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By Stanford O. Grodd

The Sanford Lake district encompasses an area covering 24 square miles in the central Adirondack Mountains of northern New York State. Discovery of the titaniferous magnetite deposits dates back to 1826. Several attempts to exploit the ores for iron prior to 1942 proved uneconomical because of difficulties with the associated titanium, lack of transportation facilities, and the isolated location. Since 1942, the National Lead Company has produced ilmenite concentrates for the titanium pigment industry, and a magnetite by-product used in the steel and refractory industries. Rocks of the area are Precambrian in age and of igneous origin. The area has a history of erosion, deformation, and metamorphism, subsidence, and finally uplift and glaciation. The resulting topography is extremely rough with drainage patterns controlled by a combination of fault patterns and glacial modifications. The district is within the large anorthosite massif making up the central high peak area of the Adirondacks. All of the various lowsilica rock types associated with the massif are found within the boundaries of the district. These consist of both the Marcy and Whiteface types of anorthosite and of gabbroic anorthosite, gabbro, and different grades of titaniferous magnetite ores. All of the rocks contain the same minerals and differ only in their percentages of these consitituents. Gabbro, and ore associated with it, demonstrate flow structure as both have foliation and lineation. Anorthosite and its associated ores are massive and show very little primary structure. Minor pegmatites and diabase dikes provide evidence of remobilization in selected areas and of late intrusion as well. Faulting is prevalent and follows a regional pattern of major faults trending northeastsouthwest and of minor faults at nearly right angles to them. There are four mineralized areas where an economic grade of ore has been found. Three of these have both gabbroic-type ore and anorthositic-type ore. The fourth has only gabbroic ore. Ores are graded according to their TiO, content, and these range from 9.5 per cent to over 30.0 per cent TiO,. Ore bodies of both types are related to gabbro and conform to the configuration of the gabbro bodies within the anorthosite. At least three distinct theories of ore genesis have been expounded by different investigators. Others propose some variations of one or more of these. Although complete agreement probably never will be reached, it is certain that no one process of ore emplacement can explain the complicated picture as seen today. Further understanding of the ores and their origin will require detailed mapping, sampling, and mineralogical studies of the entire district, and then it may never be understood without qualification.

Jan 1, 1968

By S. E. Clay

In the chemical reaction control regime employed in the laboratory dissolution experiments, calcined trona ore dissolves in aqueous solutions according to a first order, irreversible reaction rate. The study showed that the reaction is first order with respect to solution NagCO3 concentration. The activation energy was determined to be 20.233 kJ/g. mol with a rate constant equal to 1235 mm/s (2917 in. per min). The dissolving particle may be described by shrinking particle behavior.

Jan 1, 1986

By Robert E. Green, Wolfgang Sachse

Simullaneous ultrasonic attenuation measurements of both quasishear waves propagating in single cryslals of aluminum indicate that, in the undeformed annealed state, the dislocation density is generally not uniform on all slip systems. Change oof attenuation measurements made during plastic defortnation of crystals , which possessed specific orientations ideal for studying the orientation dependence of dislocation damping, indicate that, for low strain levels, dislocation motion occurs on additional slip systems besides the primary one, even for crystals oriented for plastic deformation by single slip. THE sensitivity of internal friction measurements permits such measurements to be used successfully in studying the deformation characteristics of metal crystals. On the basis of experimental observations, T. A. Read1 was the first to associate internal friction losses with various dislocation mechanisms. Since that time further work2-' has been performed and a dislocation damping theory has been formulated by Granato and Lucke.6 In the amplitude independent region, this theory predicts the attenuation a to be dependent on an orientation factor O, a dislocation density A, and an average loop length L. if is a constant, independent of crystallographic orientation. For a given crystallographic orientation, changes in dislocation density and loop length give rise to the observed attenuation changes accompanying plastic deformation. The Granato-Liicke theory suggests the investigation of the orientation dependence of attenuation measurements in hopes of obtaining information to separate dislocation motion losses from other losses.7 An experimental study of the orientation dependence of attenuation in undeformed annealed single crystals should yield an insight into the uniformity of dislocation distribution throughout the entire specimen. A similar study on crystals plastically deformed in a prescribed fashion should give information about the alterations in the dislocation distribution on the slip systems activated during plastic deformation. The possible modes of elastic waves which can be propagated in aluminum,8 copper,9 zinc,10 and other hexagonal metals" have been calculated. Associated with each mode of wave propagation are dislocation damping orientation factors, which are based on the resolution of the stress field of that particular elastic wave onto the various operative slip systems in the material. These orientation factors have also been calculated as a function of crystallographic orientation in the papers cited above. Einspruch12 obtained agreement between predicted and observed attenuation values of longitudinal and shear waves in (100) and (110) directions of two undeformed aluminum crystal cubes. He ascribed the slight deviations between predicted and observed values to a nonuniform dislocation distribution, or to other loss mechanisms. In shear deformation of zinc crystals, Alers2 found that the attenuation of shear waves having their particle displacements in the slip plane was very sensitive to the deformation, while the longitudinal wave attenuation was affected only when the wave propagation direction was not normal to the slip plane. Using aluminum single crystals oriented for single slip, Hikata3 et al. found that during tensile deformation the change of attenuation of the shear wave (actually quasishear) having particle displacements nearly perpendicular to the primary slip direction exhibited the easy-glide phenomena, while longitudinal waves did not. Similar results were reported by Swanson and Green5 during compressive deformation of aluminum crystals. These results are in qualitative agreement with the calculated orientation factors for specimens of this orientation. In well-annealed, undeformed aluminum crystals, the damping is expected to be due to dislocations vibrating on all twelve slip systems. The orientation factors associated with this initial damping will be designated by O2 and O3, where a, represents the average orientation factor for the slow shear (or quasishear) wave and O3 represents the average orientation factor for the fast shear (or quasishear) wave. The calculation of these values for aluminum crystals by Hinton and Green8 shows that they vary very little as a function of crystallographic orientation—at most, by a factor of 2.47. If the dislocation density and loop length are uniform, then in the initial undeformed state, Here the subscript zero refers to the initial value of the attenuation. Also for aluminum, the calculations8 show that the orientation factors for primary slip only, associated with each shear wave, exhibit a sharp minimum for particular crystallographic orientations. A composite plot of the two shear wave orientation factors for primary slip only is shown in Fig. 1. Since these orientation factors are associated with dislocation motion occurring on the primary slip system only, the proper condition to check these factors might be attained by slightly deforming a single crystal oriented for primary slip. For dislocation motion on the primary slip system only,

