, to much discussion, only one will be considered here. It is apparent that two balls hitting together or a ball striking the lining, if there is no intervening material, will produce the maximum sound. If a complete cushion of material is placed between the balls or ball and liner, so that the energy is dissipated without doing useful work, the balls will be unable to create enough pressure or force to fracture the particles, and the sound will be at a minimum. At some point in between—that is, where there is sufficient material between the balls or ball and liner so that the ball will fracture the particles without mashing them unduly—the sound

Jan 1, 1939

By L. L. Brundred

The major portion of the production of the Gulf Coast area, represented by South Texas and South Louisiana, comes from the flanks of well-defined salt domes. This oil, containing an excellent lubricating stock, ranges from 17° to 28° Be. gravity. Some lighter oil is encountered but the life of such fields is, in general, an open question. In fact, there are few light-gravity fields which have proved of much value. In all of the fields water encroachment, or, more properly, water produced with the oil, is a vital factor. After the first head of high-pressure gas is removed, ever-increasing percentages of water appear, and naturally the life of the wells is materially affected thereby. The sands are, as a rule, extremely fine, very soft, and must be carefully excluded from the hole by the use of fine screen to prevent sanding up. All sands are tipped at such extreme angles as to make coring essential for the location of water strata, oil-bearing sands and important shale. beds. Even with modern coring, the correlation of logs is a difficult problem. Due to the fact that the bulk of the oil is refined for its lubricating properties, little attention has been paid to losses by evaporation in the field. This is largely influenced by the fact that the major companies have set a price schedule, showing but two grades, "A" and "B." The average oil company, therefore, does not attempt to use the gas-lift but relies primarily on the air-lift and then only on wells considered to be particularly adapted to its use, namely those capable of producing large quantities of fluid and yet not having sufficient "kick" to flow. Furthermore, as the gas contained in the reservoirs is mostly ricthane such gas being very quickly vaporized and produced in large quantity in the early life of the fields, there is little gas left after the first flush flowing period of the wells. In fact, it is very generally conceded that gas is a precarious fuel to depend on in any of the coastal fields. This situation largely accounts for the fact that air, as the lifting medium, is almost universally used. In the average field, wells are drilled on the flanks of the domes in close proximity to one another, largely on account of the extreme dips of the formation and "town lot" leases, and space to set up machinery and

Jan 1, 1928

Jan 1, 1970

By Charles Berkey

CONTENTS PAGE C. P. Berkey-Responsibilites of the Geologist in Engineering Projects (with discussion) 4 Kirk Bryan-Problems Involved in the Geologic Examination of Sites for Dams 10 0. E. Meinzer-Relation of Ground-water Conditions to Leakage of Reservoirs (with discussion) 19 Charles Terzaghi-Effect of Miner Geologic Details on the Safety of Dams (with discussion) 31 G. H. Matthes-More and Better Geologic Data for Use in Hydraulic Projects (with discussion) 47 L. W. Fisher and R. D. Ohrenschall-Geologic Examination of Dam Sites in the Tennessee and Cumberland River Basins 60 C. K. Wentworth-The Geology of Dam Sites (with discussion) 78 L. C. Glenn-The Geology of Dams and Reservoirs 97 H. T. Stearns-Success and Failure of Reservoirs in Basalt (abstract) 111

Jan 1, 1929

By Arthur Knapp

The law of supply and demand is, in general terms, that law which governs the price of any commodity in an unrestricted competitive market. There are several variables which, for the purpose of this discussion, will be defined only as they apply to the petroleum industry: Production: The volume of petroleum that is moved from leases. Stocks: The volume of petroleum that is in the hands of the tank farm and pipeline companies. Inventory: The value of the stocks at the market. Consumption: The indicated delivery of oil to others than those who hold stocks. Demand: The potential absorbing power of the consuming market. Demand is the expression of the needs of the consumer and may depend on the economic value of the oil to the consumer. In times of low prices, the demand is the same as the consumption but during periods of high prices or deficiency in supply, the demand may be greater than consumption. A general expression of the law is as follows: production or consumption Some relation between stocks and or controls price or demand inventory The Law as Applied to Crude-oil Market The above general expression of the law shows that there are six relations between variables that must be investigated in any attempt to establish the exact status of price control at any time. Production vs. Consumption If stocks of crude oil were very low, so that the flow of oil to the market was directly from the producer to the consumer and not, in a large measure, through stocks, some relation between production and consumption would be proportional to price changes. We have no criterion whereby we can tell, at present, what volume of stocks and production

