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By R. Philip Hammond

Monazite has had a Cinderella-like history. Although nearly go per cent pure rare-earth compound (rare-earth phosphate) it was sought at first not for the rare earths but for the sake of a minor constituent—thorium. The thorium, essential for the Welsbach gaslight mantle, was present in only small quantities and the principal constituents, the rare earths, were largely discarded. Gradually, however, the rare earths have developed uses of their own and today have left the thorium far behind in value. Occurrence Monazite was first produced commercially about 1886, in North Carolina, where it was collected in small sluices by farmers who found it in stream beds on their land. The deposits were later exploited on a larger scale, but were mostly abandoned in a few years, when monazite from Brazil came upon the market in far larger quantities. Domestic production ceased entirely in 1906. The Brazilian source is still active, together with Indian, Dutch East Indies, and Australian deposits. Several other localities in the United States have yielded monazite, but none of these has produced commercially as yet. Monazite occurs originally in pegmatite~ and gneisses, through which, unfortunately, it is scattered in highly dispersed form. All commercially useful deposits consist of transported monazite sands liberated by erosion and concentrated by the action of water, which has sluiced away lighter materials and concentrated the heavy (D = 5.0 to 5.2) grains of monazite, together with ilmenite, zircon, garnet, and other dense minerals. The Carolina deposits were in stream beds; most of the other deposits mentioned are on or near the seashore, where the action of the waves has served to concentrate the monazite. In most cases today, the sands are worked to obtain the ilmenite and zircon, as well as monazite. The minerals are separated by means of sluices, dry tables, and magnetic separators, and each is finally obtained nearly pure. No crushing or grinding is necessary. The concentrates are shipped in fiber bags. Composition of Monazite As Table I illustrates, monazite is the anhydrous orthophosphate of the cerium Table i.—Typical Analysis of a Monazite Sand (India). Per Cent Thorium oxide............................. 8.1 Cerium oxide.............................. 30.6 Lanthanum oxide........................... 15. 7 Neodymium oxide.......................... 10.5 Praseodymium oxide........................ 2. 9 Samarium oxide............................ 1.0 Europium. gadolinium, and terbium oxides.... 0.7 Yttrium oxide.............................. 0.4 Dysprosium, holmium, erbium. thulium, ytterbium. and lutecium oxides................. 0. 1 Silicon oxide............t................... 2.4 Calcium, aluminum, and iron oxides.......... 1.0 Uranium oxide............................. 0.3 Phosphorus pentoxide....................... 26. 2 a The values given for the rare earths following samarium are approximate. being based upon analyses of concentrated fractions derived from monazite. The composition given represents Travancore monazite carefully freed from other minerals. goup of rare-earth elements. A small amount of yttrium and terbium group phosphate is also present.* All the rare-

Jan 1, 1948

By Lester Guttman

The connection between short-range order and thermodynamic activities in binary solid solutions has been pointed out by Birchenall1 who calculated approximate values of the energy of interaction of Zn and Cu and of the degree of short-range order in alpha-brass at one composition and two temperatures. The purpose of this note is to call attention to a somewhat more accurate theory than that used by Birchenall and to extend the calculations to a wider range of temperatures and compositions as a means of testing its applicability. This is an example of the well-known general method of comparing measured thermodynamic functions of a system with those calculated from a microscopic model by means of statistical mechanics. In this case, mathematical approximations must be used which make difficult any decision about the validity of the model. Birchenall's statistical method resembles closely that calletl by Fowler and Guggenheim2 the "quasi-chemical" method which has been shown to lead in certain cases to results identical with those obtained by the method of Bethe.3 The quasi-chemical method has been extended by Takagi4 to give general formulas for the free energy of binary solid solutions based on several lattices at all compositions and temperatures. Specifically, he treats the four systems typified by: I. ß—brass; 2. a— brass; 3. AuCus; 4. AuCu. When the temperature is so high that no long-range order exists, these formulas reduce to the same form for all lattice types, namely: F - FO = (E - EO) - T(S - S°) = ½N(c — x)(2vAB — vAa - Vbb) + M1/2KTzN[x log x + 2(c - x) log (c - X) + (I - 26 + X) log (1 - 2c + x)] -kT(z - I)N[c log c+(I-c) log (I -c)] Eq 1 Here the symbols have the following meanings: F—Helmholtz free energy E—nergy 5—ntropy k—the gas constant per molecule z—coordination number, (e.g. I2 in a-brass). N—total number of atoms c—atomic fraction of A Vaa, vbb, vab—nergy per bond of the corresponding bonds log means log, throughout The superscript ° denotes the thermodynamic fuliction in the standard state, which has been chosen to be pure A or B with the same crystal structure as the solid solution. The quantity x is the ratio of the number of A-A bonds to the total number and for minimum F satisfies the equilibrium condition Vaa + Vbb — 2Vab _ (c — x)2 kT l0g x(i - 2C + x The free energy may also be written in terms of /La and B, the chemical potentials or partial free energies per alom:

