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By J. T. Crawford

ALTHOUGH nearly 10 pct of the total tonnage of coal produced annually within the United States is handled by bulk freighters on the Great Lakes, very little of the detail connected with it has been published other than occasional newspaper stories and publication of tonnage statistics. Of the total tonnage floated on the Lakes each year some 10,000,000 is stored and distributed from the port of Duluth Superior, at the western end of Lake Superior commonly known as the Head of the Lakes. This port has the largest single area concentration of coal docks in the world. Since this area contains the largest ore docks, the largest movable material handling bridge, the largest and highest grain elevator and the largest coal briquetting plant in the world, it is entirely fitting and proper that here also should be located the largest coal dock and what we believe to be the worlds largest clam shell. Of the sixteen coal docks operated by ten companies, five are owned and operated by the North Western-Hanna Fuel Co. which has two docks on the Superior, Wis. water-front and three docks in Duluth, Minn. It is with these five docks that we are primarily concerned. GENERAL HISTORY In the summer of 1871 a small sailing vessel entered the harbor of Duluth Superior with the first commercial coal cargo. All the coal brought up that first year did not amount to more than 3000 tons. During the year 1877 the first dock equipped for handling coal was built in Duluth. Coal receipts increased to 52,785 tons in 1879 the first year for which an official record was kept. Since then the volume of water-borne coal to the Head of the Lakes steadily increased to a maximum of 12,688,321 tons in the year 1923. This tonnage was nearly equalled in the year 1927 and the next highest tonnage recent year was in 1946 when 10,105,703 tons were unloaded. The average annual bring-up over a ten year period 1938 to 1947 was 8,605,231 tons. Approximately 30 pct of the coal unloaded at the Head of the Lakes is handled over the docks of the North Western-Hanna Fuel Co. Competition of other fuels coupled with expansion of coal fields in the mid-west have held coal receipts for Duluth-Superior at a relatively constant figure during the last eight years although the total tonnage of coal floated on the Great Lakes has more than doubled in the past 25 years. From the shovel and wheelbarrow method of unloading early cargoes to the horsepowered windlass derrick with a wooden tub was but a short step. The first movable coal handling, steam operated,

Jan 1, 1948

By Albert Sauveur

It is delightful to read a technical paper like that of J. E. Johnson, The Effect of High Carbon on the Quality of Charcoal-Iron, presented in October, 1912, at the Cleveland meeting of the American Institute of Mining Engineers.' The clear, simple, and straightforward manner in which he describes his experiments and results makes you feel as if you had been, so to speak, at his elbow during the course of his investigations, while his method of procedure is so rational that you can fairly anticipate each step in the logical sequence of the tests performed. The following notes suggested by Mr. Johnson's paper are presented here in the hope that they may help, if only a mite, towards the final solution of a problem of considerable scientific and industrial importance. Physical Properties of Cast-Iron us. Its Ultimate Composition. Mr. Johnson writes that " an investigation along the lines of consumption showed that different irons have different characters totally independent of their analyses," and he declares that " the presence or absence of these elements [meaning carbon, phosphorus, silicon, and manganese] alone will not account for all, scarcely for a half, of the facts which have long been known." He further tells us that some foundries have " proved, by the most irrefutable tests, that they could take a certain iron of a given analysis and produce certain results," while with " another iron of the same analysis they could not produce these results at all." I feel confident that every experienced and thinking metallurgist will readily believe Mr. Johnson's statements and will share his views in regard to the hopelessness of inferring the

Jan 1, 1914

By Warren E. Wilson

THE transportation of solids in pipe lines is a matter of deep concern in many fields of engineering. Much experimental and theoretical work has been done in an effort to devise means of designing pipe lines that will satisfactorily transport given solid loads, but there remain many unanswered questions in this field. The present discussion will be confined to a rather narrow portion of this field and will endeavor to point out certain factors that may well be considered when comparing the relative economy of various installations. The data have been presented previously but a new interpretation was prompted by a suggestion in a paper by Professor O'Brien,1 of the University of California, that the friction work per pound of dry material should be considered in determining the relative efficiency of various installations. This method of considering relative economy in various pipe lines leads to some rather unexpected conclusions, especially with reference to the economy of large pipe sizes. A previous suggestion by the writer3 concerning the economy of a rather peculiar type of installation is strengthened. It is not believed that the considerations set forth herein apply directly in the case of dredge lines, where economy is largely a matter of a high rate of pumping in order to reduce the unit overhead charge. However, it is believed that some value may be gained from these considerations in cases involving the disposal of a fixed amount of solids per unit time with a minimum expenditure of energy and at a low cost for replacement of worn pipes. Such situations are not uncommon in the disposal of mill tailings and the disposal of solids deposited from irrigation waters. It was found that data leading to general conclusions for various pipe sizes were not available but certain definite trends are indicated and methods of analyzing available data are presented in the hope that they may be of assistance in preparing engineering estimates on designs of pipe lines of the type described above. ENERGY. REQUIREMENTS Carrying out the idea contained in Professor O'Brien's paper concerning the method of computing energy required to transport solids, the following analysis leads to some rather interesting conclusions. Let us represent: [Solids load in terms of mass per unit time by W Ratio of mass of suspended solids to total mass of mixture flowing by p Volume rate of flow of mixture by Q Length of pipe by L Slope of energy grade line by s Mass per unit volume of solids by m, Mass per unit volume of liquid by ml Mass per unit volume of mixture by m,,, We then have as an expression for the solids load: W = pQm¬] The work done per unit mass, P, on the mixture to move it along the pipe the

Jan 1, 1945

By H. E. Hawkes, D. A. Barr

Time variations in the copper content of the sediments of streams draining mineralized areas were studied in two areas of contrasting climatic environment, one in northern and one in southern British Columbia. In each area, samples were collected and observations made of rainfall, stream discharge and air and water temperature at intervals throughout the summer season. Samples were analyzed for total and cold-extractable copper. Results showed a weak inverse relation between cold-extractable copper and discharge in two out of the three test sites in the southern area, and a decrease in ratio of COld-extractable to total copper over the duration of the test period at a highly anomalous site in the northern area. In suspended rock flour resulting from glacial erosion of mineralized rock in the northern area, virtually all the copper was found to be soluble in cold, dilute hydrochloric acid. None of the variations observed is sufficient to cause serious problems in geochemical sediment surveys. Systematic collection and trace analysis of stream sediments has seen wide application in recent years as a method of primary prospecting in primitive areas. Common practice is to collect fine-grained samples of sediment either from the active channel or from the flood plain near the channel. Samples are dried, sieved and the -80-mesh fraction analyzed after breakdown of the sample by a relatively strong attack, such as by fusion or by treatment with hot perchloric acid. Drying, sieving and rigorous chemical attack requires established facilities, either in a well equipped central laboratory or in base camp. Thus analysis for total metal involves a substantial delay from the time the samples are collected until the analytical data can be reported. An alternative system uses a cold aqueous extrac-tant in place of the hot acid or flux.4 Advantages of the cold-extraction techniques are that kits can be prepared for use directly at the sample site and that, in some problems, the patterns in cold-extractable metal, usually abbreviated cxMe, are more useful as ore guides than the patterns in total metal.' In the course of operational geochemical sediment surveys, a problem that has come up repeatedly is failure to reproduce anomalous values or patterns by resampling the same areas. The mystery of the vanishing anomaly has led to speculation as to whether there is a significant variation in the metal content of sediment samples with the weather or with the time of year. Review of the published literature shows that a number of experiments have been carried out on time variations in the metal content of stream water.1,2,5,7-9 The only published report on time variations in stream sediments that has come to the authors' attention, however, is by Govett,3 working in Northern Rhodesia.