Jan 1, 1969

By John Randall

It is a fair assumption that the main purpose of any diagram is to present facts to the eye in more convenient form than they could be tabulated in figures, and this implies that a screen diagram should set forth in a convenient and familiar form certain facts as to the character of the material screened regardless of the screen standards used, and it seems particularly desirable on account of the well-known differences in the size of openings of different laboratory screens having the same nominal mesh. In making screen-sizing tests it has been customary first to consider the largest size, going progressively to the smallest, and this seems to have led to the practice of placing the smallest size .at the right-hand side of the diagram and measuring toward the left. This is not altogether convenient and might be changed to advantage, but for illustration I have preserved that feature and present the method just as I have used it for over 2 years. Direct plotting in which the intervals on the diagram are proportional to the sizes of the openings, or to the arithmetical difference between them, seems at first sight more natural and is extremely useful for certain purposes, but it makes the diagram very crowded in the smaller screen sizes while the larger ones occupy unnecessary space, making it less convenient for most purposes, and for that reason the method here discussed is the well-known one based on the ratio between openings, and is plotted in logarithms instead of the direct values of the screen opening. Metric coordinate paper is convenient, although not necessary; it is recommended, as the use of the metric scale gives a diagram of convenient size, but any scale of equal parts may be used. In order to make any screen diagram translatable in terms of any standard screen size, it is necessary to have noted on the size scale of the diagram all points corresponding to the openings of the various screens in question, instead of a single series of points as with a single screen. In drawing the diagram assume 0.001 in. (corresponding approximately to 0.025 mm.) to be the smallest size to be considered and fix this as the zero point at the lower right-hand corner of the diagram. This value is selected because the values are to be plotted in logarithms, and the logarithm of 1 is zero. Then lay off to the left for the position of each screen

Jan 1, 1918

By J. H. Nelson

An outline survey of the economic outlook for the United States export trade in petroleum products resolves itself broadly into two general divisions; first, a consideration of our present position in this trade, and second, a discussion of the visible factors which promise to affect appreciable changes in the immediate future in that trade. The United States PetRoleum Exports of majoR Petroleum Products 1925, 1926 and 1927

Jan 1, 1928

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Unmodified disilicide coatirigs were applied to sheet-tensile specimens ofCb-Dg3 and Mo-TZM veJractovy- metal alloys. Coating thickness, degree of coating-substrate interdiffusion, and specimen geonzetry (notched and plain were included in the variables studied. Tensile tests were made to determine the ductile-lo-brittle transition temperature. The disilicide coating modestly increased the transition temperatlre of TZM, but had no effect on 043. Neither material condition (recrystallized or stress-velieved) nor specimen geometry (notched or unnotched) significantly altered the effects of coatings on the transilion temperatures of. the alloys. Cracks in the brittle coatings did not propagate into the substrate, and fracture modes appeared to be the same for both un-coated and coated specimens. MOST potential structural applications for refractory metals and alloys involve exposures to oxidizing environments at elevated temperatures. The general lack of oxidation resistance of these metals will require protective coatings to allow fulfillment of their potential. Currently preferred coatings for the oxidation protection of refractory metals are brittle intermetallic aluminides or silicides. These are typically formed on the surface of the refractory-metal substrate by a diffusion reaction between the substrate and a gaseous or liquid medium that is rich in aluminum or silicon. Because of the brittleness of these coatings, they will sustain no plastic deformation at low temperatures. They are frequently cracked by cooling from the coating temperature because of the thermal-expansion mismatch with the substrate alloy. Even if they survive cooling intact, they crack rather than sustain deformation under load at low temperatures. Thus, when a coated refractory metal is strained beyond the elastic limit of the coating at low temperatures, the mechanical environment of the substrate would include both static and dynamic cracks. These might be expected to influence the flow and fracture behavior of the substrate. This could be manifested in an altered fracture mode and/or an increase in the normal ductile-to-brittle transition temperature of the refractory-metal substrate. This paper presents the results of a research program that was conducted to determine the influence of the presence of a brittle surface coating on the low-strain-rate tensile behavior of typical refractory metals at low temperatures. EXPERIMENTAL PROCEDURES Material Preparation. Thirty-mil-thick sheets of molybdenum TZM alloy (Mo-0.5Ti-O.1Zr) and colum-bium D43 alloy (Cb-IOW-1Zr-O.1C) were obtained commercially. These alloys were selected as substrate materials representing two classes of materials important in current refractory-metal technology. The TZM was in the stress-relieved condition, and exhibited a heavily fibered grain structure. The D43 had been processed by the duPont "optimum" fabrication schedule,' and exhibited slightly elongated grains typical of this process. Tensile specimens of two geometries were prepared from these materials: 1) plain specimens with 0.2-in.-wide 1.0-in.-long gage sections; 2) specimens similar to above, but with a 0.06-in.-diam hole drilled in the center of the gage section, providing a stress concentration factor, Kt, of 2.5. The "notch" geometry was selected to represent a typical condition of a rivet hole or other geometric discontinuities as might be encountered in various applications. Machined specimens were degreased, with a final rinse in acetone, prior to the application of coatings. Specimens of each substrate and configuration were pack-siliconizedin a particulate mixture of 80 pct A1203, 17 pct Si, and 3 pct NaF. Specimens were embedded in this mix (contained in graphite retorts) and coated in an electrically heated argon-atmosphere furnace under time-temperature conditions to effect nominal 1- and 3-mil-thick silicide coatings: Coating Thickness, mils Thermal Treatment 0.6 to 1.4 24 hr at 982°C 2.4 to 3.2 48 hr at 1093°C Coating kinetics were similar for both the TZM and D43 substrates. These treatments had little or no visible effect on the substrate microstructure as determined by optical metallography. The coatings on TZM were essentially single-phase unmodified disilicides, while those on D43 showed substantial evidence of modification by proportionate reaction with the respective substrate elements or phases, as shown in Fig. 1. It was recognized that these coatings might not be particularly desirable regarding protective capability. However, it was desired to circumvent possible inter -ferring chemical interaction with the substrate by pack additives such as chromium, titanium, boron, aluminum, and other elements that typify the better protective coatings for these materials.' Thus, the results presented apply specifically to the simple silicide coatings investigated. They may not be rep-