Jan 1, 1924

By Percival Roberts

I DESIRE to present this evening a few notes from the standpoint of a manufacturer upon the subject of tests of iron for structural purposes; not that I have any new facts to which to call your attention, but rather a statement of a few of the objectionable features of the present modes of operation, showing the absolute necessity of important and very radical changes. At the present time, as most of you are well aware, proposals for materials are accompanied by certain specifications as to quality and tests to which the manufactured article must conform. Evolved in many cases from the inner consciousness of some one more expert in theory than in practice, we find a few of the specifications to be good, many bad, and some indifferent. Appended are specimens of specifications of the most prominent engineers and railroad companies, which may be taken as representing the best and most intelligently framed specifications which we now have, arid yet in some pints scarcely satisfactory, owing to misunderstanding of tests as now made. To show the very varied opinions held as to proper quality of iron for bridge-work, I give the tests of two lots of fron made by inspectors with the results, which were referred to the maker with the following commensts : Lot No. 1. Teat of Iron for Eyebars. Reduced area. Elongation. Size. Per cent. Per cent. Breaking load. 4" x 1 3/8 26 25 68,500 Bent 120° around 1 1/2" bar with fracture. Reduced area. Elongation. Size. Percent. Percent. Breaking load. 6" x 1 7/15 24 24 48,820 Bent 110° around 2" bar. This iron should bend 180° without fracture, and is therefore rejected. Lot No. 2. Test of Iron for Brirlye. All measurements taken upon a parallel section of 10". Iron for tension members. Breaking load Elongation. size. per aquare inch. Percent. 1 5/8 49,600 20 14 61,600 27

Jan 1, 1882

By R. W. Guard

ALTHOUGH etching techniques have been developed for revealing dislocation sites in several metals and ionic crystals,h t is valuable to extend the technique to new metals. An etch pit method for nickel has been developed on the basis some suggestions of Dr. John R. Cuthill of the National Bureau of Standards who had observed etch pits in creep specimens of nickel. The etchant used was proposed first by wensch2 for revealing grain size in nickel. The present paper describes the evidence that the technique can be used to reveal dislocations and gives the conditions under which etching can be carried out. The specimens examined were vacuum melted high-purity Ni (99.985 pct Ni) and commercial "A" nickel (99.8 pct Ni). Both materials contained greater than 0.008 pet C and had been annealed in nitrogen or dry hydrogen at 1100o to 1200°C. This gave a grain size of 1.5 mm in the high-purity nickel and 0.050 mm in "A" nickel. Tensile specimens (0.254 in. diam) were deformed from 0.25 to 10 pct at room temperature and then heated for 1/2 hr at different temperatures from 400" to 900°C. The specimens were sectioned longitudinally then polished electrolytically in 60 pct H2SO4 and etched in 35 pct H3PO4 solution at 0.2 to 0.4 v for 30 sec to 3 min. The best method for setting the proper voltage for etching is to increase the voltage until gas bubbles are evolved vigorously from the specimen and then cut it back by 10 pct. It is necessary to heat the specimen above 500°C after deformation in order that etch pits will be formed. This "decoration" treatment permits carbon to segregate to the dislocation rendering them sensitive to etching. It was demonstrated that carbon was the decorating impurity by decarburizing some specimens in wet H2 at 1200°C. The susceptibility to etch pitting was lost following this treatment but could be restored by carburizing in contact with graphite. Some rearrangement of the dislocations in the as-deformed structure occurs on heating at 500oC and above so that the technique can not be used to study the nature of dislocation patterns in deformed specimens. Extended etching does not change the number of pits although the background becomes rough and the pits quite large. The polycrystalline specimens with various strains were examined after annealing at different temperatures. Typical patterns are shown in Figs. 1 and 2. In the unstrained specimen, Fig. 1, the density of pits is 2.5 X 10' per sq cm. All grains show pits regardless of their orientation although there is a