Jan 1, 1949

By Lester Guttman

The connection between short-range order and thermodynamic activities in binary solid solutions has been pointed out by Birchenall1 who calculated approximate values of the energy of interaction of Zn and Cu and of the degree of short-range order in alpha-brass at one composition and two temperatures. The purpose of this note is to call attention to a somewhat more accurate theory than that used by Birchenall and to extend the calculations to a wider range of temperatures and compositions as a means of testing its applicability. This is an example of the well-known general method of comparing measured thermodynamic functions of a system with those calculated from a microscopic model by means of statistical mechanics. In this case, mathematical approximations must be used which make difficult any decision about the validity of the model. Birchenall's statistical method resembles closely that calletl by Fowler and Guggenheim2 the "quasi-chemical" method which has been shown to lead in certain cases to results identical with those obtained by the method of Bethe.3 The quasi-chemical method has been extended by Takagi4 to give general formulas for the free energy of binary solid solutions based on several lattices at all compositions and temperatures. Specifically, he treats the four systems typified by: I. ß—brass; 2. a— brass; 3. AuCus; 4. AuCu. When the temperature is so high that no long-range order exists, these formulas reduce to the same form for all lattice types, namely: F - FO = (E - EO) - T(S - S°) = ½N(c — x)(2vAB — vAa - Vbb) + M1/2KTzN[x log x + 2(c - x) log (c - X) + (I - 26 + X) log (1 - 2c + x)] -kT(z - I)N[c log c+(I-c) log (I -c)] Eq 1 Here the symbols have the following meanings: F—Helmholtz free energy E—nergy 5—ntropy k—the gas constant per molecule z—coordination number, (e.g. I2 in a-brass). N—total number of atoms c—atomic fraction of A Vaa, vbb, vab—nergy per bond of the corresponding bonds log means log, throughout The superscript ° denotes the thermodynamic fuliction in the standard state, which has been chosen to be pure A or B with the same crystal structure as the solid solution. The quantity x is the ratio of the number of A-A bonds to the total number and for minimum F satisfies the equilibrium condition Vaa + Vbb — 2Vab _ (c — x)2 kT l0g x(i - 2C + x The free energy may also be written in terms of /La and B, the chemical potentials or partial free energies per alom:

Jan 1, 1949

By J. V. Gluck

In the present paper," as in earlier publications, V1'2"1 the authors present experimentally obtained relations for the free energy of solution of oxygen in various metals as a function of temperature. The relations are linear and given in slope-intercept form. The authors give values for the "probable error" of the slope and intercept, citing Birge's method17 for obtaining these quantities. Birge discussed these methods as early as the period 1929-32.25726 In Ref. 25 the probable error is defined as "the numerical value which the true error is as likely to exceed as not", i.e., 50 pct probability. Ref. 26 is even more detailed and includes a lengthy discussion of the applicability of the Gaussian distribution to experimental data. However, the use of the "probable error" has come under some question. For example, Ezekiel'~ states that "the use of the probable error tends to make the results appear rather more accurate than the standard error". Moroney28 stated (in 1951) that "the term 'probable error' was used in former times to denote 0.67450 (50 pct confidence using the normal distribution)....the term, a poor one, is now very much obsolescent. It has been said that 'it is neither an error nor probable' ". Bennett and Franklin in 1954" in discussing statistical confidence levels mentioned that "the customary use of the 5 and 1 pct levels is not completely a matter of chance; these levels probably represent a balance between the desire to be correct and the desire to be specific. Also in most people's minds the borderline between something that could possibly happen and something that is not likely to happen is somewhere in this region. Certainly 5 or 1 pct confidence limits are to be preferred to limits such as the 'probable error' which has only a 50/50 chance of including the correct value." It may readily be seen that the 95 pct confidence level, which is given by 1.960 (assuming large sample size), thus corresponds to approximately three times the "probable error". Indeed, limits of one standard deviation correspond only to about 68 pct probability. Even if we triple the tolerances given by the authors in the equations of their Table 111, the deviations do not become excessive and would not detract from their excellent results. It could then be said with a high degree of confidence (95%) that the precision of the slope and intercept values is about *3-5 percent of their absolute levels rather than the 1-2 percent implied in Table 111. This is then compatible with an earlier suggestion of Gokcen~' of a probable accuracy of 5 pct in dissolved oxygen measurements by the technique employed. Alternatively, the authors could have