Jan 1, 1967

By I. S. Servi, N. W. Marr

TIN markedly increases the softening temperature of pure copper with only a moderate effect on conductivity. Smart and smith' indicated a substantial increase in softening temperature upon addition of different levels of tin up to 0.05 pct in oxygen-free copper. However, after finding no effect of tin in copper containing about 0.025 pct O, they concluded that "the presence of oxygen completely nullifies these changes in properties by precipitation of SnO2.'' Since preliminary tests on Cu-Sn-0 alloys indicated that this conclusion is not valid outside the extremely limited tin range investigated by Smart and Smith, research was primarily directed toward the partition of tin between the copper-base matrix and the oxide phases. Experimental. Material was prepared by sealing an 80 to 100-g charge consisting of oxygen-free copper, tin, and copper oxide into a y-in.-ID quartz capsule which was evacuated and back-filled with tank-grade argon to 3 atm. The sealed vials were heated to 1125ºC, kept at temperature for 30 min, occasionally agitated, and then allowed to air-cool outside the furnace ("as-cast"). The castings were cold-swaged to 0.370 in., annealed 1 hr at 600°C ("as-annealed"), and cold-swaged 16.5 pct ("as-swaged"). Cross sectional wafers were annealed for 1 hr at various temperatures and Rockwell F hardness measured. The "softening temperature" was defined as the interpolated temperature at which the hardness was 50 Rockwell F. Electrical resistance was measured by an ac poten-tiometric method on 0.040-in.-diam wires after a 1 hr anneal at 600°C. Relative accuracy was of the order of 1 pct. Chemical analyses for tin were performed by two methods, identified as "Acid flux" and "HN03 dissolution". The first consisted of fusing the sample with potassium pyrosulfate and leaching the resulting melt with 10 pct sulfuric acid. The spectrophotometric procedure which followed is described in Ref. 2. Oxygen analyses were performed by the vacuum-fusion method with a bath temperature of 1650°C. Tin content of oxides and copper phases was measured with the X-ray microprobe, using a calibration curve based on a series of oxygen-free Cu-Sn alloys. Results. In Fig. 1, the nominal tin composition for alloys containing nominally 400 ppm O was plotted vs the analyzed or the computed tin content—the latter derived from one of the following: 1) "acid flux" chemical analysis; 2) "HN03 dissolution" chemical analysis; 3) X-ray microprobe analysis of the copper matrix; 4) equivalent tin content, based on the measured increase in electrical resistivity (an increase in resistivity of 1.6 microhm-cm is approximately equivalent to 1 wt pct of sn1,3). It is evident from Fig. 1 that the results of the acid flux analysis are consistent with the nominal composition while the HNO3 dissolution method generally yields lower values, consistent with those obtained from electrical resistivity measurements and somewhat higher than those obtained by microprobe analysis. Microprobe and resistivity values are affected only by the tin in solid solution; hence the HN03 method

Jan 1, 1970

By G. Carman Ridland

In conjunction with a geological investigation of the silver-bearing veins at Contact Lake, Northwest Territories, Canada, a survey was made with a Geiger-Miiller counter of the gamma-ray emissions from the rocks in the vicinity of the mine workings. Discontinuous pitchblende veins have been encountered occasionally in the silver-bearing fissures, and the geophysical survey was undertaken with the hope that abnormally high gamma-ray intensities, if detected, might lead to larger and more continuous pitchblende discoveries. Before the instrument was used at Contact Lake, preliminary tests were made, first with laboratory specimens at Princeton University, and later over known pitchblende deposits at the Eldorado property, LaBine Point, N.W.T. The Geiger-Müller counter, as adapted for field use, is described; the technique of transporting and operating the instrument is outlined; and the general precautions to be observed are discussed. The results obtained at Great Bear Lake show that the instrument is capable of detecting not only a pitchblende ore shoot in a shear zone, but also the mildly radioactive "host rock" at a considerable distance from the ore body. Hence, use of the Geiger-Müller counter is urged, not just for the detailed search for an ore body in a shear zone, but for the detection of possible radioactive "host rocks" in large-scale reconnaissance surveys of unexplored regions made by prospectors and members of federal geological survey parties. Location.—Along the rocky eastern shores of Great Bear Lake, in the Northwest Territories of Canada, lies one of the world's great radium-producing areas. The Eldorado mine, owned and operated by the Eldorado Gold Mines, Ltd., is at LaBine Point; while the Contact Lake mine, operated by Bear Exploration and Radium, Ltd. (B.E.A.R.), lies 9 miles to the southeast of LaBine Point and 2 miles south of Echo Bay, an indentation in the eastern shore line of Great Bear Lake. Geology.—The Eldorado company obtains its radium by the mining of the mineral pitchblende, which is found associated with a complex variety of metallic and nonmetallic minerals1 in quartz-carbonate veins occurring in metamorphosed pre-Cambrian sediment aries. Most of the pitchblende is intimately associated with a brown quartz and belongs to an early hydrothermal stage of mineralization during which safflorite-rammelsbergite and minor cobalt-nickel minerals were also deposited. Some pitchblende occurs with a group of minerals belonging to a later stage of mineralization in which the gangue is mainly dolomite and sometimes ferruginous rhodochrosite. Associated with this group are native silver and lead-zinc-copper sulphide minerals. The Contact Lake property owes its existence to the mining of rich, native silver ore shoots, which are