Jan 1, 1961

By Robert S. Schecter, Mark P. Walsh, Michael J. Humenick

In recent years in situ leach mining has emerged as a viable technology for the recovery of uranium from strata in South Texas which contain relatively low concentrations of uranium ore. Because the ore bodies lie within ground-water aquifers, a significant determinant in the economics is the requirement that such aquifers be protected from contamination. Since ammonia is one of the constituents of the leach solutions now being field tested, one environmental problem to be resolved is the removal of ammonia at the end of mining. A second related question is the fate of the ammonia which is not removed by the restoration procedure. This paper considers the displacement and migration of ammonium in a flowing electrolyte with concomitant ion exchange. The ion exchange is an important feature since, during the solution mining phase, ammonium saturates the mineral exchange sites and must be removed from these sites. A mathematical model is used to simulate this process and the model is tested against the results of laborator.y experiments. It is found that the simulations are adequate if an appropriate selection of parameters is made. The model is then used to investigate the effect of cation composition and concentration of the restoration medium as well as dispersion on the overall effectiveness of the process. It is concluded that increasing the concentration of monovalent ions in a solution containing a mixture of both monovalent and divalent ions decreases the adsorption selectivity of the divalent ions with respect to all monovalent ions including ammonium. Thus increasing the ionic concentration of a restoration fluid by increasing the concentration of a nonselectively adsorbed (with respect to ammonium) ion may have a very limited benefit.

Jan 1, 1979

JUDGE Samuel E. Schull, in the Court of Quarter Sessions of Monroe County, Pa., handed down a decision on July 2, declaring the Pennsylvania law for the Licensing of Professional Engineers and Land Surveyors to be in violation of the Constitution of the State of Pennsylvania and also of the 14th amendment of the Constitution of the United States. The case was that of George E. Stevenson, who was arrested in June, 1922, charged with the practice of the profession of land surveying without first obtaining a state license. Mr. Stevenson had had forty years of practical experience as an engineer and land surveyor, and as set forth in the findings "had attained unusual skill, distinction and reputation in his said profession, and, on said date and for a considerable period thereto-fore and down to the present time, was and is President of the Engineer's Society of Northern Pennsylvania." That part of the decision referring to the unconsti-tutionality of the act is quoted in full as follows: This matter now comes on to be heard on argument as to the constitutionality of the said Act of May 25, 1921, P. I. 1131. The defendant urges that the same is unconstitutional: First: Because it is in violation of Article 3, Section 3, of the Constitution of Pennsylvania, which provides: "No bill, except general appropriations bills, shall be passed containing more than one subject which shall be clearly expressed in its title." Second: That the same is discriminatory and, therefore, in violation of the 14th Amendment of the Federal Constitution. In this case, we: are confronted by the Act of Assembly bearing the title "an act to regulate the practice of profession of Engi-neering and Land Surveying; creating a State Board for Regis-tration of Professional Engineers and Land Surveyors; defining its powers and duties, imposing certain duties upon the Common-wealth and Political subdivisions thereof, in connection with public work and providing penalties." We meet in the title of this act, a recognition of the fact that it is the legislative intent to deal with two professions: First: Engineering. Second: Land Surveying.