Jan 1, 1963

By Jim F. Lemons

INTRODUCTION A nickel doesn't buy much anymore. That's even true in the cost of recovering nickel -- the commodity. A 5[C] per pound (11 [c] per kilogram) increase in the nickel price won't cover a 10-percent increase in fuel costs for processing laterite ores, nor will it cover a 10- percent increase in wages for recovering nickel from a sulphide ore. It won't even cover a 5- percent increase in the capital cost necessary to mine and process ocean nodules. The basis for this statement and a quantitative analysis of the variations in costs to recover nickel from different types of nickel ores will be discussed in this paper. During the early part of the 1970's, the interest in nickel and its potential development was shifting from Canada to the Pacific Basin area. Canadian growth rate was slowing and each additional increase in nickel capacity was very expensive (Argall, G.O., 1970). Laterite ores were attractive to developers since they were easy to mine at a low labor cost, and technologies were being developed that would allow the recovery of nickel in marketable forms (Mohide, T.P., Warden, C.L., Mason, J.D., 1977). During the last decade, new laterite production was achieved in the Philippines and Botswana, and a significant increase in production from Indonesia and New Caledonia occurred. However, recent reports on nickel identify numerous problems plaguing the industry, i.e., high energy costs that are forcing shutdowns (INCO, 1980), (Mohide, T.P., Warden, C.L., Mason, J.D., 1977), high Canadian sulphide mining labor costs (Anon., 1976), and rapid inflation of nickel capital costs (Anon., 1981b). No definitive study has been made to determine how sensitive the total cost of production is to rising energy, labor, or capital costs, or to identify to what extent increased byproduct revenues could be used to offset these production costs. The purpose of this paper is to quantify the effects of increases in energy, labor, capital costs, and by-product credits on the future cost of production from nickel reserves and/or resources. METHODOLOGY OF ANALYSIS In order to evaluate the sensitivity of nickel production costs to changes in energy, labor, and capital costs, and in byproduct revenues, an analysis was made of existing and proposed nickel operations, their costs, and their sensitivity to change. The data for these analyses were obtained from numerous sources including international govern¬ment and university publications, professional journals, company reports, private communications, U.S. Bureau of Mines contracts, and estimates by Bureau of Mines personnel. These data were collected, in part, as an ongoing effort of the U.S. Bureau of Mines Minerals Availability System (MAS) to systematically measure and classify identified mineral resources according to their respective extraction technologies, economics, and commercial availability. The MAS Program is currently evaluating the present and potential availability of nickel to the United States in relation to mining, beneficiation, smelting, refining, leaching, transportation, infrastructure, environment, land use, labor, productivity, technology efficiencies, operating capacities, deposit life, and political factors. As a summary of this data, the following briefly describes nickel ore types as each relates to energy, labor, capital, and byproducts. Sulphide Operations Nickel is currently available from sulphide deposits. Roughly 55 percent of the current world nickel production in market economy countries is from sulphide ores, although only about 20 percent of the known land-based nickel reserves and/or resources are sulphides (INCO, 1981). In 1979, the Western World sulphide reserves were estimated at about 9.2 million metric tons of nickel (Little, A.D., 1979). Sulphide ores are typically mined underground, thus resulting in high mining costs; however, these ores can often be upgraded by flotation prior to final nickel recovery and require about one-third of the energy required to recover nickel from laterites (Anon., 1981c). In addition, nickel in sulphide ores may be associated with economically recoverable byproducts, which include copper, cobalt, gold, silver, and other precious metals. Laterite Operations Forty-five percent of current nickel production is from laterite deposits. Laterite deposits account for 80 percent of the known land-based nickel reserves and/or resources (INCO, 1981). In 1979, the Western World laterite reserves were estimated at over 35 million metric tons of nickel (Little, A.D., 1979). Nickeliferrous laterites are residual soils formed by weathering, typically under tropical or near tropical conditions. They can be easily mined by open-cut methods, but generally cannot be beneficiated; thus, recovery of nickel must entail processing of the total mined ore. Usually, these ores have high moisture content (20 to 30 percent by weight) that result in additional fuel costs to dry the ore. Nickel silicates, garnierites, are, processed by pyrometallurgical methods; limonite nickel oxides are normally leached. Byproduct cobalt is not recovered from most ferronickel operations, and is only recovered to a limited extent from many leach operations.

Jan 1, 1982

MARCH 15-Industry is rapidly snapping back from another coal crisis, other business news is in general favorable and the outlook through the Spring is by most observers considered quite promising. Most industries report comfortable backlogs of unfilled orders, department store sales in recent weeks have equalled in dollars those of the corresponding period last year, retail sales of automobiles show again over the same period a year ago, and new orders for machine tools are at the highest figures since August 1946. Orders for railway freight cars have shown a very encouraging pickup, with a total of 9385 cars in January and the N. Y. Central alone ordering 4500 in February. Construction continues very active. In January new housing starts totaled 80,000 against 50,000 a year ago and the daily average contract awards, according to the Dodge reports, were 57 pct larger. In the first 22 days of February the increase in awards was 27 pct. Lumber orders since Jan. 1 have run 22 pct above last year. All of these favorable factors bolster the opinion that the upturn in industrial output and employment which began last summer has not yet spent itself and that the setback caused by the strikes will be made up when people get back to work. Only in a few lines are there indications that primary production may be outrunning the consumption of finished goods, although inventory build-up would seem to be rather modest as the National Association of Purchasing Agents reported in February that 78 pct of its members were buying for 60 days or less. Industrial prices as a whole show no significant trend despite the continued alarm over both the immediate and the long-term possibility of inflation caused primarily by the government's increasing expenditure and its inability to balance the budget. A recent advance of 1.9 pct in primary market prices is viewed by some people as the surface symptom of renewed inflation, but even so it is more than two years since the alltime high was reached by the daily index of sensitive commodities in November 1947. Over two years have passed since prices received by farmers hit their peak and about a year and a half since all wholesale prices and the consumer price index touched their highest points in August 1948. The decline in the wholesale price index has been almost continuous, interrupted only twice by slight advances in the monthly figures from February to March 1949, and, later in the year, from August to September. Of course, this continued decline in the last half of 1949 largely reflects a downward movement in farm and food prices. Wholesale prices for commodities other than farm and food leveled out after June and now stand only slightly under the June level. Farm products are down by 22 pct from January and by 18.6 pct from August 1948. Food prices are down only slightly less. Consequently, the farm price support program is in serious trouble and has imposed a heavy financial burden on the Treasury. In those commodities other than farm products only building materials, chemicals and textiles have come down as much as the average, while housefurnishings and metals and their products have fallen hardly at all. Glancing away from the domestic front, the results of the British general election indicated a highly inconvenient situation, that public opinion there is so exactly deadlocked as to divest the victors of much ability to make forceful decisions or create significant policy. It is generally considered that another election in the near future would give substantially the same result. The British people are equally divided and the politicians are not likely to precipitate another appeal to the country until there is manifest reason to believe that external and internal circumstances have changed sufficiently to permit one party or the other to obtain a decisive verdict. Because of the lack of a clear mandate steel nationalization will likely lag in Britain. In the meantime there is considerable discussion going on as to whether the European steel industries as a whole are at a disadvantage in world competition with the American industry. An article in the "Statistical Bulletin" for January of the British Iron and Steel Federation takes issue on this point with the authors of the Geneva report, observing that they wrote before devaluation, and this particular conclusion "has been overtaken by events." The "Bulletin" also contends that the statement was in any case incorrect so far as Britain was concerned, and that it was based on scanty and insufficient evidence. To support the rebuttal a detailed and extensive comparison is made of the home prices of certain steel products in Britain and in other countries of the world. The accompanying table gives a selection of the prices published. It sets out the changed position since devaluation and since the recent increases in American steel prices. These are home market prices; no doubt in competitive export business some of the price levels could be brought closer together at need.

Jan 4, 1950

By H. Sigurdson, C. H. Moore

Extensive studies have been carried out on electric furnace and blast furnace slags obtained in the winning of iron from its ores. These slags normally consist of elements of the gangue minerals present in the ores, as well as the added flux materials. In consequence, melts of CaO, MgO, Al2O3 and SiO2 can be considered as representing typical slag compositions. When a slag of this composition cools, it usually crystallizes according to predictions possible from an equilibrium diagram of these constituents, providing the melt is not undercooled to form glass. The melt is either viscous or fluid, depending upon the ratio of binary cations to silica, and crystallizes easily or forms a glass for the same reasons. If the melt is not overheated so that carbides of the metal components of the slag are formed and if the composition of the slag is so adjusted that it has a high fluidity, liquid equilibrium is attained and the slag can be held in a liquid state for extended periods of time. Upon tapping, the slag crystallizes into minerals, the type and proportion of which are determined by the melt composition. Since equilibrium is attained, the holding period is not critical. In melts containing a large increment of titanium, however, the normal slag procedures are not applicable. Titanium, as one of the atomic transition elements, is, at elevated temperatures, capable of being reduced to form metalloid compounds much more readily than the refractory oxides present in normal slags. In consequence, an oxide melt containing titanium never reaches equilibrium in a reducing environment, but continues to shift its composition until cooled. If melts of this nature are cooled and samples submitted to metal-lographic and X ray analysis the course of reaction and crystallization in this type of slag can be determined. Preparation of Slag The slags investigated fell into the system CaO-MgO-TiO2-Al2O3-SiO2 and were produced from ilmenite ores reduced by carbon in an electric furnace. Since the equilibrium series1 and the laboratory smelting of ilmenite2 are described in two of the accompanying papers, detailed description of the smelting procedure is not required here. However, certain essentials must be mentioned. Two types of melts were used to produce slags studied in this investigation. The first series of smelts made to determine proper flux addition were produced in a 4 lb Ajax induction furnace. The charge, consisting of ore with the proper flux addition, was heated in a graphite crucible until fluid, held fluid for a sufficient time period to obtain 1-5 pct FeO content, and poured. Because of the small size of the charge only the final sample of these melts could be examined. In the melts made in the 50 lb arc furnace, however, grab samples taken at 10 min. intervals between time of initial melting and final pouring were available for examination. These samples allowed a much clearer picture of the course of reaction and crystallization. amounts of ferrous oxide and reduced titanium compounds is opaque to transmitted light. Therefore, all petro-graphic studies had to be made on polished slag sections. A representative sample of slag was cut or broken, mounted in a thermosetting plastic, ground flat using 400 grit silicon carbide, the coarse scratches removed with 600 grit silicon carbide and polished on billiard cloth using levigated alumina. Rouge was avoided because of the entrainment of the red particles in pores in the slag, causing a possible confusion with some of the mineral phases. In order to prevent sample projection above the plastic surface red bakelite was used to hold the sample, and backed up with clear lucite. In this manner sample labels could be permanently retained in the mounting. The polished samples were examined on a Bausch and Lomb metallograph at magnifications of 250 X, 500 X, 1000 X and 1800 X. The instrument was equipped for examination of specimens under bright field illumination and with crossed nicols. A magenta tint plate to aid in color tone differentiation was also used. Petrology of Slags In order to determine the composition and mineral relatinos of a previously unreported system petrologically, it is essential that the starting composition, reaction temperature and final composition be known. The chemical composition of the ilmenite ore used in these smelts is given in Table 1, and the complete analysis of a typical high titanium, low iron slag is given in Table 2. In the winning of TiO2 from ilmenite by a smelting process it is necessary to produce a slag which will melt at an economically feasible temperature, remain molten as the iron is removed by reduction, be fluid enough to be readily removed from the furnace, contain a high percentage of TiO2 and a low percentage of reduced titanium com-