Jan 1, 1946

By G. Carman Ridland

In conjunction with a geological investigation of the silver-bearing veins at Contact Lake, Northwest Territories, Canada, a survey was made with a Geiger-Miiller counter of the gamma-ray emissions from the rocks in the vicinity of the mine workings. Discontinuous pitchblende veins have been encountered occasionally in the silver-bearing fissures, and the geophysical survey was undertaken with the hope that abnormally high gamma-ray intensities, if detected, might lead to larger and more continuous pitchblende discoveries. Before the instrument was used at Contact Lake, preliminary tests were made, first with laboratory specimens at Princeton University, and later over known pitchblende deposits at the Eldorado property, LaBine Point, N.W.T. The Geiger-Müller counter, as adapted for field use, is described; the technique of transporting and operating the instrument is outlined; and the general precautions to be observed are discussed. The results obtained at Great Bear Lake show that the instrument is capable of detecting not only a pitchblende ore shoot in a shear zone, but also the mildly radioactive "host rock" at a considerable distance from the ore body. Hence, use of the Geiger-Müller counter is urged, not just for the detailed search for an ore body in a shear zone, but for the detection of possible radioactive "host rocks" in large-scale reconnaissance surveys of unexplored regions made by prospectors and members of federal geological survey parties. Location.—Along the rocky eastern shores of Great Bear Lake, in the Northwest Territories of Canada, lies one of the world's great radium-producing areas. The Eldorado mine, owned and operated by the Eldorado Gold Mines, Ltd., is at LaBine Point; while the Contact Lake mine, operated by Bear Exploration and Radium, Ltd. (B.E.A.R.), lies 9 miles to the southeast of LaBine Point and 2 miles south of Echo Bay, an indentation in the eastern shore line of Great Bear Lake. Geology.—The Eldorado company obtains its radium by the mining of the mineral pitchblende, which is found associated with a complex variety of metallic and nonmetallic minerals1 in quartz-carbonate veins occurring in metamorphosed pre-Cambrian sediment aries. Most of the pitchblende is intimately associated with a brown quartz and belongs to an early hydrothermal stage of mineralization during which safflorite-rammelsbergite and minor cobalt-nickel minerals were also deposited. Some pitchblende occurs with a group of minerals belonging to a later stage of mineralization in which the gangue is mainly dolomite and sometimes ferruginous rhodochrosite. Associated with this group are native silver and lead-zinc-copper sulphide minerals. The Contact Lake property owes its existence to the mining of rich, native silver ore shoots, which are

Jan 1, 1946

By Welton Crook

UNLESS present in considerable proportion, metals of the precious-metal group-other than gold and silver-are not readily detected by the methods of fire assaying usually applied to ores and metallurgical products. Platinum, when present in small quantity, will ordinarily be reported as silver unless special methods of parting are used. Other elements occurring in the gold itself are all fluxed and slagged in the assay operation and if analyses are made on bullions the melting and slagging operations to which the bullion has been subjected may eliminate most of the associated elements. On the other hand, the analysis of precipi-tate from the cyanide treatment of gold ores may reveal the presence of many unexpected elements, such as tungsten and molybdenum. It is uncertain, however, whether many of the elements present in the pre-cipitate are derived from the ore gangue or from the gold itself. No very general survey of the distribution of metallic elements in gold seems to have been made. Rose and Newman,1 in connection with the composition of native gold, say in part as follows: Gold is occasionally found alloyed with copper and sometimes also with iron, bis-muth, lead, mercury, tin, antimony, palladium or rhodium. Rhodium gold from Mexico was found to be of the specific gravity 15.5 to 16.8 and contained 34 to 43 per cent of rhodium. The native alloy of palladium, gold, and silver from Porpez con-tains 85.98 per cent of gold, 9.85 per cent palladium and 4.17 per cent silver. Mal-donite, from Victoria, contains gold 64.5 per cent, bismuth 35.5 per cent (Louis). Dana' says that native gold is usually alloyed with silver in varying amounts, and that sometimes it also contains traces of copper and iron. Rare varieties contain palladium, rhodium and bismuth. Other authors, for instance Zeigler3 and Clark,4 give similar information. Most refer-ences on the subject agree that ordinary native golds contain, in common, the elements silver, copper and iron. After completion of the work of which this paper is a record, the conclusion is reached that all ordinary native gold probably does contain these elements and, although in certain cases other elements may be found to be present, that it is difficult to

Jan 1, 1939

By B. F. Buie

For over 200 years meerschaum has been a significant item of trade between the Near East and countries to the west. Best-known for its use in making smoking pipes and cigar and cigarette holders, it is also used in making a variety of decorative and ornamental items. It is easily carved, and is given an attractive, lustrous finish by rubbing. No published specifications are known, but compact form, purity, uniform whiteness or light color, and uniform, porous texture appear to be requisites. Fig. I a shows the appearance of a piece of crude meerschaum from Turkey; Fig. lb a carved item; and Fig. lc, d, and e show the fibrous and porous texture as revealed by the scanning electron microscope. Neither a major industrial mineral nor a precious stone, meerschaum nevertheless holds a record of long-and continuing-association with art and personal affairs of man. It is also a mineral to which modem methods of exploration and production probably could be profitably applied. An interesting account of the preparation and use of meerschaum in the early part of this century is given by Sterrett (1907). Geology and Mining Mineralogy Meerschaum is recognized now to be the compact variety of sepiolite, the claylike variety of which is one of the minerals included in the chapter on clays. The word meerschaum, from the German meaning "sea foam," was in earlier times used synonymously with sepiolite, a word of Greek origin suggestive of the resemblance of the compact variety-then the only variety known-to cuttlefish bone. At one time meerschaum was used as the commercial name, and sepiolite for the scientific name. However, to think of meerschaum as the name by which sepiolite is known commercially is no longer valid, in view of the recent emergence of the earthy variety as a competitor of bentonite and other clay materials. Present tendency is to restrict the term meerschaum to the compact variety, and to use the term sepiolite as a more general name to include both the compact and earthy varieties. This is the terminology followed in this publication. Meerschaum typically is white to light gray, has a hardness of 2 to 2 ½ , conchoidal to irregular fracture, and specific gravity varying with porosity from about 2 to less than 1. The composition is somewhat variable,- but is near that determined by Schaller (1936) for sepiolite as 2MgO.3SiO2.4H2O. A more modern for mula based on X-ray determination of the crystal structure is given by Caillére and Henin (1961) as (Site) (Mg9)030(OH)6(0H2)46H20. The reason for the firm, compact nature of meerschaum, in contrast with the earthy variety of sepiolite, is not fully understood. It may be due to the presence of a very minor amount of some bonding material such as silica. Scanning electron microscope (SEM) photographs of a specimen from Turkey (Figs. lc-le) indicate that the meerschaum is composed predominantly, if not entirely, of crystalline fibers which merge into sheetlike forms in a complex, intertwined mass. Detailed X-ray and crystal structure data, as well as some data on thermal stability range, are given by Caillère and Hénin (1961) for the sepiolite family of minerals. Mode of Occurrence and Origin Most authors have attributed the origin of meerschaum to alteration of serpentine or other magnesian minerals. The occurrence in alluvium and other surficial deposits does not necessarily indicate that the alteration was supergene. In fact, hydrothermal origin appears more likely for some deposits, though not for all.