Jan 1, 1967

Prospectors were digging silver in the Ray mine area in 1873, and by 1880 high-grade copper ore was feeding a 30-ton copper furnace. In 1910, D. C. Jackling and his associates organized the Ray Consolidated Copper Company, known in mining circles as Ray Con, to exploit the Ray orebody. For 50 years, all mining was underground and the Ray mine was known the world over for innovations in mining methods. It was the first to mine important tonnage (8,000 tpd) by block caving methods. The mill at Hayden, 26 miles (41.6 km) from the mine, kept pace with the new mining methods developed at Ray and in the early 1920's flotation replaced gravity concentration by the vanner machines. First mining by open pit methods began in 1950 and in January 1955 all underground mining was discontinued. The new primary crushing plant, installed in early 1967, featured design simplicity with a low capital cost. The 54 in. gyratory crusher was installed within a total height of 6 1 ft (18.65 m) from the truck dump road bed to the floor beneath the feeder-conveyor under the surge pocket. The crusher is fed by 120-ton trucks dumping from one side only into a 200-ton hopper equipped with a horizontal splitter bar to protect the crusher spider. The crushed ore pocket, of 120 -ton live capacity underneath the crusher, discharges to a 0 to 200 fpm (61.2 mpm), variable-speed, 72 in. by 80 ft long (1.83 m by 24.4 m) sloped belt feeder, probably a first in the industry. Wood-picking stations are provided on either side of the belt so that old mine timbers and tramp iron can be removed from the crushed ore and the wood can be dropped into Dempster containers located below the belt. Counter-weighted finger gates control the bed depth on the belt at 14 in. (356 mm) and a low- level radiation unit automatically maintains a minimum of a 3 ft bed (900 mm) of material on the belt directly under the surge pocket. The conveyor is skirted for its full length and is approximately 60 in. (1.52 m) wide inside its metal skirt liners. Ten impact idlers at 12 in. (305 mm) spacing are provided under the loading pocket and remaining idlers are spaced at 18 in. (457 mm). The belt is 1 ¼ in. (31. 8 mm) thick; and, while it has occasionally been damaged by tramp material, belt life averages 11 million tons. When the belt is changed, the coiled new belt is lowered into position onto one of two belt stands mounted over the feeder, the old belt is cut, and one end is attached temporarily to the new belt. The other end of