Jan 8, 1923

By J. Tarwater

The torsional testing of cylindrical medium-carbon steel specimens, heat treated to a high strength level, revealed a stress-strain relationship that was dependent on the direction of torsional plastic pre-strain. This Bauschinger effect was observed in prestrained specimens both with and without subsequent elevated-temperature strain aging. Yield stresses in strain-aged specimens exceeded those of simply prestrained specimens and the difference in stress was greater when the prestrain direction opposed the test direction. This behavior is discussed in terms of the classical dislocation pile-up using Cottrell's equation, A plastically prestrained strain-hardenable member, loaded in a direction opposite to the direction of prestrain, produces a stress-strain relationship differing appreciably from the curve representing reloading in the prestrain direction. This phenomenon, referred to as the Bauschinger effect, will be discussed in terms of the stress differences ob- served at a specified strain. The effect, dating back to the 1880's, was first attributed to grain boundary stresses. When later work revealed that the effect was also present in single crystals, revised theories attributed the diminished applied reverse stress to assistance from internal long-range stresses. These stresses have been associated with dislocation pile-ups or with dislocation arrays having analogous stress patterns. The stress patterns are subject to alteration by interaction with interstitial solute atoms and acceleration of the interaction may be accomplished with elevated-temperature strain aging. As discussed herein, the interaction showed a directional effect with regard to the applied stresses necessary for small plastic strains. Aside from the rigorous Bauschinger stress-strai relationship, which compares prestrained members, it is interesting to compare the stress-strain curve of a member being prestrained with that of a prestrained member being reverse loaded. For small strains which are a fraction of the prestrain deformation, the applied stresses of the reverse reloaded member are smaller. However, as the reverse strain approaches the prestrain value, the stresses approach equivalence. It has been reported1 that the stress required to return a prestrained specimen to its initial "zero" position generally exceeds the prestrain stress because of the work hardening occurring on potential slip systems during prestrain.

Jan 1, 1963

By L. L. Newman

As soon as the Congress recognized the alarming rate at which our domestic oil resources were being depleted during the war, it took action to step up the rate of research and development which the Bureau of Mines had been conducting for several years on the production of synthetic liquid fuels from coals. Under Public Law 290, approved April 5, 1944, funds were authorized for the Bureau to proceed with research, development, design and construction of demonstration plants for the hydrogenation of coal, the synthesis of oil from carbon monoxide and hydrogen, and the distillation of oil from shale. During the latter part of 1944, when it became evident that the collapse of Germany was near, a Technical Oil Mission was organized to study the Ger- man techniques of synthetic oil production. Since the cost of hydrogen or synthesis gas is one of the major factors of expense in the operation of hydrogenation or synthesis gas processes, the Bureau of Mines considered it of prime importance to include on the mission gas engineers whose instructions were to examine closely the methods employed by the Germans in solving the problem of providing low- cost hydrogen or synthesis gas for their very extensive operations on synthetic liquid fuels. The Solid Fuels Mission and the Utilities Mission, as well as the Army and Navy Missions, also included teams for the study of German gas production. Although their objectives naturally differed from those of the Technical Oil Mission and from each other, it was recognized that there was considerable overlapping of their fields of investigation. Duplication of effort, however, was largely avoided through the close cooperation between the group leaders of these missions. For example, although I went to Europe as a member of the Technical Oil Mission, my first German assignment was actually made by Dr. Harry F. Yancey, leader of the Solid Fuels Mission- to investigate the brown-coal gasification methods in central Germany. The art of gasification in the United States and England, and to a large extent in the proximity of the coking-coal regions of Germany and the rest of continental Europe, depends essentially on two stages of operation; namely, carbonization and intermittent water-gas generation. As far as the United States is concerned, complete gasification in a single stage of operation is rarely practiced, except in gas-producer operations where the product is a relatively lean gas consumed close to the point of manufacture, and for water-gas production with anthracite as a generator fuel. Complete gasification of bituminous coal has been the subject of numerous investigations. Many relatively simple modifications of the water-gas generator have been tried to permit the direct gasification of low-cost bituminous coal instead of high- cost coke and anthracite for the production of water gas. Although varying degrees of success have been achieved and the water gas produced generally has been higher in calorific value, in only a few isolated in- stances has there been any sustained use of bituminous coal for water-gas production for public utility uses after the shortages of anthracite and coke have been lessened.