Jan 1, 1983

By Robert Gillham, Victoria Yablonsky, Grover R. Castle

INTRODUCTION The commercial paper market, unique to the United States, is a direct exchange of funds between high-grade borrowers and large lenders; because it eliminates both the bank's role as middleman and also some significant transaction costs, commercial paper is the lowest cost short term instrument in the world. For this reason, virtually all borrowers would like to enter the market, but only issuers with the highest rating from Moody's and Standard & Poor can attract purchasers at the best rates. COMMERCIAL PAPER The commercial paper market, in existence for over 100 years, has traditionally been used for short-term financings, with most paper maturing within 30-45 days. Under the U. S. Securities Act of 1933, (section 3(a)3) industrial paper can avoid registration only if it matures within 270 days and is used for current transactions. It was first used to finance the short-term seasonal working capital needs of manufacturing companies. Since World War II, commercial paper use has grown steadily, serving in the 1950's as the market in which finance companies financed the explosion in consumer credit purchases of heavy consumer durables. LETTER OF CREDIT BACKING As far as is known, the use of letters of credit to support energy-related commercial paper began about 13 years ago with an arrangement to finance the nuclear fuel for Con Edison's Indian Point 3 Plant. Goldman, Sachs was the architect of this financing and Chemical Bank provided the letter of credit support. After an early burst of interest, this type of financing wobbled severely in the difficult credit markets of the mid-seventies before regaining serious momentum in 1976 and 1977. A mining project would not normally qualify as a borrower in the commercial paper market because of its credit standing and because its large capital needs require long term financing. However, lately, commercial paper has begun to take the place of a bank term loan in limited recourse project financings. L/C backed commercial paper took this new and startling turn in 1982 when it was used as part of the $700 million financing for the development of the Newlands-Collinsville coal mines of Mount Isa Mines Ltd. in Australia. This was the first use of L/C backed commercial paper in a long-term limited recourse project financing. First Boston acted as financial advisor and, again, Chemical Bank provided sole letter of credit support of $155 million. The $785 million BHP financing for the acquisition of the Queensland (Australia) coal assets of Utah International from General Electric Company followed the next year; there we acted with two other Front Banks to provide $270 million of L/C support. These two important transactions indicate that not only has commercial paper become an integral part of a long-term financing package, but also that it is no longer the exclusive domain of the best known U. S. companies. Lesser-rated companies and a multitude of foreign borrowers have gained access to this "exclusive club." How has this become possible? OPERATION OF AN L/C An instrument of the commercial banks, the "direct pay" letter of credit, has enabled lesser-rated companies to issue commercial paper in their own names. The letter of credit allows the issuer to substitute the credit rating of the supporting bank for its own. The L/C in effect allows a lesser-rated company to rent the bank's credit rating. This upgrading is possible because the bank is unconditionally obliged to pay the note-holders at maturity and then turn to the Issuer for reimbursement. The Issuer commonly "rolls over" a new short-term issue and reimburses the supporting bank from the sale of the new issue until cash flows from the project allow the borrower to reduce the level of paper outstanding. The commitment for an L/C facility, up to 12 years in the case of the Broken Hill transaction, governs the life of the commercial paper tranche of the financing. The term of the L/C commitment thus has the power to extend the ordinary 30-45

Jan 1, 1985

By M. Cohen, P. E. Beaubien, D. Caplan

Addition of 1 pct Mn to Fe-26 CY ca/(ses a12 increase in scaling rate at 870° and 1090°C. Whereas only the rhombohedral oxide, formrs on tire manganese-free alloy, with manganese present major amounts of the spinel .Mn0 . Pro-duced through which diffusion is more rapid. At 1090°C the scale formed OH Mn is highly, irregular due to blistering and sintering, This is a second cause of faster oxidation Since much of the blistered oxide does not participate as part of the protective layer. The oxide phases that form at different times depend on the degree to which the surface metal has become depleted, in manganese by preferential oxidation. PREVIOUS work has demonstrated that the oxide scales formed on chromium steels at high temperature consist of both spinel and rhombohedra1 phases and may contain considerably more manganese, especially in the spinel phase, than is present initially in the alloy.' It has further been observed that a binary Fe-26 Cr alloy scaled less rapidly than an equivalent commercial steel and formed no spinel.' However, it is not established if manganese in chromium alloys actually promotes formation of spinel nor if it affects oxidation resistance. It seemed expedient to try to evaluate the specific effect of manganese by oxidizing an Fe-26 Cr alloy containing a small manganese addition under the same experimental conditions as used for the manganese-free alloy.' EXPERIMENTAL Table I shows the composition in weight percent of the Fe-26 Cr-1 Mn alloy and of the Fe-26 Cr alloy used as reference. The alloy with manganese was prepared from the vacuum-melted Fe-26 Cr alloy by remelting in vacuum with the proper manganese addition. The ingot was rolled to strip and specimens 1.1 by 0.035 by 5 cm and 1.1 by 0.5 by 4 cm cut out or machined. As previously described2 the specimens were smoothed by abrading through 600-grit Sic paper, electropolished in acetic-perchloric acid (20 to 1) to remove 10 p of metal, annealed at 1100°C in 20 torr of purified argon, and electropolished to remove a further 10 p of metal. They were then either rinsed in water and methanol and blotted dry or immediately etched for 45 sec in deoxy-genated 4 N HC1 under cathodic polarization at 10 pa per sq cm. Oxidation runs were carried out in a vertical tube furnace in a flow of purified oxygen at 1 atm while the weight increase was recorded continuously on a* automatic balance.3 Alter 98 hr at 870.C or 20 hr at 1090"C the specimens were removed to flowing argon and observed microscopically for evidence of spalling as they cooled. Subsequently they were examined by X-ray diffraction, the oxides analyzed chemically, and metallographic cross settions prepared. RESULTS Figs. 1 and 2 show the oxidation curves of Fe-26 Cr-1 Mn at 870' and 1090C. The Fe-26 Cr reference runs are shown as dashed curves. Experimental details of the six runs are included in Table 11. The first 20 hr of run 1 is repeated in Fig. 2 to show the effect of temperature. At 8'70°C the weight gain for Fe-Cr-Mn is about twice that of Fe-Cr (curve 1 vs curve 2, Fig. 1). Both alloys show regular oxidation curves. On parabolic coordinates (right-hand scale of Fig. 1) the