Jan 1, 1978

By C. S. Barrett, D. F. Clifton

THE transformation that occurs in lithium and its solid solutions containing magnesium1,2 is similar in many respects to other diffusionless transformations of the martensitic type. This general similarity makes it desirable to investigate the transformation curves in detail. The current interest in the phenomenon of stabilization in martensitic transformations has created a need for a careful appraisal of possible stabilization effects in both cooling and heating transformations in lithium alloys. The effect of prior heat treatment on the temperature at which transformation begins and the effect of various temperature cycles in partially transformed alloys also merit attention. Limited data on some of these features were presented previously,' but the present studies have been made with improved apparatus, in which erratic fluctuations were smaller than in the earlier work, and include many independent determinations of certain critical observations. Material and Methods Geiger counter X-ray spectrometers were used: a Norelco instrument, original model, and a General Electric XRD-3. The low-temperature specimen holder has been described elsewhere." Specimens 10 mm in diam and 1.5 mm thick were held in firm contact with a copper block which was attached to the lower end of a stainless steel tube that extended up to a reservoir of liquid nitrogen. A heating coil on the tube permitted a controlled temperature gradient along the tube, so that desired temperatures and rates of heating and cooling could be obtained by controlling the heating current. The specimen was surrounded by an atmosphere of evaporated nitrogen in an insulated chamber having double cellophane windows. The temperature of the specimen was read by a thermocouple imbedded in it close to the irradiated area; the specimen could be held at constant temperature within 1°C for long periods. The body-centered cubic 200 reflection near 8 = 26" was used as the index of the amount of b.c.c. material present; occasional checks were made using the most suitable line of the low-temperature phase, the close-packed hexagonal 110 line near 8 = 29". Copper radiation was used throughout. A continuous record was made of the reflected intensities on a strip chart recorder, both when the peak intensity of a line was being followed and when the lines were being scanned at constant temperature. On the continuous recordings of peak intensity, periodic checks were made on the background intensity between the lines, and on the setting of the spectrometer for maximum intensity. The lithium-base solid solution containing 12.4 atomic pct Mg (33.3 wt pct) that had been used previously' was chosen, as it had a transformation range at relatively high temperatures, so as to permit wide temperature cycling within the range. Just prior to use a pellet was cut from the ingot,

Jan 1, 1951

By J. F. Haseman, J. E. Davenport

IN the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1-2 results in inadequate beneficiation. INVESTIGATION OF FLOTATION METHODS Flotation has been used in Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate.3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over-all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P205 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P205, 20; Si02, 40; CaO, 29; Fe203, 2; A1203, 3; F, 2.3. The particle-

Jan 1, 1947

By J. G. Giddings, R. Kobayashi

Residual viscosity, the ViSCOSitY at a given pressure and temperature minus the dilute gas viscosity at the same temperature, has been found to be independent of temperature for pure components and mixtures for simple molecules and light hydrocarbons. The residual viscosities for methane, ethane, propane and four mixtures were correlated as a function of reduced density and molecular weight. INTRODUCTION Earlier efforts in correlating the viscosity of light hydrocarbons and associated gases under pressure, primarily by some form of the corresponding states principle, have been reported elsewhere.7 The formal theory of corresponding states principle for viscosity from non-equilibrium statistical mechanical arguments for simple molecules has been developed by Helfand and Rice.13 The most serious obstacle to the development of a generalized corresponding states representation of viscosity data, even for simple molecules, has been the limited quantity of precise viscosity data of pure components and mixtures over a wide range of pressure and temperature conditions. Viscosity data on light hydrocarbons have recently been contributed by several laboratories.2,6,8,23,25,26 In the study of the viscosity of nitrogen, Michels and Gibson" observed that the viscosities of nitrogen as a function of density gave parallel isotherms. The same behavior has since been reported for other gases.".= The observed behavior indicates that the residual viscosity or the viscosity at a given pressure and temperature minus the dilute gas viscosity at the same temperature is a unique function of the density. Abas-Zade,1 Michels and Botzen,18 and Michels, Bot-Zen, Friedman and Sengers,19 observed similar behavior for thermal conductivity, the residual thermal conductivity being defined in a manner parallel to that of residual viscosity. Thodos and co-workers 4,15,24 applied the residual viscosity concept to the viscosity of pure monatomic and diatomic gases. Ellington and co-workers10,25 made the residual viscosity vs density plots for ethane and propane, but omitted the region below a residual viscosity of 15 micropoise and showed a systematic separation of the ethane isotherms in the low density region. Eakin correlated the residual viscosity of methane, ethane, propane and n-butane empirically as a function of density and molecular weight: Carmichael and Sage6 recently presented ethane residual viscosity vs density values in the gaseous liquid, and near critical regions as a single univariant function of density. Flynn, Hanks, Lemaire and ROSS" have contributed extremely accurate viscosity data to confirm that the residual viscosity concept is essentially correct, but may not be accurate within 0.1 per cent of the viscosity value for the gaseous state- The recent studies by Giddings12 indicate that the residual viscosity of methane, propane and each of four methane-propane mixtures are unique functions of density Over the temperature and the density ranges studied.