Jan 1, 1950

By Murray F. Hawkins, W. J. Ainsworth

In all types of subsurface pressure gauges the extension which occurs in the pressure-sensitive element is a function of the difference between the external (well or calibration) pressure and the internal pressure within the gauge, rather than a function of the external pressure only. The internal pressure is near atmospheric and depends upon (a) the quantity of air sealed within the gauge at the time of calibration or measurement, (b) the quantity of moisture (liquid water), if any, sealed within the gauge, and (c) the temperature at which the calibration or well measurement is made. Part of this correction for the change of internal pressure with temperature is taken care of by the customary temperature coefficient of the gauge. However, part of it is not, and while this portion may be only a few psi, it is nevertheless predictable or preventable, and should be considered in precision measurements. ERROR NO. 1 If air is sealed in the gauge at the same temperature and pressure for both the calibration and the well measurements, the usual temperature correction will take care of any difference between calibration and well measurement temperatures. However, if air is sealed within the gauge at temperature T1 and pressure P1 at calibration but at temperature T2 and pressure P2 for a well measurement, because different amounts of air are sealed within the gauge in each case, the internal pressure at. or corrected to, calibration temperature Tr will he different by where all temperatures and pressures are absolute. The calibration temperature is used, and not the well measurement temperature, because the usual temperature correction reduces the well measurements to calibration temperature. The correction term as calculated by the above equation is separate from. and in addition to, the usual temperature correction. Example: T, = 540°R, sealing temperature at calibration P, = 14.7 psia, sealing pressure at calibration T2 = 460°R, sealing temperature at well P2 = 14.7 psia, sealing pressure at well Tr = 660°R, calibration temperature AP = 660 [14.7/460 — 14.7/540] = 3.1 psi While this error is small even under these somewhat maximal conditions, it nevertheless represents a practical situation which did occur, and which as a matter of fact gave rise to this note. Where AP is positive, as above, the correction is added to the measured pressure; where negative, subtracted from the measured pressure. This correction should also be considered in successive calibration runs where the gauge, for example, may be warm from a previous calibration at an elevated temperature. ERROR NO. 2 Where a small quantity of moisture (liquid water) is sealed within the gauge at atmospheric conditions, the increased vapor pressure of the water at higher well or calibration temperatures will cause an increase in internal pressure. This moisture will come presumably from condensation within the gauge following temperature changes, from moisture on the operator's hands, and from atmospheric moisture (rain, mist, fog, etc.). Calculation shows that approximately 0.2 cc of water (three to four drops) is sufficient to saturate the air within an Amerada RPG-3 Gauge at 160°F, at which temperature the vapor pressure of water is about 5 psia. As the vaporization occurs in a sealed volume, the increase in internal pressure will be in excess of this 5 psi. At higher temperatures the pressures will be higher; however more water will be required to saturate the air within the gauge. Some experimental work was carried out with an Amerada RPG-3 Gauge at 200°F fitted with a 1,000 psi element, both with a dry recording chamber and with a small amount of water added. The results directly proved the existence of the error due to the presence of moisture, and, it is felt, indirectly, due to the differences in sealing temperatures and pressures, as both effects may be ascribed simply to an increase in the moles of gas within the recording chamber. SUMMARY In precision measurements the error introduced by sealing the gauge during a well test at a different temperature and pressure from that of calibration may be corrected for by using the equation presented, or it may be prevented by taking care always to seal the gauge at near calibration conditions. The error introduced by sealing moisture in the gauge may be prevented by taking care to keep moisture out of the gauge, or by removing the moisture by either warming or evacuating the gauge. Both of these errors are independent of the range of pressure measurement and the type of gauge, and are in addition to the usual temperature correction. ACKNOWLEDGMENT Appreciation is expressed to W. B. Kendall, Geophysical Research Corp., Tulsa, Okla., who pointed out the error from differences in sealing temperatures during some winter work in Canada. ***

Jan 1, 1956

By M. M. Fine

Normally the U. S. produces less than 10 pct of its annual manganese requirement. About 95 pct of domestic consumption is used by the steel industry.' The strategic and critical nature of manganese has been recognized by its inclusion in the national stockpile and by intensified research directed toward cataloging and evaluating domestic manganiferous deposits. The USBM has participated in these activities for many years with field and laboratory studies to assess the extent and potential utilization of domestic manganese ores. One area of particular interest is in the vinicity of Batesville, Ark., where deposits have been mined since 1849 for both manganese and ferruginous manganese ores. Production is centered in Independence County, but deposits are also found in Sharp, Izard, and Stone counties in north-central Arkansas. Miser has described the geology and manganese mineralization in some detail.'. * "he rocks of the area are sedimentary, consisting of sandstone, limestone, shale, and chert. The two formations of greatest importance,' Fernvale limestone and Cason shale, are host rocks of the primary manganese mineralization. Through 1955 the district produced some 230,000 long tons of manganese ore (35 pct Mn or more) and 236,000 tons of ferruginous manganese (10 to 35 pct Mn).5 Most of the ore has been mined from deposits of manganese oxides in residual clays resulting from weathering of the two formations noted above. Concentration methods have been primitive, consisting for the most part of washing. hand picking, and jigging. A significant accomplishment in the district in recent years was the USBM recognition and investigation of the huge manganese potential represented by unaltered Fernvale limestone. systematic reconnaissance of manganiferous limestone and other occurrences has been in progress since 1953 to delineate the extent and tonnage of manganiferous materials. Results of that survey have appeared in two recent publications,1-5 which ascribe to the district an inferred reserve of 166 million long dry tons at a grade of 5 to 6 pct Mn. Most of this was mancaniferous limestone with an estimated content of 5 pct Mn. Specifications: Beneficiation was carried out on a group of manganiferous limestones to develop a way to recover commercial-grade concentrate from this extensive resource. The following chemical specifications were established by the GSA for metallurgical manganese ore acceptable for delivery to the national stockpile: Size specifications were not considered, as it was assumed that the concentrates could be pelletized or sintered. Manganiferous Limestones: Of the 11 samples tested to date, six were taken by cutting vertical channels across beds of limestone outcrops. Diamond drilling through overlying barren chert into unex-posed limestone provided four samples, and the last was a churn drill sample. In general, the samples were dlrk, fossiliferous limestone containing small amounts of braunite, hausmannite, rhodochrosite, massive and micaceous iron and manganese silicates, quartz, barite, and glauconite. The braunite and other manganese oxides partly to completely replaced some of the calcite and fossil material. The calcite was generously stained with mangenese and iron oxides. Phosphorus was present in all samples as collophanite grains, calcium phosphate fossil replacements. or an unidentified manganese-bearing carbonate. The difficulty in separating this complex array of minerals was further complicated by a very intimate association. Although some manganese grains as large as Ik in. were noted, grinding to subsieve sizes would have been necessary to liberate the components. Figs. 1 and 2 are micrographs, at X100, of typical polished sections in which white areas are manganese. gray is gangue, and black areas are surface depressions. By comparison with the 100 mesh opening, it is seen that some of the grains are coarse enough to respond, perhaps to tabling or flotation, but many are obviously beyond the scope of ohysical processing. Partial chemical analyses of the eight samples that were ultimately amenable to concentration are presented in Table 1. BENEFlClATlON RESEARCH Tabling: To take advantage of the presence of sand-size grains, both jigging and tabling were considered at the outset. Jigging was largely ineffective, but tabling achieved a partial recovery from most samples. As an example, the surface material from Baxter Hill was crushed to —28 mesh, hydraulically classified, and the coarsest spigot fraction was tabled to yield a concentrate, middling. and tailing. The latter two were reground to pass 48 mesh, combined with the primary fines, re-classified, and retabled. The middling and tailing were again ground, this time to pass 150 mesh, and deslimed at 20µ in a 3-in. hydraulic cyclone. The cyclone underflow was returned to the table to reclaim a small amount of high-grade manganese. An interesting facet of the gravity concentration developed on certain samples in which braunite was the principal manganese constituent. Since braunite has a Mohs hardness of 6 to 6.5, while the host rock, limestone. is only 3, a differential size reduction took place during crushing, and the