Jan 1, 1965

By E. V. Kleber, V. F. Novy, R. C. Vickery

The constitutional diagram for the gadolinium-cobalt system has been determined. Seven intermetallic compounds have been found at compositions corresponding to the follwing gadolinium-cobalt ratios: 3:1, 1:1, 2:3, 1:2, 1:3, 1:4, 1:5. The GdCor compound has a congruent melting point above 1600°C. whereas the remaining compounds melt incongruently. Eutectics exist at 16 wt pct Co and 84 wt pct Co, with melting points of 620° and 1260°C, respectively. PREVIOUS papers'" have recorded constitutional data for systems of gadolinium with iron and nickel. This paper presents data obtained on alloys of gadolinium with the remaining 3d transition element-cobalt. voge13 found that cerium forms, with cobalt, the intermetallic compounds; Ce3Co, CeCo, CeCo2, CeCo3, CeCo4, and CeCo5 Other workers4-' found the 1:2 compound in this series to exist in a C-15 (face-centered cubic) structure and the 1:5 compound to exist in a hexagonal crystal system. Comparison of earlier data with that now reported will be made subsequently. EXPERIMENTAL Methods of alloy preparation, annealing procedures, and experimental techniques have been previously reported.' The cobalt content of alloy specimens was determined volumetrically. RESULTS Microstructure—The alloy containing 10.5 wt pct Co corresponds closely to the composition of the first intermetallic compound Gd3CO. In Fig. 1 the microstructure is essentially single phase composed of Gd3Co which formed peritectically. The globular areas are remnants of the peritectic reaction which did not quite go to completion. A eutectic occurs between Gd3Co and the next higher compound GdCO, which is followed by a series of peritectic compounds. Fig. 2, an arc-cast alloy containing 20.2 wt pct Co, shows large primary crystals of GdCo etching either white or black (depending on crystallographic orientation), embedded in the eutectic. Similarly, in Fig. 3 at 31.2 wt pct Co, a compound, probably GdCo3, has separated from the melt. Subsequent peritectic reactions were almost completely by-passed as the alloy cooled, the residual liquid freezing as a fine eutectic. In the 47.5 wt pct Co alloy, Fig. 4, the high melting point compound, GdCO4, has solidified as massive, white-etching grains, which reacted with the liquid to form GdCo3 as the second phase. The microstructure of an arc-melted alloy containing 60.5 pct Co is complex, Fig. 5, and presents some difficulty in interpretation. The grey etching matrix is probably primary GdCO4. The dappled phase represents grains of GdCO5 which have separated from the melt on cooling. The discrete spots in this phase are eutectic liquid. Small light etching crystallites are probably GdCO5 formed by the incomplete high-temperature peritectic reaction. GdCO4 is retained in arc-melted specimens containing 70.5 wt pct Co, Fig. 6. White areas of this compound are held in a matrix of GdCO5 the appearance of which is mottled slightly by inclusions of the second eutectic in this system. The development of the spheroidized eutectic at high cobalt contents is depicted in Fig. 7 (80.3 wt pct Co) in which the white massive crystals are GdCO5 compound. Further development of this eutectic is seen in Fig. 8, the primary white phase here being pure cobalt. Thermal Studies—Differential thermal analyses and melting point determinations have yielded the data shown in Fig. 10. The high gadolinium eutectic, indicated by microscopy, was confirmed at about 16 wt pct Co, melting at 620°C . A eutectic also occurs at about 84 wt pct Co melting at about 1260°C. The thermal arrests at 8803 960°, 1060; and 1210°C,

Jan 1, 1962

By Thomas Fraser, H. F. Yancey

The jig may be termed the standard coal-washing machine. Although exact figures on the relative tonnages of coal treated by the various coal-cleaning processes are not available, it is known that a large part of all the coal given special cleaning treatment is handled by jigs. This wide use of the jig warrants a special study of its performance. In this paper are presented the results of an analysis of work done by a three-compartment jig in treating bituminous coal from the Thick Freeport bed in Allegheny County, Pa. Certain systems of washing coal require sizing before washing, while others treat unsized coal. The prevailing practice, however, for the preparation of coking coal from the more easily washed coal is to treat an unsized or natural feed of about — 1 in. size and smaller. Under such conditions, the minimum size of particle that is beneficiated has long been and is still a matter of discussion and conjecture. In a careful laboratory investigation J?ngstl concluded that the practical limit of settling of fine coal is reached at from 0.02 to 0.008 in. On the other hand, Hancock2 has found that single-compartment jigs, used in preparing coal for the domestic market, usually allow most of the heavy (refuse) particles smaller than 1/4 in. to go into the washed coal. He also states that it is impossible with the ordinary coal jig to make any noticeable improvement in the quality of the coal finer than 20 mesh (about 1/30 in.). Because of its importance in coal cleaning, the work described in this paper was undertaken for the purpose of obtaining information on this subject, as a part of the general coal beneficiation program being carried out by the Bureau of Mines.