Jan 1, 1965

By R. Philip Hammond

Monazite has had a Cinderella-like history. Although nearly go per cent pure rare-earth compound (rare-earth phosphate) it was sought at first not for the rare earths but for the sake of a minor constituent—thorium. The thorium, essential for the Welsbach gaslight mantle, was present in only small quantities and the principal constituents, the rare earths, were largely discarded. Gradually, however, the rare earths have developed uses of their own and today have left the thorium far behind in value. Occurrence Monazite was first produced commercially about 1886, in North Carolina, where it was collected in small sluices by farmers who found it in stream beds on their land. The deposits were later exploited on a larger scale, but were mostly abandoned in a few years, when monazite from Brazil came upon the market in far larger quantities. Domestic production ceased entirely in 1906. The Brazilian source is still active, together with Indian, Dutch East Indies, and Australian deposits. Several other localities in the United States have yielded monazite, but none of these has produced commercially as yet. Monazite occurs originally in pegmatite~ and gneisses, through which, unfortunately, it is scattered in highly dispersed form. All commercially useful deposits consist of transported monazite sands liberated by erosion and concentrated by the action of water, which has sluiced away lighter materials and concentrated the heavy (D = 5.0 to 5.2) grains of monazite, together with ilmenite, zircon, garnet, and other dense minerals. The Carolina deposits were in stream beds; most of the other deposits mentioned are on or near the seashore, where the action of the waves has served to concentrate the monazite. In most cases today, the sands are worked to obtain the ilmenite and zircon, as well as monazite. The minerals are separated by means of sluices, dry tables, and magnetic separators, and each is finally obtained nearly pure. No crushing or grinding is necessary. The concentrates are shipped in fiber bags. Composition of Monazite As Table I illustrates, monazite is the anhydrous orthophosphate of the cerium Table i.—Typical Analysis of a Monazite Sand (India). Per Cent Thorium oxide............................. 8.1 Cerium oxide.............................. 30.6 Lanthanum oxide........................... 15. 7 Neodymium oxide.......................... 10.5 Praseodymium oxide........................ 2. 9 Samarium oxide............................ 1.0 Europium. gadolinium, and terbium oxides.... 0.7 Yttrium oxide.............................. 0.4 Dysprosium, holmium, erbium. thulium, ytterbium. and lutecium oxides................. 0. 1 Silicon oxide............t................... 2.4 Calcium, aluminum, and iron oxides.......... 1.0 Uranium oxide............................. 0.3 Phosphorus pentoxide....................... 26. 2 a The values given for the rare earths following samarium are approximate. being based upon analyses of concentrated fractions derived from monazite. The composition given represents Travancore monazite carefully freed from other minerals. goup of rare-earth elements. A small amount of yttrium and terbium group phosphate is also present.* All the rare-

Jan 1, 1948

By Kenneth S. Johnson

Oklahoma is the only; state in the nation that is currently producing iodine. The iodine is extracted from iodine-rich natural brines being pumped from deep wells drilled into Pennsylvanian sandstones in the Anadarko basin of northwestern Oklahoma. Woodward Iodine Corp., started in 1977, was the first plant in the United States built for iodine recovery since the 1930s. At present, three companies are operating four iodine-producing facilities in northwestern Oklahoma. The combined production of these facilities, 1,321,000 kg in 1997, is about 26% of the U.S. annual consumption. Iodine is present in concentrations ranging from less than 100 ppm (parts per million) to as much as 1,560 ppm in brines in various Paleozoic strata in the subsurface of northwestern Oklahoma; these concentrations are exceptionally high, and are well above those of any other known brines in the world. Strata with the highest iodine content in the area (Mississippian limestones) have low permeabilities, and thus would yield only small amounts of brine. On the other hand, the lower Morrow sandstones (Lower Pennsylvanian) have a relatively high permeability and are capable of yielding large quantities of brine that average 300-350 ppm iodine. The Morrow brine reservoir was deposited in shallow-water-marine and intertidal-shelf environments and now is buried 6,000-10,000 ft below the land surface. Production is localized to Morrow channel deposits confined to an Early Pennsylvanian paleovalley that is 1-2 mi wide, is about 70 mi long, and is referred to informally as the "Woodward trench." All three companies are producing iodine-rich brines from Morrow sandstones in three different parts of the Woodward paleovalley, and one of the companies also is extracting iodine from oil-field brines coming from several petroleum reservoirs near Dover, about 80 mi east of Woodward. The basic extraction method employed by Woodward Iodine Corp. was used in Louisiana and California operations in the late 1920s. This method is commonly called the air-stripping process. Lower Morrow brine containing dissolved sodium iodide is pumped to the plant through a series of pipelines, where by-product natural gas is separated and processed. The brine is then acidified and subsequently oxidized with chlorine to convert the iodide to iodine. The iodine is air stripped and reabsorbed with sulfur dioxide and water, converting it to hydriodic acid, or process liquor. The process liquor is then processed, using chlorine once again, to crystallize the iodine as a solid. This is then melted and frozen to form a solid product, which is packaged in 110-lb (50-kg) drums and shipped to end users throughout the world.