Jan 1, 1960

By S. R. Bardsley, S. T. Algermissen

Induction, nuclear and sonic well-logging methods were employed in a Green River formation oil-shale analysis and evaluation study conducted in northeastern Uintah County, Utah. The physical and chemical properties of an oil-shale section, previously cored and assayed by conventional methods, were used to evaluate the response of the various logs. The logging program was designed to measure variable properties of oil shale which relate to oil-yield potential in order that a relationship between assay-oil yield and log-determined properties could be identified, thereby permitting a direct determination of yield potential from logs alone. All of the major oil-shale zones and section ttlarkers are recognizable on the logs used in the study. The relationship between the response of the Density and Sonic logs and the assay-oil yield in gallons per ton was suficient to perinit the derivation of equations expressing the relationships. These equations can be used to determine the potential oil yield in gallons per ton of an oil-shale zone or section. The Neutron log response distinguishes the rich oil-shale intervals from the lean intervals, but does not appear to permit establishment of a quantitative relationship. The Garnma-Ray and Induction logs indicate only a qualitative relationship to oil-shale yields. Logging oil shale by Gamma-Gamrna Density and/ or Sonic logging methods will permit a fast, economical and accurate means of evaluating the potential yield of oil-shale deposits. Considerable sums of money have been allocated to Green River formation oil-shale evaluation during the past years by both private enterprise and Federal and state governments. The result of the work accomplished to date is commendable, but the task of fully exploring and evaluating one of the world's greatest reserves of potential energy for economical exploitation is enormous and much information is still needed. Present methods of evaluation consist primarily of sampling and assaying the oil shale for potential yield. The data received are excellent, but are both costly (inasmuch as it requires funds specifically allocated for the evaluation purpose) and time-consuming (as each representative sample must be assayed in the laboratory by specially trained personnel). At the present time, the Green River formation oil-shale province is one of the most active areas in the Rocky Mountain region for exploratory oil and gas drilling. This activity could play a twofold role and serve the function of spear-heading many oil-shale evaluation programs, as it could provide both cutting samples for assaying, geophysical data and modern well logs. This paper deals with a recent study conducted on Green River formation oil shale in which the application of induction, sonic and nuclear well logs to oil-shale evaluation was tested and proved. THEORY AND DEFINITIONS Oil shale may be described as siliceous marlstone, rich in solid organic matter called "kerogen". Kerogen is only slightly soluble in organic solvents, but it will decompose and yield oil vapors and gas when heated to destructive distillation temperatures at about 800 F. The mineral constituents of Green River formation oil shale are found in essentially uniform proportions with one another. The dominant types are, in the general order of abundance, dolomite, calcite, feldspars and quartz. Kerogen is also essentially uniform in its composition, and is about 80 per cent carbon and 10 per cent hydrogen by weight. The ratio of kerogen to the mineral constituents determines the richness or potential yield of the oil shale. This ratio also determines the total physical and chemical properties of the rock and provides a basis by which oil-shale richness may be determined from well logs. Because Green River formation oil shale was deposited in a lacustrine environment, the lithology is laterally consistent over wide areas. The vertical section consists predominantly of thin bands of alternating rich and lean oil shale which have been described by Bradley' as varves. The varves are occasionally broken by thin bands of volcanic ash and tuff and by zones of lean vugular oil shale. The effect that the thin non-oil shale beds and vugular zones would have on the well log analysis was a prime concern in the study. To cope with this possible problem, the logs used in the study were of two types: (1) logs believed to respond favorably to those properties of oil shale which are dependent upon the kero-gen-to-mineral ratio, these logs being the Gamma-Gamma Density log, the Sonic log and the Neutron log; and (2) logs that would respond to litho-logies and properties within the oil-shale section not associated with yield that might result in anomalous responses by the yield-measuring logs. Logs of the second type were the Gamma-Kay log, the Induction log and the Caliper log. THE PRESENT STUDY The present logging study was con-

By R. M. Brown, W. J. Murphy, B. M. Kapadia

An investigatiott was conducted to study the influence of nitrogen, titanium, and zirconium on the boron llardenabilzty effect in a low-carbon constructiona2 alloy steel. The experimental steels investigated exhibited a significant variation in hardenability, the variation being dependent on the interactions of boron, titanium, and zirconium with the nitrogen. Only the boron not combined with nitrogen was effective in increasing hardenability. Titanium, and with lesser effectiveness zirconium, combined with available nitrogen, thereby protecting the boron. The hardenabil-ity effect mas related to an empirical expression for the "effective" boron content, P, deduced from experimental evidence of these interactions. The hardenabzlity effect reached a maximum at about 0.001 wt pct 0, and decreased somewhat as P increased further. The physical understanding of this relationship is discussed. FOR many years boron has been added to steels to obtain high hardenability. Although a great deal of research has been conducted on boron-treated steels, certain aspects of the boron hardenability effect have not been fully understood. For instance, the magnitude of the hardenability effect has been observed to vary markedly, depending on the steelmaking technique, even when the amount of boron in the steel was essentially constant. Furthermore, the optimum amount of this element to be added has not been definitely established. A better understanding of the boron hardenability effect is essential because too small an addition of boron is likely to be ineffective, while an excessive amount can cause brittleness'' and hot shortness. The findings of earlier investigations have shown that the hardenability effect cannot be consistently related to the amount of boron added or retained in the steel. Grossmann observed that in a 0.60 pct C steel the hardenability increased to a maximum with mold additions up to about 0.0025 pct B and then decreased with larger additions. Other investigators5 likewise reported a maximum in the hardenability at about 0.003 pct B. Crafts and Lamont, however, found that in commercial open-hearth heats of medium-carbon steel the hardenability increased linearly with boron up to 0.001 pct and remained essentially unchanged with larger percentages up to 0.006 pct. Other investigators7,' also observed a rather constant hardenability effect in the range about 0.0005 to 0.0035 pct B. These observations and other evidence suggest that the effectiveness of boron in increasing hardenability probably depends, in addition to the amount, on the form of boron retained in the steel, this form being influenced by the presence of other elements. Both oxygen and nitrogen apparently exert the strongest influence on the hardenability behavior, since, at the temperature of liquid steel, boron readily combines with these elements, thereby losing its effectiveness as most experimental evidence seems to indicate. For consistent recovery of the boron effective in increasing hardenability, it is necessary that the oxygen and nitrogen in the steel be either reduced to extremely small amounts by the steelmaking practice or neutralized by combination with other elements before the addition of boron. The importance of achieving adequate deoxidation prior to the addition of boron in order to realize the full hardenability effect of boron has been sufficiently emphasized by earlier investigators. Digges and Reinhart' and others have investigated the role of nitrogen and have shown that nitrogen also interacts with boron and reduces or nullifies altogether its effect on hardenability. Moreover, their work also demonstrated that the addition of strong nitride formers such as titanium and zirconium reduce the deleterious effect of nitrogen on boron hardenability by combining with nitrogen to form stable nitrides. Another element which has a pronounced influence on the boron hardenability effect is carbon. It has been shown7'10 that the hardenability effect of boron diminishes with increasing carbon content, and becomes almost negligible at the eutectoid composition. This observation is useful in comparing the potential increase in hardenability from boron of steels with different carbon contents, but is not relevant to a study of the effects of normal steelmaking variables. The amounts of oxygen and nitrogen in steel vary with the steel composition and steelmaking practice employed. Most commercia1 low-alloy steels are fully deoxidized by the addition of silicon and aluminum, or other strong deoxidizers, which adequately protect the boron from oxidation. In addition, one or more of the elements such as titanium or zirconium are usually added, either separately or in combination with boron, in the form of complex ferroalloys, to protect boron from combination with nitrogen in the steel. However, the actual amount and type of addition employed for a given processing requirement are usually selected by trial and error, and have a rather limited range of applicability. As a result, substantial variations in the hardenability of boron-treated steels are often observed in practice, particularly when the nitrogen content of the steel is a significant processing variable. These variations might therefore be reasonably attributed to the interactions between boron, nitrogen, and titanium or zirconium present in the