Jan 1, 1946

By Glenn C. Waterman

THE diamond drill is a very important tool in exploration and development testing and its use is increasing. In almost all cases results of diamond drilling are analyzed on the basis of grade and tons. A proper evaluation of core and sludge assays is important if drilling results are to be acceptable as a basis for geologic and engineering appraisal. The relatively wide variation in assay averages as calculated by various well-known combining methods indicates that the engineering choice of a method may affect the outcome of the drilling in terms of ore and waste. The problem of combining assay results from core and sludge samples has been discussed many times in conference and in the literature.'-' Most writers agree that the field of disagreement in methods is large and that the engineer on the job must consider features unique to his drilling, pick one of several combining methods, and depart from the rules when abnormal results come in. All the discussion to date can be summed up by the admission that as yet there is no fairly simple, generally acceptable combining method that is practicable over a wide range of drilling conditions, ground conditions, and ore occurrence. The combining problem is important in evaluating drilling results at Chuquicamata. Recently a reappraisal has been made of recovery variables and their effect on assays, with the result that a new combining method is offered which fits average drilling conditions and is mathematically reasonable. It is simple in application, fundamentally correct, and an improvement over most combining methods. At Chuquicamata diamond drillholes are used to outline the grade and position of blocks of normal and marginal grade oxide, mixed, and sulphide ore. Most holes penetrate all classes of material (and waste), and it is important for mining programs as well as ore reserves to know almost precisely the soluble and insoluble copper content of mineralized ground. At present three classes of ore are mined and treated differently. For an orderly sequence of mining operations which can provide regular daily tonnages of all three ore types and keep grade at certain levels with minimum variation, ore type and its grade must be predicted. Diamond drilling plus geologic mapping and bench sampling are tools for prediction. And drilling data are largely used to calculate grade of material more than a few meters away from bench faces. The orebody at Chuquicamata" is criss-crossed by millions of barren or mineralized weak to fairly strong slips and fault fissures. Mineralization is diverse and encompasses many quartz and oxide or sulphide-bearing copper veins, as well as seams and disseminated grains. Copper occurs in oxide or sulphide minerals or mixtures of these two mineral types. Rock conditions vary from intensely seri-citized (soft and porous) through clay-altered ground to almost fresh granodiorite. The result is an orebody which offers many obstacles to good and consistent core recovery in diamond drilling. Recovery varies considerably in the several alteration zones, the various types of oxide and sulphide ores, and the position and inclination of the drillhole within the complex fracture pattern. As core recovery drops sludge samples must be used with core samples to calculate grade. Many years of drilling at Chuquicamata indicate that in good grade oxide zones and in the sulphide areas core recovery is good and the ground uniformly mineralized. Moderate loss of core, therefore, does not markedly affect grade calculations based on core assays. An early core-sludge combining method used core assays at face value as indicating grade down to 50 pct core recovery, but below this recovery percentage sludge samples were used and weighted according to the standard Longyear chart. This method apparently did not introduce serious errors, but it abruptly used sludge assays with high weighting factors representing 100 pct return irrespective of actual percentage of sludge recovered. Recent drilling activities have been directed toward outlining the marginal ore areas. The non-uniform mineralization and generally poorer core recovery in such ground indicated that a more exact core-sludge combining method was required to equate wide differences between core and sludge assays and recovery. In fringe ore areas at Chuquicamata core recovery averages about 50 pct, from a minimum of 10 to 15 pct to a maximum of 100 pct. Sludge recovery is likewise variable and averages perhaps 80 pct even though holes are cemented as water return falls off. In a homogeneously mineralized area cut by many slips and faults, with hard and soft ribs, loss of core is loss of ground which has a grade similar to that of core recovered, and core assays approximate true grade. In this case sludge samples need not be used. However, it would be unusual to know beforehand that an area is uniformly mineralized, and in fact this condition is probably uncommon. Generally the distribution of valuable minerals in the ground does not exactly compare with their recoverability in core. Thus, in the usual case, loss of core decreases the