Jan 1, 1925

By D. Walton, W. C. Winegard, W. A. Tiller, J. W. Rutter

It is shown that the cellular substructure observed in binary alloy crystals grown from a melt of known concentration can be eliminated by the proper choice of growth conditions. For a given solute concentration, there exists a critical ratio of temperature gradient G in the melt to the rate of solidification R of the crystal, i.e., of G/R, which must be exceeded before the cellular structure can be eliminated. A secondary substructure is observed which is related to the cellular substructure. IN crystals grown from the melt, a prismatic substructure has been observed by Buerger,1 Pond and Kessler,2 and Rutter and Chalmers." This structure is columnar in the direction of growth and appears as a network of hexagonal cells in the plane of the solid-liquid interface. Rutter and Chalmers3 have shown that this substructure occurs as a result of the presence of a layer of high impurity concentration in the melt adjacent to the solid-liquid interface. The formation of the substructure is accompanied by a redistribution of this impurity in the neighborhood of the interface. The structure can be controlled by proper adjustment of the variables in the solidification process such as a rate of solidification and the temperature gradient in the liquid. The redistribution of solute during the solidification of metal crystals has been treated theoretically

Jan 1, 1956

By R. Sprycha, J. Szczypa, W. Janusz, J. Neczaj-Hruzewicz

INTRODUCTION Because large aqueous suspensions of various fine solids originate during the beneficiation of ores, the Mining Industry constantly requires efficient and feasible dewatering methods. Among the techniques currently in use (1,2), filtration (vacuum, press) and centrifugation are fairly expensive and thus are limited to use with more valuable materials. Furthermore, installations of reasonable size produce only moderate outputs. Therefore, tailings from ore dressing plants are usually treated by sedimentation or settling techniques with a tailings dam as the ultimate sedimentation basin (3). Apart from growing environmental and economic questions, the solid product obtained from the tailings dam basin has in most cases, a rather high moisture content and a persistent semi-fluid consistency. Thus, it is difficult to transport and use further. On the other hand, the solids may be utilized as a filling material, fertilizer, etc. providing they are dry enough and properly granulated. Demands for an improved technique are met to a great extent, by the technique presented in this paper. AGGLOMERATION OF FLOCCIJLATED SLIMES Origin and Qualitative Description of the Process Phenomena of consolidation and pellet formation in flocculated fines were first observed by Yusa and Gaudin (4) while studying rheological properties of flocculated kaolinite. On this basis, methods of separating liquid from solids have been worked out (5-7) and many possibilities for application have been suggested (5,6). Yusa termed the technique "wet pelletization''.

Jan 1, 1980

By A. E. Bibb, F. W. Kunz

A platelet form of zirconium hydride was found in zirconium and ZY-1 wt pct U single crystals containing hydvogen in the range of 50 to 100 ppm. The habit planes for the hydride plateletg in the zirconium crystals were found to be {1012}, {1121}, and (1122) while the habit planes in the ZY-1 wt pct U crystals were {1121), {1123}, and (1.231). With the exception of the {1231} plane, these have been identified as the twin planes in zirconium. The different effect of hydridc on the mechanical puoperlies of zirconium at high and low strain rates has been explained in terms of the defornzation mechanism and the habit planes of the hydride. ZIRCONIUM and zirconium-base alloys are considered for many nuclear reactor applications, where the pick-up of hydrogen is a distinct possibility, if not an unavoidable occurrence. An excellent example of this is the absorption of hydrogen by zirconium and its alloys during aqueous corrosion, where as much as 30 pct of the hydrogen produced by the corrosion reaction is picked up by the metal. Under the proper conditions, the absorbed hydrogen would precipitate as zirconium hydride and consequently alter the mechanical and physical properties of the zirconium-base alloys. The knowledge obtained from a study of the crystallographic aspects of the hydride precipitation is necessary for the interpretation of the observed changes in the mechanical and physical properties. The deleterious effect of hydrogen on zirconium-base materials is not always observed in normal slow tensile loadings at or above room temperature, but becomes immediately obvious under impact loading, where the energy absorbed decreases with increasing hydrogen content,' and in notched specimens where triaxial loadings are attained.2 This effect is of serious consequence in the applications of Zr where shock loads or high strain rates are experienced. The purpose of this investigation was to determine the crystallographic planes of the Zr and Zr-1 wt pct U matrices upon which zirconium hydride will precipitate and to correlate these with the observed mechanical property data. PROCEDURE Crystal Growth—Single crystals of Zr and Zr-1 wt pct U alloy were used in this investigation. The Zr crystals were made from sponge that had a typical analysis as shown in Table I. Large grains were grown in this material by rapid cooling an arc-melted charge in a button furnace. This operation undoubtedly lowered the volatile impurity concentration below those listed in Table I. Back-reflection Laue patterns of these large grains showed the presence of considerable substructure and lattice distortion within each grain. It was found that an 18-day anneal in an argon atmosphere at 840°C (a high a heat-treatment) followed by furnace cooling, resulted in the further growth of the large grains and removed the detectable substructure ana lattice distortion. Equiaxed crystals with a cube edge of approximately 1/4 in. were produced in this manner. Large crystals of Zircaloy-2 (1.5 wt pct Sn, 0.15 wt pct Fe, 0.1 wt pct Cr, 0.05 wt pct Ni) also were produced by this technique but the large amount of substructure formed could not be removed by annealing. The Zr-1 wt pct U solid solution crystals were produced from an alloy rod consisting of Westing-house-Foote hafnium-free crystal bar zirconium and depleted uranium. The chemical analysis of the alloy is also given in Table I. Three-inch sections were cut from an 0.120-in.-diameter alloy rod and tapered to a fine point on each end. The samples were sealed in evacuated Vycor tubes, homogenized for 5 hr at 1000°C in the ß-phase field, and slowly lowered in a gradient furnace into the a phase (800°C), annealed for 60 hr at this temperature to produce grain growth and furnace cooled. This technique produced large grains approximately 1/2 to 3/4 in. long over the entire cross section of the rod, which were free of observable substructure. Metallographic examination up to X1000 did not show the existence of any second phase in these grains. Crystal Orientation—All crystals were abraded on fine emery paper to produce two flat surfaces 90 deg to each other. The crystals were analyzed by the standard Back-Reflection Laue technique to obtain the crystal orientation with respect to the abraded surfaces. The Back-Reflection Laue Photograms of all crystals used were clear and sharp indicating that the crystals were free from any substructure that could be detected by these means. Hydriding—Only samples containing four to five grains were used for hydriding. Samples that exhibited fine grained patches were discarded. The samples were hydrided using the following technique. After etching in 48 vol. pct HNO3, 48 vol. pct H2O, and 4 vol. pct HF (48 pct) solution, the specimens