Jan 1, 1969

By R. G. Aspden

The cold rolling and annealing textures were studied for 3 pct Si-Fe grains initially (001) [hkl]. A concentration of (001) [loo] primaries were observed only in the annealing textures of crystals initially having [loo] within 8 deg of the rolling direction. Eke annealing textures of the (001) [I101 cold rolling textures were sensitive to the initial orientation of the grains. Single crystal data were used to explain the formation of (001) [loo] in poly-crystalline malerial. CUBE texture formation in 3 pet Si-Fe sheet occurs during the final high temperature anneal. Its formation is dependent on the proper distribution of (001) plane primaries with reference to the rolling direction&apos; and on the growth of these primaries by secondary recrystallization. The selective driving force for these primaries with (001) within 7 deg of rolling plane is derived from the difference in surface energy between the annealing atmosphere and the crystallographic planes exposed at the surface of the sheet.&apos;-= The alignment of [loo] directions of (001) secondaries with the rolling direction is required for optimum magnetic characteristics7 and is dependent on processing.&apos; A high degree of alignment has been observed when the final cold rolled texture has a strong (111) [ll2] type component3 and the normal grain growth texture prior to secondary recrystallization has components with a [loo] parallel to the rolling direction and planes from (001) to (110) parallel to the rolling plane.1,3,8,9 Generally, this (001) component is much weaker than the (110) component. The growth rate of (001) plane primaries to secondaries has been found to be independent of the orientation of the primaries with reference to the rolling direction, i.e., the secondaries have the same degree of alignment of [loo] directions with the rolling direction as the (001) primaries.&apos; Hence, the rolling and annealing textures of individual grains or single crystals are of interest in understanding the development of the (001) [loo] secondary recrystallization texture. (001) components have been observed in the annealing textures of cold rolled grains initially having a [loo] parallel to the rolling direction and an (001) rotated up to 30 deg from the rolling plane. Crystals initially near the (001) [loo] orientation when rolled under the influence of constraints imposed by neighboring grains form deformation bands and ro- tate in both directions toward (001) <110>.10,11 Deformation bands have been reported also for crystals initially with an (001) within 1 deg of the rolling plane and a [loo] within 1 deg of the rolling direction when rolled as a free single crystal.12 These crystals have weak recrystallization textures and contain near an (001) [loo] component.10-12 When near (001) [loo] crystals are rolled as free single crystals no deformation bands form and the crystals rotate by a single rotation toward (001) [110]. Recrystallization after a 70 pct cold reduction yielded near an (001) [loo] component13 and after a 90 pct cold reduction an (001) [I201 component." Crystals initially near (210) [001] had a texture after a reduction of 70 and 84 pct which was similar to the (111) [li2] but rotated 10 to 15 deg in the transverse direction. These crystals recrystallize to (210) [OOl] or (410) [001] and contain an (001) [loo] component.10,13 An (001) component has not been detected in the normal grain growth textures of other single crystals. Crystals initially having orientations between (110) [001] and (111) [ll2] have a cold rolled texture of principally (111) [ll2] .10>16 Other crystals with a [I101 parallel to the cross direction rotate to (111) [112] and/or (001) [110] stable end orientations. Crystals initially having from (001) [110] to (111) [lie] retain this orientation after cold rolling.15 The cold rolled textures having [I101 directions parallel to the rolling direction had components in the annealing textures related to the deformation textures by 25 to 30 deg rotations about common (1 10) poles. Cold rolled textures of the (111) (112) type recrys-tallized to (120) [001] or (110) [00l]. The purpose of the present work was to further the understanding of the alignment of [loo] directions of (001) secondaries with the rolling direction. The cold rolling and annealing textures of grains initially (001) [hkl] were studied. These data were applied to the formation of (001) [loo] by secondary recrystallization. PROCEDURES AND EXPERIMENTAL TECHNIQUES The (001) poles near the sheet normal and rolling direction are given in Fig. 1 for the 10 grains studied. Each of these grains was located in the center of a polycrystalline specimen approximately 25 mm wide and 50 mm long. The lower case lettered grains, a through dl were about 1.2 mm in diam and near the (001) [loo] orientation. Specimens containing these grains were from a commercial 3 pct Si-Fe alloy with the principle orientation of (110) [001] as obtained by impurity inhibition of growth with manganese sulfide inclusions.17,18 Upper case lettered grains, A through F, were about 6 mm in diam and had (001) planes near the rolling plane and [hkl] di-

Jan 1, 1963

By Nicholas J. Grant, Ulf Kalling, John Chipman

THE operation of a blast furnace is dependent to an important extent upon the sulphur content of materials charged and the desired limit of sulphur in the product. It has long been known that the blast furnace is the most efficient tool for desulphurization in common use and that this efficiency is associated with the strongly reducing conditions of the hearth and is enhanced by increased basicity and fluidity of the slag. The chemical reactions of desulphurization may be studied from the viewpoint of the ratio of the process or of the final equilibrium conditions. Both kinds of studies contribute to an understanding of the process and both are included here. A simple measure of the desulphurization power of a slag is given by the ratio: Pct sulphur in slag (Pet S) Pct sulphur in metal [Pct S] This ratio was used by Holbrook and Joseph&apos;,&apos; to measure relative desulphurizing powers under controlled laboratory conditions. It was also used by Hatch and Chipman3 as a measure of the equilibrium distribution. For the latter purpose it would be preferable to employ thermodynamic activities rather than percentages, but until very recently this has been impossible for lack of data. Now, thanks to the work of Morris and Williams and Morris and Buehl," the effects of carbon and silicon upon the activity of sulphur in the metal are known. The confirmation of this work and its extension to include the effects of other elements by Sherman and Chipman and by Rosenqvist and Cox&apos; make it possible to calculate the activity of sulphur in pig iron of any composition. Hence it is now possible to use data on the equilibrium distribution of sulphur to find its activity in the liquid slag and to approach an ultimate solution of the thermodynamic aspects of the problem. The rate of transfer of sulphur from metal to slag is the problem of major industrial importance and indeed the principal need for equilibrium data has been as a necessary adjunct to the kinetic studies. The rate of approach to equilibrium under laboratory conditions seems slow compared to the requirements of industrial practice, and it is clear that further laboratory studies of rates are needed. In the research reported below, the items which were investigated were the following: I—The role of mechanical stirring on the approach to equilibrium. 2—The role of MgO in desulphurization as compared to CaO. 3—The role of MnO in desulphurization. 4— The limiting reactions which constitute the slow steps in desulphurization. Experimental Procedure The experimental set-up and procedure previously described by Hatch and Chipman" were essentially followed with several small modifications. The graphite crucible containing the slag and metal charge was altered to provide considerably more active stirring and mixing of the slag and metal in the carbon monoxide atmosphere. For this purpose the crucible was machined to provide two deep cylindrical wells which were interconnected at top and bottom as shown in Fig. 1. A graphite screw with a flat thread and of shallow pitch (4 threads per in.) spinning at 600 to 800 rpm was used to lift the slag and metal over the partition between the two wells and throw them over into the second well, where the metal settled through the slag into the reservoir at the bottom. It was possible to see actual particles of slag and metal being thrown over the partition. In this respect, the stirring was more vigorous than used in the work of Hatch and Chipman. A charge of 400 g of wash metal was first melted, and 20 g of FeS was then added to yield a bath containing 1.65 pct S. Immediately 400 g of slag (as pure mixed oxides) was added and fused. The slag was generally fused in 1 hr * 10 min. Within 30 to 45 min after melting, the temperature was adjusted to 1525"C, and the first slag and metal samples were taken. The slag was picked up on the end of a cold Armco iron rod, whereas the metal was sucked into a silica tube. The wash metal composition was (in percent): 4.29 C; 0.022 S; 0.021 P; 0.38 Si. The slags used were of four fixed starting compositions covering a wide range of acid-base ratios shown in Table I. Deliberate variations in MgO were made in these slags to check the role of MgO in blast-furnace desulphurization. Changes due to additions and reactions were followed by analysis of samples. Additions of Mn and MnO were made to most of the heats to note the role of Mn and MnO on desulphurization. Three heats (62 through 64) were made in an open pot induction crucible (graphite) using a