Jan 1, 1956

By Paul Billingsley

THE term Boulder batholith was first applied in 1897 by W. H. Weed'2 to the extensive mass of granite in western Montana within whose borders occur the ore, deposits of Butte. In a general, way this was known to extend from Helena on the north to the Highland Mountains near Butte on the south, and to be relatively narrow in its east-west diameter. Its intrusive relations to the surrounding sedimentary , rocks, and its probable Tertiary age, were described by Weed, but in many ways his statements, based upon incomplete data, have required revision. Most notable of the errors of this description of the batholith were the failure,3 since corrected, to recognize the intrusive contact of the granite with the capping of andesite, and the complete absence of any reference to the many extensions of the granite beyond the somewhat narrow limits of its largest exposure.

Jan 1, 1915

By H. William Ahrenholz

The coal industry had another prosperous year in 1966. Since the turn of the decade, production has been climbing at an average rate of 6% per annum. Although the fast pace slackened somewhat, 1966 production showed a gain of almost 3 % over that of 1965. An impressive record can be drawn from the fact that output per man-day in 1966 was more than twice that of the early 1950's, and more than three times that of the early 1940's. And even though man-power requirements lessened, those men retained by the industry worked longer hours and benefited through higher hourly pay rates. However, cost to the customer increased a little. Such statements can only be made for a healthy industry -one that is constantly improving its efficiency. Coal currently provides more than 25% of the total U.S. energy output. About 50% of all U.S.- mined bituminous coal goes directly to the electric utility market. It should be noted that, now, well over one trillion kwh of electricity is generated annually. Dependence of the giant electric utility industry on coal is based on economy and an abundant, dependable supply of this fuel.

Jan 2, 1967

In a letter to Prof. L. P. Breckenridge, chairman, urging the continua-tion of the Fuel Conservation Committee of the Engineering Council, Edwin Ludlow calls attention to the millions of tons of culm in the an-thracite region that can be utilized in properly equipped plants and the electricity generated transmitted to. New York, Philadelphia, and other nearby cities. He says: "Experiments have shown the economic value of No. 4 Buckwheat, which passes through a 1/16-in. mesh and over a 1/32-in. mesh. Culm passing through a 1/32-in- mesh is pulverized until it passes through a 300 mesh and is then burned under boilers. Two plants of this kind are now in successful operation in the anthracite region. Another rather interesting experiment was using 30 per cent. of this pulverized coal with 70 per cent. of oil in the generation of steam in the place of pure oil. This utilization of the fine anthracite, which has always been a waste product and thrown away, is not only fuel conservation in its truest sense but in the case of a bituminous strike, when no strike is contemplated in the anthracite field, will furnish fuel to manufacturing plants that otherwise would be obliged to shut down."

Jan 12, 1919

Australian research scientists at the University of Melbourne's Institute of Materials Research have discovered two methods of extracting metals from raw ore, using brown coal. The discoveries could lead to extensive new markets for the brown coal producers of Australia (boasting the world's largest brown coal deposits in the Latrobe Valley region of Victoria), the United States and West Germany. Research on the extraction processes began at the University's Department of Metallurgy in mid-1969 under the direction of Geoffrey Cullen, manager of the Materials Research Institute. In June of this year. Cullen announced that both metal extraction processes, using brown coal, had proven successful.