Jan 1, 1961

By A. S. Malicsi, I. Iwasaki

The removal of hydrophobic coatings of flotation collectors from iron ores becomes of interest when a duplex flotation process is considered for upgrading, when a pelletizing process is considered for a concentrate floated with a fatty acid or a soap collector, or when a disposal of froth products from cationic silica flotation is of environmental concern. Ozone can oxidize organic compounds rapidly, thereby removing the hydrophobic coatings of flotation collectors. Ozone is widely used for treating and purifying drinking water, waste water treatment, and for chemicals processing (Murphy and Orr, 1975; Rice et al., 1980). Its uses in metallurgical operations, however, are very sparse (Allegrini et al., 1970; Chernobrov and Rozinoyer, 1975; Ishii et al., 1970; Iwasaki and Malicsi, 1985; Matsubara et al., 1978). Yet, its high reactivity and the absence of potentially hazardous byproducts become of interest in destroying flotation reagents adsorbed on mineral surfaces or remaining in mill water for recycle or for discharge. Duplex Flotation A duplex flotation process, as applied to oxidized iron ores, would involve a fatty acid flotation of iron minerals followed by an amine flotation of the siliceous gangue from the rougher iron concentrate. Such a process has been used in the Florida phosphate fields. Fatty acid coatings cannot be removed as readily with a simple acid or alkali treatment from iron oxide surfaces as from Florida phosphates. A combination of reagents, such as lime and quebracho, lime and alkali phosphate, or sulfuric acid and oxalic acid, has therefore been proposed. In a previous article (Iwasaki et al., 1967) , the use of activated carbon was found to be effective in removing fatty acid coatings both in the duplex flotation and the pelletizing processes. The use of ozone offers another approach to the removal of fatty acid coatings from iron oxide surfaces. To investigate the possible application of the duplex flotation process, a specularite ore from Michigan analyzing 36.5% iron was used. A 600-g (1.3-1b) sample was ground in a laboratory rod mill together with 250 g/t (0.5 lb per st) of sodium silicate to -150 µm (-100 mesh). This was transferred to a Fagergren laboratory flotation cell, and deslimed four times at 20 µm (quartz equivalent). The deslimed pulp was transferred to a laboratory conditioner, diluted to 40% solids, and conditioned with 250 g/t (0.5 lb per st) of soda ash and 250 g/t (0.5 lb per st) of oleic acid. The conditioned pulp was then transferred back to the Fagergren cell, floated until barren of froth, and the rougher froth product was returned to the cell and cleaned. The results are presented in Table 1. The cleaner concentrate at this point analyzed 45.3% Fe. The cleaner concentrate coated with fatty acid was transferred to a 2-L (0.53-gal) beaker. While the pulp was agitated with a glass T-stirrer, ozone was bubbled into the agitated pulp for 15 minutes at a rate of 10 mg/min (0.00035 oz per min) ozone (250 g/t or 0.5 lb per st 03 feed). It was observed that the pulp ceased to froth after about 10 minutes. The amine flotation of siliceous gangue from the ozonated pulp was carried out first by conditioning with a dextrin, a commonly used starch depressant for iron oxides. This was followed by flotation with a stage addition of an ether amine at increments of 100 g/t (0.2 lb per st). Three stages were required to float the siliceous gangue to near completion. The three froth products were combined and cleaned twice. When the cationic flotation Rougher, Cleaner 1 and Cleaner 2 cell products were combined, an iron concentrate analyzing 64.5% iron was obtained at an overall iron recovery of 72.8%. Pelletizing Fatty acid flotation concentrates have been pelletized successfully in northern Michigan mills. But at other locations, fatty acid coatings on iron flotation concentrates proved so undesirable in agglomeration that other methods of concentration had to be sought. For example, a sinter mix containing iron ore concentrates upgraded by fatty acid flotation resulted in decreased productivity. This occurred because the micropellets of particles with the hydrophobic coating are less tolerant of moisture. Thus, the bed permeability is lost (Beebe, 1965). The agglomeration of concentrates obtained by the fatty acid flotation alone, and the hydrophobic coatings destroyed by ozonation or by the duplex flotation process, is not expected to cause any difficulty since the surfaces of the concentrates would be hydrophilic. Removal of the fatty acid coating with activated carbon, indicated by the loss of floatability, was shown to restore the decrepitation temperature of wet balls during drying cycle (Iwasaki et al., 1967). Disposal of Cationic Silica Flotation Froths Recent demands of iron blast furnaces place the silica content of the magnetic taconite pellets at about 5%. Conventional process for magnetic taconite involving fine grinding and magnetic separation often produces magnetic concentrates analyzing in excess of 5% silica. This is due to the presence of the middling grains of siliceous gangue and magnetite. Cationic silica flotation of magnetic taconite concentrates (DeVaney, 1949) may be used to reduce the silica content. But the amine coating on siliceous gangue becomes of environmental concern when the flotation tailings are discarded in tailing ponds.

Jan 1, 1986

PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. PAST' PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F..RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY K. KENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y

Jan 6, 1914