Jan 1, 1952

By A. Lubinski, W. D. Greenfield

Bumper subs are currently used in offshore operations to permit a constant weight to be carried on the bit while drilling, regardless of the vertical motion imparted to the drill pipe by drilling vessel heave. As shown in this paper. the vertical motion of the lower end of the drill pipe (the bumper sub end) may be appreciably greater than the vessel heave. Therefore, the necessary stroke of bumper .rubs for successful operation is greater than thought in fie past. Also, there is an appreciable tendency of the drill pipe to buckle above the unbalanced type of bumper sub. Thus, more drill collars than previously used should be carried above unbalanced bumper subs to keep drill pipe straight. INTRODUCTION Drilling bumper subs are placed in the drilling string for various reasons. This paper is concerned with their use only as an expansion and contraction joint while drilling from a floating rig. In this application the bumper subs are normally located just above the drill collars and their function is to allow the driller to maintain accurate weight control on the bit regardless of up-and-down movement of the drilling vessel. This paper analyzes the effects of bumper subs on the drilling string and presents recommendations for their future use. When subjected to vertical oscillations, the drilling string behaves like a long, distributed system of mass and spring. The magnitude of vertical motion at the bumper sub is always greater than the heave of the drilling vessel due to the dynamic reponse of the drilling string. The ratio of these motions increases with the length of the drilling string, and may reach values of 1.5 or even 2 with strings 16,000 ft long. Thus, the total travel required in bumper subs can be considerably more than the motion of the drilling vessel. Lack of knowledge of this fact could have contributed to problems previously experienced with bumper subs. This fact can also lead to fatigue problems in the drilling string for very deep wells. Satisfactory operation should be obtainable whether hy-draulically balanced or unbalanced bumper subs are used in the drilling string. Theoretically, the balanced sub is preferable since its use does not require placing drill collars above the bumper sub to prevent drill-pipe buckling, an inherent characteristic of the unbalanced bumper sub. The current method of calculating weight of drill collars required to prevent helical buckling of drill pipe above unbalanced bumper subs is erroneous. Placing drill collars above the sub to prevent drill-pipe buckling has the same effect on dynamic response as increasing the length of the drilling string by an equal weight of drill pipe. Thus, total travel required in the subs is increased. Means for calculating the correct weight, which is much greater than previously thought, are given in this paper. BALANCED VS UNBALANCED BUMPER SUBS A drilling bumper sub is essentially a telescopic joint capable of transmitting torque at every position of its stroke. Thus, it allows the operator to isolate the weight of the drilling string from the weight of the drill collars above the bit. This permits the driller on a floating rig to maintain accurate control over the weight on bit — a control that is unaffected by vertical motion, due to wave and tide action of the drilling vessel. UNBALANCED BUMPER SUBS The unbalanced bumper sub is simply a splined tele~copic joint (Fig. I). Ordinarily, this arrangement will operate satisfactorily, but the presence of drilling fluid under pressure results in a pressure force that acts downward on the drill collars and bit, tending to open or extend the bumper sub. This downward force is equal to the pressure drop across the bit times the area indicated by diameter d2 in Fig. 1. Denoting this force by Fd, and the pressure drop across the bit by ?p yields Fb = (p/4)d22(?P) .........(1) There is also an upward-directed force given by Fu = (p/4) d22-d21)(?p) .......(2) which puts the drill pipe immediately above the bumper sub in compression, resulting in helical buckling. However, buckling is actually more severe than expected in that buckling occurs as if the compression were equal to Fd, rather than to Fu. This surprising phenomenon is well known as far as tubing is concerned;1-3 but, in contrast with the case of tubing, this force may shorten drill pipe only a few inches. Thus, this cannot explain the operating difficulties that sometimes have been encountered. However, having the drill pipe in compression and helically buckled is contrary to current practice; therefore, drill collars whose weight in mud is equal to the force Fd should be added above the bumper sub. Since the value of Fd depends on the pressure drop across the bit, the

By C. S. Roberts

The creep mechanism and kinetics of fine-grained magnesium have been studied over the temperature range 200&apos; to 600°F. As a result of a photographic study of microstructural changes, transient and steady-state creep components have been correlated with slip, subgrain formation, and cyclic deformation at the grain boundaries. THE approach of this research has been the blend of a quantitative study of the creep strain of polycrystalline magnesium as a function of time, stress, and temperature with direct microstructural observations of the operative deformation processes. The validity of the conclusions is dependent on the condition that the microstructural changes seen on the polished surface qualitatively represent those occurring in the bulk of the metal. The work was intended as much to lay a background to a study of highly creep-resistant magnesium alloys as to provide a description of the behavior of the base metal itself. The spectroscopic analysis of the electrolytic magnesium used in this study is as follows: Al, 0.009 pct; Ca, <0.01; Cu, 0.0011; Fe, 0.021; Mn, 0.012; Ni, 0.0004; Pb, 0.0012; Si, <0.001; Sn, <0.001; and Zn, <0.01. The impurity level is approximately that of commercial magnesium alloys. The original ingot was melted under Dow type 310 flux and cast as a 3 in. diam billet. It was extruded into 1 in. flat stock under the conditions: billet preheat 800°F (1 hr), container and die temperature 800°F, speed 3 ft per min, and area reduction ratio 45:1. The extrusion process was chosen in preference to rolling and recrystallization because it allowed easier grain size control from specimen to specimen. The grains of the extruded metal were fairly equi-axial and uniform in the size range of 4 to 6 thousandths of an inch. The preferred orientation of basal planes about the transverse direction was determined by an X-ray diffraction surface reflection method. A beam of filtered copper radiation was directed at an angle of 17" to both the transverse direction and the surface yet perpendicular to the extrusion axis. Analysis of the (002) diffraction arcs in the resulting photographic patterns gave an approximate intensity distribution along the great circle which extends through the center of the basal plane pole figure and to the extrusion axis poles. Successive layers of metal were removed by macro-etching between exposures. The extruded texture is relatively sharp, but the most significant point is the position of the maximum basal plane pole density and its variation with depth below the surface. Fig. 1 shows that this maximum is rotated 15" from the normal at the surface toward the extrusion direction. Such an inclination has been reported for extruded 1 pct Mn and 8 pct A1-0.5 pct Zn alloys.&apos; The inclination decreases until the maximum splits at about 0.025 in. depth into two elements of equal and opposite rotations from the ideal. The double texture persists to as great a depth as was experimentally convenient to examine. It probably continues to the very center of the extrusion. There is no great change in the sharpness of the individual elements of the texture with depth. A plate of metal about 0.015 in. thick at the surface of the extruded stock was produced by etching. A transmission diffraction pattern was made for the purpose of determining any preferred orientation of a direction in the basal planes. Relatively uniform {loo) and {101) rings were produced. There is little tendency for parallelism of a given direction in the plane with the projection of the extrusion axis on it. The creep specimens were machined from 6¼ in. lengths of the extruded stock. Creep was measured on the reduced section, ½x1/8X2¼ in. long. This section was electropolished on one side for the studies of microstructural changes during creep. An orthophosphoric acid-ethyl alcohol electrolyte was used under the conditions recommended by Jacquet.² Hand polishing was used for previous mechanical preparation. Electropolishing was continued until all mechanical twins had been removed. The electro-polished surface was protected from oxidation during creep testing by a thin layer of silicone oil. All micrographs were taken at room temperature on conventional metallographic equipment and after removal of the oil film. The creep tests were performed with machines which have been described in detail by Moore and McDonald." Five testing temperatures, 200°, 300°, 400°, 500°, and 600° ±3°F were used. Difference in temperature between the two ends of the specimen reduced section was 2°F or less. The testing was done at constant load. Strain readings were taken as frequently as necessary to develop usable creep curves. Tensile Creep vs Time, Stress, and Temperature A definition of terms is necessary. Whenever successive sections of a creep strain-time curve show decreasing, constant, and increasing slope with time they will be termed primary, secondary, and tertiary

Jan 1, 1954

By D. H. Desy, L. C. Fincher

The magnesium-rich end of the Mg-Ti phase diagram was investigated. The liquidus, solidus, and solvus boundaries to 1 pct Ti were established. All alloys were prepared by saturating molten magnesium with titanium in a consumable titanium crucible under inert gas maintained at 230 psig. The liquidus of the Mg- Ti system was determined by analysis of dip samples taken from 700° to 1300°C under equilibrium conditions in a pressurized inert atmosphere furnace and by analysis of small ingots rapidly poured and quenched from 1400° to 1500°C. The solubility of titanium in magnesium ranged from 0.018 wt pet Ti at 700°C (0.012 wt pet at 650°C by extrapolation) to 1.035 wt pet Ti at 1500°C. The solidus for compositions ranging from 0.03 to 1.00 wt pet Ti was determined to be 650° ± 1°C by thermal analysis. The titanium solid solubility values ranged from 0.08 wt pet at 350°C to 0.19 wt pet by extrapolation to 650°C. The freezing reaction is peritectic. No intermetallic compounds were found in the system; the phase in equilibrium with molten magnesium saturated with titanium was found to be titanium with magnesium in solid solution. Solid titanium will dissolve at least 1.32 wt pct Mg. PREVIOUS investigations of the Mg-Ti system have shown considerable disagreement on the solubility of titanium in liquid magnesium. Furthermore, the solid solubility of titanium in magnesium has not been well established. Liquidus curves for previous work and for the present investigation are shown in Fig. 1. Aust and Pidgeon1 used a dip-sampling method on molten magnesium held in equilibrium with solid titanium under a protective atmosphere to determine the solubility and found that it ranged from 0.0025 wt pet Ti at 651°C to 0.015 wt pet Ti at 850°C. Eisenreich2 introduced titanium into molten magnesium by means of TiCL4 adsorbed on BaCl2. Ingots were then cast at various temperatures. Making the assumption that only the titanium dissolved in magnesium at the time of casting was soluble in H2SO4, Eisenreich determined the solubility of titanium in molten magnesium to range from 0.003 wt pet at 655°C to 0.115 wt pet at 800°C. Eisenreich also determined the solid solubility of titanium in magnesium to be 0.015 wt pet at room temperature and 0.045 wt pet at 500°C. Since the solid solubility just below the freezing temperature for the bulk of the alloy was much larger than the liquid solubility just above the freezing temperature, Eisenreich concluded that the freezing reaction was peritectic. Obinata et al.3 equilibrated molten magnesium with titanium in hermetically sealed titanium containers which were then furnace-cooled. The titanium content of the magnesium was then determined and found to range from 0.170 wt pet at 700°C to 0.85 wt pet at 1200°C. No intermetallic compound was found in the system. The Armour Research Foundation4 determined two points on the solvus by electrical resistivity methods: 0.00057 wt pet at 200°C and 0.0008 wt pet at 300°C. At higher temperatures, data were meaningless with no trends observable. The authors of this report believed that the lack of significant data at the higher temperatures was due to variations in specimen geometry, although there was no positive evidence to verify this supposition. The present investigation was undertaken to clarify the uncertainty in both the liquidus and solvus of the magnesium-rich end of the Mg-Ti system. EQUIPMENT AND MATERIALS The equipment used in this investigation, with some modifications, was essentially that used by Crosby and Fowler5 in their determination of part of the Mg-Zr phase diagram. The equipment, as modified for this work, is shown in Fig. 2. It consists of a sealed furnace chamber which can be pressurized with inert gas so that melts can be made above the boiling point of magnesium at atmospheric pressure. Melts are made by induction heating in a titanium crucible which, after diffusion of sufficient magnesium into the walls of the crucible to saturate the titanium at the sampling temperature, comprises the solid phase in equilibrium with the molten magnesium. Dip samples may be taken with the sampling tube, or the entire furnace may be tilted so that ingots may be poured into a mold in the side chamber. The principal difference from the earlier apparatus is in the thermocouple, which in the present equipment is enclosed in a protection tube and immersed directly in the melt. The tips of both the thermocouple protection tube and the sampling tube, which dip into the melt, are made of high-purity titanium. The 4 1/2-in.-long titanium tip of the sampling tube is threaded into a steel tube, O in Fig. 2, which extends through the top of the furnace. To determine whether the temperature at the tip of