Jan 1, 1971

By P. Chiotti, J. T. Mason

Ther?nal, X-ray, metallographic, and vapor pressure data were obtained to establish the phase diagram and standard free energy, enthalpy, and entropy of formation for the compounds in the Sw-Zn system. Four compounds, SmZn, SmZn2 , SmZn4.s, and SmZn8.5, melt congruently at 960°, 94Z°, 908°, and 940°C, respectively. The cornpounds SlnZns, Sm3Znll, and SnzZn7.3 undergo peritectic decomposition at 855", 870°, and 890C, respectively. Another compound of uncertain stoichiometry, SmZn11, undergoes peritectic decomposition at 760°C. Four entectics were observed with the following compositions in weight percent zinc and eutectic tenzperatures in degrees Centigrade: 12 pct, 680°C; 36 pct, 890°C; 58 pct, 850°C; and 72 pct, 900°C. An allotropic transformation and a composition range were observed for the SmZnz compound. The transfor)nation varies from 905" to 865°C as the zinc content increases from 16.0 to 48.5 wt pct, respectively. The free energy of formation of the compounds at 50PC varies between -15.9 kcal per mole for SmZn to -51.1 kcal per mole for SmZn,.,. Corresponding enthalpies vary between -19.2 to -78.3 kcal per mole. The ther-modynamic properties for the liquid alloys are described by the relations: A search of the literature revealed very little information on the Sm-Zn system. Chao et al.&apos; as well as Iandelli and palenzonai have reported the structure of SmZn to be cubic B2 type and Kuz&apos;ma et al3. have reported the structure of -sm2zn17 to be of the Th2Ni17 type. The purpose of this work was to establish the phase diagram of this system, to determine the zinc vapor pressure over the solid two-phase regions of the SYstem, and to calculate the thermodynamic properties of the compounds. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in this investigation were Bunker Hill slab zinc 99.99 wt pct pure and Ames Laboratory samarium. Analysis of the samarium by chemical, spectrographic, and vacuum-fusion methods gave the following average impurities in ppm: Nd, <200; Eu, <100; Gd, <100; Y, <50;Ca, 225; Ta, 400; Mg, 10; Cu, ~50; 0, 175; H, 20; and N, 15. The elements Fe, Si, Cr, Ni, Al, and W were not detected. The samarium was received as sponge metal and was kept under argon except when being cut with shears and when being weighed. Tantalum was found to be a suitable container for alloys with zinc contents up to the Sm2Znl, stoichio-metry. At higher zinc contents the grain boundaries of the tantalum containers were penetrated by the alloy and the containers failed during prolonged annealing. About 25 g of massive zinc and samarium sponge were sealed in tantalum crucibles equipped with thermocouple wells. These crucibles were in turn sealed in stainless-steel jackets. All closures were made by arc welding under an argon atmosphere. The samples were equilibrated in an oscillating furnace and in some cases were given various heat treatments in a soaking furnace. After appropriate heat treatment the steel jackets were removed and the alloy subjected to differential thermal analysis. The apparatus was calibrated against pure zinc and pure copper and found to reproduce the accepted melting points within 1°C. Alloys were subsequently subjected to metallographic examination and those of appropriate compositions were used for X-ray diffraction analysis and for zinc vapor pressure determinations. The vapor pressures were determined by the dewpoint method. Both the differential analysis and dewpoint measuring apparatuses have been described in earlier papers.4, 5 All alloy samples were etched with Nital (0.5 to 3 pct nitric acid in alcohol) except the samarium-rich alloys. These more reactive alloys were electro-polished in a 1 to 6 pct HClO4 in methanol solution at -700c at a potential of 50 v. EXPERIMENTAL RESULTS Phase Diagram. The results of thermal analysis are indicated by the points on the phase diagram, Fig. 1. Eight compounds and four eutectics were observed. The composition of the compounds and their melting or peritectic temperatures are given on the phase diagram. The four eutectic compositions in wt pct zinc and eutectic temperatures in % are: 12 pct,- 680°C; 36 pct, 890°C; 58 pct, 850°C; and 72 pct, 900°C. The stoichiometry of the most zinc-rich compound is still uncertain, but is very likely either SmZnll or SmZnlz. However, to simplify the presentation which follows it will be referred to as SmZnll. As shown on the phase diagram the phase regions for some of the samarium-rich alloys have not been unambiguously established. A sample of pure samarium was observed to transform at 924°C and to melt at 1074"C, in good agreement with corresponding val-

Jan 1, 1968