Jan 1, 1969

By Michel Dupuy, Daniel Calais

The study of self-diffusion of plutonium in E phase has been carried out by the welded couples method. The tracer used was puZ4O which is detected by its X-ray emission (conversion lines of uranium which are computed between 13 and 21 kev). Intensities were measured with a scintillation counter. Each layer was removed in a direction parallel to the original interface with a grinding machine and a thickness measured with a pneumatic comparator. The concentration-penetration curves obtained were corrected for the effect of heating time from room temperature to annealing temperature and for the expansion due to phase transformations of plutonium. They were analyzed by the generalized Gruzin method. Self-diffusion of plutonium in E Phase is very fast cm per sec between 500" and 620°C) and the diffusion zones are 2 to 3 mm wide for annealing times ranging from 30 min up to 10 hr. The Arrhenius law gives the temperature dependence in the form: From the point of view of self-dqfusion, PUE phase falls into the anomalous bcc metals category (Tip , Hfp, Zrp, Uy) with a low-frequency factor and an activation energy lower than those provided by standard correlations. No theory proposed hitherto to explain these anomalies (influence of dislocations, of extrinsic vacancies bonded to inlpurities, of bi-vacancies) can clearly explain the self-diffusion coeffzcients of plutonium. DIFFUSION in bcc metals is a present-day problem. A recent symposium (Gatlinburg, 1964), followed by a book,&apos; has been devoted to it. A great many experiments seem to show that diffusion in certain bcc metals obeys unexpected laws. The activation energies measured are sometimes strangely low (B hafnium, y uranium). For certain metals (0 zirconium, p titanium) the curves of log D (D = diffusion coefficient) as a function of 1/T (T = absolute temperature) are not linear. The frequency factors Do, which are of the order of 1 sq cm sec-&apos; in fcc metals, vary from 1 to 10~6 sq cm sec-&apos;. Various theories have been put forward to explain these anomalies; none is yet satisfactory. We wished to introduce a new experimental result by studying the self-diffusion in c plutonium. This allotropic phase, stable from 475°C up to the melting point (640°C), is in fact bcc. Unfortunately, nothing is known of the characteristics of the point defects in this phase, which limits the scope of the hypothesis which can be made about the mechanism(s) of self-diffusion in plutonium. 1) EXPERIMENTAL METHODS 1) Principle. We used the welded couple method. The two pellets of the couple initially have different 240 isotope contents (X emitter). After diffusion, the concentration/penetration curves are drawn up by the generalized Gruzin method. 2) Gamma Spectrography. The metal used in our study is plutonium, either low in puZ4O (isotopic content 1 pct) or high in puZ4O (8 pct). The latter also contains plutonium 241 (-1 pct) and 300 ppm of ameri-cium produced by the reaction Pu2U-AmM1 + 8-. The emission spectra of these two plutoniums placed in leak-tight vinyl bags have been studied by y spectrograph~. The detector is a thin crystal of thallium-doped sodium iodide. The activity of the plutonium rich in 240 is about twice that of the plutonium low in 240 in the energy band of 17 kev (L conversion lines of uranium); this band was used in these measurements. 3) Preparation and Examination of the Diffusion Couples. Diffusion couples were made from plutonium with a high and low PU"&apos; content. Pellets (6 6 mm. thickness 3 mm) mounted on a polishing disc with ground parallel faces were polished mechanically on both sides. In this way, pellets with two parallel faces were easily obtained. The polished pellets were joined by a 6 phase anneal (420°C, 1 hr) in a small screw press (pressure of 20 kg per sq mm cold); a centering ring enabled the two pellets to be pressed coaxially. The couples then were subjected to the diffusion treatment by annealing in the E phase in sealed silica ampules in argon at atmospheric pressure. The annealing temperatures and times are given in Table I. The couples were encased in a mild steel ring, the joint interface being thus parallel to the ground face of the ring. The diffusion couple/ring assembly underwent successive abrasions by means of a magnetic plate grinder. The thickness of the abraded layer was measured with a Solex pneumatic comparator when it was less than 0.1 mm (accuracy 0.2 p) or with a mechanical micrometer (accuracy 3 p) for passes of the order of 0.2 mm. All these operations were done in glove boxes, as plutonium is particularly toxic. After each abrasion we determined the emission spectrum of the ground face. The emissive surface is defined by means of a diaphragm 3 mm in diam. We noted more particularly the X activity in the 17-kev

Jan 1, 1969

By R. T. Hukki

John F. Myers (Consulting Engineer, Greenwich, Corm.)—Since the art of comminution has lain practically dormant for many years, it is very interesting that R. T. Hukki approaches the subject with a new concept. One is reminded of the research carried on by A. W. Fahrenwald of Moscow, Idaho, a few years ago. Fahrenwald mounted a steel bowl on a vertical shaft. The balls and ore placed in the bowl were rotated at fast speeds, thus simulating the supercritical speeds used by Hukki. The rolling action of the balls against the smooth shell liner has pretty much the same effect. The action is horizontal in one case and vertical in the other. Both researchers report good grinding activity. It is also constructive that such able investigators give to the students of comminution their interpretation of their laboratory results in terms of large-scale operation. History shows that it takes a lot of time for such radically new ideas to be absorbed by the industry. Typical of this is the present-day activity of cyclone classification in primary grinding circuits. The idea of cyclone classification has been kicking around for 30 or 40 years. Certainly we all suspect that the ponderous grinding mills of today, and their accessory apparatus, large buildings, etc., will ultimately give way to small fast units, just as this has occurred in other industries over the past 50 years. At the moment there is no evidence that ball and liner wear is prohibitively high. In fact, at the time Fahrenwald was demonstrating his high-speed horizontal machine at the meeting of the American Mining Congress, several years ago, he assured this writer that the balls retained their shape much longer than they do in conventional tumbling mills. Rods and balls that slide (as some operators in uranium plants are experiencing) get flat. Apparently the balls have a rolling action. Mr. Hukki&apos;s references to the processing capacity of the Tennessee Copper Co. mills is adequate. Those studying this subject will be greatly interested in the paper presented by Richard Smith of the Cleveland-Cliffs Iron Co. at the annual meeting of the Canadian Institute of Mining and Metallurgy in Vancouver April 24, 1958. This paper will be published during the latter part of 1958 in the Canadian Institute of Mining and Metallurgy Bulletin. Hukki&apos;s pioneering spirit is to be commended. R. T. Hukki (author&apos;s reply)—It has been heartening to read the objective discussion by J. F. Myers. The sincerity of his opinions is further strengthened by the fact that the article he has discussed contradicts in a major way the parallel achievements of his life work. Myers is right in his opinion that in general it takes a long time before new ideas are accepted by the industry. On the other hand, revolutions usually take place at supercritical speeds. There are many indications at present that both the unit operation of grinding and the related subject of size control are now just about ripe for a revolution. In grinding, brute force must ultimately give way to science. Rapid progress can be anticipated in the following fields: 1) Autogenous fine grinding at supercritical speeds will be the first advance and the one that will gain recognition most easily on industrial scale. At this moment, little Finland appears to be leading the world. Crocker recently made a statement that in nine cases out of ten, your own ore can be used as grinding medium more effectively and far more economically than steel balls. This is true. The present author would like to introduce a supplementary idea: In eight cases out of the nine cited above, it can be done at the highest overall efficiency in the supercritical speed range. Fine grinding must be based on attrition, not impact. The path of attrition may be vertical, horizontal, even inclined. 2) In coarse grinding, the conventional use of rods is sound practice. However, even the rods can be replaced by autogenous chunks large enough to offer the same impact momentum as the rods. To obtain the momentum, the chunks must be provided with a free fall through a sufficient height in horizontal mills operated at supercritical speeds. Coarse grinding must be based on impact. Detailed analysis of the subject may be found in a paper entitled "All-autogenous Grinding at Supercritical Speeds" in Mine and Quarry Engineering, July 1958. 3) All conventional methods of classification, including wet and dry cyclones, are inefficient in sharpness of separation. Continuous return of huge tonnages of finished material to the grinding unit with the circulating load is senseless practice. In the near future the present methods will be either replaced or supplemented by precision sizing. These three fields are also the ones to which J. F. Myers has so admirably contributed in the past. Fine Grinding at Supercritical Speeds. By R. T. Hukki (Mining EnGineERInG, May 1958). Eq. 9, page 588, should be as follows: T , c, (a — 6&apos;) n D Ltph On page 584 of the article the captions for Figs. 4 and 5 have been placed under the wrong illustrations and should be interchanged.

Jan 1, 1959

By T. Y. Yan

SUMMARY Laboratory high pressure column tests have shown that the presence of 1-20 ppm of aluminum ion effectively prevents permeability loss during uranium leaching with leachates containing sodium carbonate. If added after permeability loss has occurred, aluminum ion can restore the permeability to nearly its original value. No deleterious effect was observed on uranium leaching performance and the technique should be quite compatible with all field operations. INTRODUCTION The recovery of uranium values from underground deposits by in situ leaching or solution mining has become economically viable and competitive with conventional open pit or underground mining/milling systems (Merrit, 1971). In situ leaching processes are particularly suitable for small, low-grade deposits located in deep formations and dispersed in many thin layers. Many such ore bodies occur along a broad band of the Gulf Coastal Plain (Eargle et. al., 1971). The advantages of the in situ leaching processes have been reviewed (Anderson and Ritchi, 1968). In the in situ leaching process, a lixiviant containing the leaching chemicals is injected into the subterranean deposit and solubilizes uranium as it traverses the ore body. The pregnant lixiviant or leachate is produced from the production well and is then treated to recover the uranium. The resulting barren solution is made up with the leaching chemical to form lixiviant for re-injection. Upon completion of the leaching operation, the formation is contaminated with leaching chemicals and other species made soluble in the leaching operation and has to be treated to reduce the concentration of these contaminants in the ground water to levels acceptable to the regulatory agencies (Witlington and Taylor, 1978). Restoration is accomplished by injecting a restoration fluid, which could be the fresh water or water containing chemicals, into the formation. As it traverses the leached formation, the restoration fluid picks up the contaminants and is then produced at the production well. This produced water is either disposed or purified for recycle. In both phases of operation, formation permeability or well injectivity is one of the most important parameters which determines the viability of the in situ leaching process. Low formation permeability limits production rates, leading to uneconomical operations. The formation is said to be sensitive if there is a sharp loss of permeability on contact with water and other fluids. Many uranium bearing formations, for example, the Catahoula formation of the Texas Coastal Plain, contain significant amounts of clay minerals which are water sensitive. Serious permeability losses can occur when the pH and chemical composition of the lixiviant is significantly different from that of the formation water. Jones has investigated the influence of chemical composition of water on clay blocking of permeability (Jones, 1964) and Mungan studied permeability reduction through changes in pH and salinity of the water (Mungan, 1965). Various mechanisms of permeability damage have been proposed and reviewed (Jones, 1964; Mungan, 1965; Gray and Rex, 1966; and Veley, 1969). When large amounts of swelling clays are present, a significant fraction of the flow channels in the formation can be reduced due to swelling. However, in most cases, swelling need not be the main cause of permeability losses. Particle dispersion and migration or clay sliming can be more important causes for formation damage. Clay particles entrained in the moving fluids are carried downstream until they lodge in pore constrictions. As a result, microscopic filter cakes are formed by these obstructions, plugging the pores, effectively restricting fluid flow and reducing the formation permeability. Moore found that as little as 1-4 percent clays present in a fine grained sandstone could completely plug the formation if they are contacted by incompatible injected fluids (Moore, 1960). It has been found that injection of NaHC03/Na2CO3 lixiviant into formations with significant clay content often leads to loss of formation permeability and well injectivity. To alleviate this problem a change of the lixiviant composition to KHC03/K2CO3 has been proposed. At present, however, many in situ leaching operations employ NH4HC03/(NH4)2C03 mixtures as a source of carbonates. This approach has been successfully used in South Texas by Mobil, Intercontinental Energy, Wyoming Minerals and U.S. Steel, etc. The use of ammonium carbonates solutions, however, contaminates the formation and requires a time-consuming restoration operation. The other approach to reduce the permeability loss is to pretreat the sensitive formation with chemicals which prevent clay dispersion and migration. Such chemicals include hydroxy-aluminum (Reed, 1972 and Coppel et. al., 1973), hydrolyzable zirconium salts (Peters and Stout, 1977), hydrolyzable metal ions in general (Veley, 1969) and polyelectrolyte polymers (Anonymous). Still another approach, is to minimize the "shock" caused by sudden injection by gradually changing the chemical composition of the injected fluids from that of the formation water. THE APPROACH Since permeability loss can be an important factor limiting the efficiency and economic viability of the in situ leaching process, a study was initiated on

Jan 1, 1982

By F. H. Froes, D. H. Warrington

Electron microscope evidence which indicates that TaC may precipitate at random sites in the matrix is presented. Initially the particles are almost spherical and coherent with the matrix. However, as they grow in conditions in which there are insufficient vacancies to relieve lattice strain, the particles rapidly lose coherency in two directions and continue to grow as plates with approximately the full lattice mismatch strain present perpendicular to the plane of the plate. The necessary relief of strain comes from dislocations loops which do not become visible until the later stages of aging. The rapid decrease of apparent strain to low values of appoximately 1 pct at small particle sizes arises not from a complete incoherency but from applying a model wrong for the particle shape and strain distribution. PREVIOUS work has shown that MC-type carbides may precipitate intragranularly in austenitic stainless steel on dislocations,1&apos;2 in association with stacking faults,3&apos;4 and randomly through the matrix,5-7 In investigations of the matrix precipitate by thin-foil electron microscopy, considerable lattice strain has been found to occur around the precipitating phase.7&apos;8 Attempts have been made to evaluate the amount of lattice strain by using the methods developed by Ashby and brown.9,10 Values of the linear strain, much less than the 17 pct theoretical mismatch (for TaC), have been reported; it has been suggested that this is due to either a loss of coherency1&apos; or vacancy absorption which occurs during either the initial nucleation or growth of the precipitate." This report is an extension of earlier work7 that dealt with the precipitation of TaC from an 18Cr/12Ni/ 2Ta/O.lC alloy after it had been quenched from 1300°C and aged between 600" and 840°C. In particular, the shape of the precipitate particles and the amount of strain in the matrix, due to the precipitate, have been studied. The work described here is part of a wider investigation of factors that affect carbide precipitation in austenitic stainless steel," details of which are to appear elsewhere. RESULTS The present investigation can be conveniently split into two aspects of the strain-fields surrounding the matrix particles: 1) information derived from the strain-field which indicates the shape and habit plane of the precipitate particles and 2) the magnitude and sign of the strain-field. The Shape and Habit Plane of the TaC Precipitate. In the early stages of aging twin lobes (normally black F. H. FROES, formerly at the University of Sheffield, Sheffield, England, is Staff Scientist, Colt Industries, Crucible Materials Research Center, Pittsburgh, Pa. D. H. WARRINGTON is Lecturer, Department of Metallurgy, University of Sheffield. Manuscript submitted November 1, 1968. IMD on white background, i.e., for the deviation parameter, S > 0) that indicate the strained region of the matrix define the position of the particles by bright field transmission electron microscopy. The actual particles were not detected until they were approximately 120Å diam; below this size they were too small to be imaged in the electron microscope. This meant that particle growth that had occurred before this stage had to be inferred from the matrix strain-field contrast. In all cases when diffraction effects were observed from the precipitate particles, a cube-cube orientation relationship (i.e., (llO)ppt Il<llO>matrix and {1ll }ppt {III} matrix) existed between the precipitate and the matrix. From the matrix precipitate particles lying along edge-on {111} planes (e.g., at A, Fig. I), the precipitates are seen to be plate-like with their diameter being roughly 18 times their thickness after 5000 hr at 650°C. However, the exact shape of the particles cannot be determined because of the masking effect of the strain-field contrast. If a dark-field micrograph, using a precipitate reflection, is studied, Fig. 2, a number of the projected images of the TaC particles [on the (110) foil surface] apear to have straight edges parallel to projected f111) planes. Thus, it appears that in the later stages of aging the TaC particles are plate-like with some tendency for the edges of the plate to be bounded by the matrix close-packed {ill} planes (though the general shape of the particles in the plane of the plate is circular and thus the "diameter" of the particles has a real physical significance). It should be noted that the bands of fine discrete particles observed in Figs. 1 and 2 are not the matrix precipitate discussed in this paper but are precipitates associated with extrinsic stacking faults3j4 occurring on (111) matrix planes. **£** ****** \ *x 23 Fig. 1—18/12/2~a/0.1~ alloy. Solution treated at 1300°C for 1 hr, water quenched, and aged 5000 hr at 650°C. The (112) directions shown are the traces of the e&e-on (111) planes. Foil normal [110]; operating reflection (331); bright field micrograph.

Jan 1, 1970