Jan 1, 1999

By D. W. McGlashan, K. N. Mcleod

IN the use of free bubbles with precise temperature control and continuous pH measurement, the contact angle apparatus differs from all previous equipment. Experimental procedures differ sharply from the captive bubble method1,2 of introducing the gaseous phase in the three-phase system. When freed from the tube and captured by a solid surface, a bubble more closely conforms to the spherical ideal set up by the usual mathematical analysis of surface free energy or surface tensional relationships of the forces involved. The assembled equipment, Fig. 1, departs from the usual contact angle apparatus in providing: 1) water circulation for fixing temperature, 2) instruments to measure and record pH during testing, and 3) a system for producing and using free bubbles. The apparatus allows testing over a broad range of closely controlled conditions, and the use of free bubbles gives contact angles independent of operator manipulation, which was unavoidable in the older captive bubble method. A bubble released below the specimen rises through the liquid and contacts the mineral. If the mineral is gas-avid the bubble adheres, developing a finite contact angle. Reaction cells (1), 2x33/8x5 3/16 in. ID, are of pyrex glass 5 mm thick. To prevent optical distortion, the sides are optical flats and are planed parallel to within five wave lengths of light over the entire surface. Special cement is required to withstand chemical attack and thermal shock. The cell is placed in a thermal jacket (2) made of welded aluminum. A water seal for the optical ports is made by using O-rings tightened against the flats of the cell by fine-threaded and adjustable ports, Fig. 2. In-flow water is discharged downward from a manifold located near the bottom of the cell jacket. Water overflows the weirs at each end of the cell jacket, discharging from both sides to a collecting manifold (24). A hose (26) leads the overflow water to the thermal-conditioner well (4), which is recessed to accommodate a reaction cell and two beakers (150 ml). Both the thermal jacket and the thermal-conditioner well are insulated to minimize the effects of temperature differentials. Water, discharging from the thermal-conditioner well, returns to a thermostat bath and pump (3), from which it is pumped to the thermal jacket. The thermostat bath permits temperatures to be adjusted from 1" or 2°C to 80°C and will maintain the selected temperature within 0.2ºC. An electrode support (22) groups the four electrodes (8) so that they fit conveniently into the reaction cell, Fig. 2. This assembly holds the glass electrode, the calomel electrode, the temperature-

Jan 1, 1957

By Harry C. Gatos, Frank J. Bachner, Mario D. Banus

The portion of the Nb-Sn phase diagram between 75 and 79 at. pct Nb at temperatures near the liquidus has been investigated by melting alloys of known composition and examining the microstmc-tzlres resulting when these melts were quenched. The Nb-Sn samples were contained in magnesia sleeves, and were mounted in a high-pressure apparatus. It was shown that Nb3Sn me1ts by a peri-tectic decomposition and that the composition of the compound Nb3Sn at the peritectic horizontal lies between 77 and 78 at. pct Nb. Analysis of the phases present in the samples was accomplished by anodic staining techniques and an electron-microbeam analyzer. DURING the past several years a great deal of work has been devoted to the Nb-Sn system, and the bulk of this work has been primarily concerned with the intermetallic phase Nb3Sn. However, the melting characteristics of Nb3Sn have not been investigated because of the difficulty in maintaining known compositions due to tin losses by vaporization, and the added difficulty of containing Nb-Sn alloys without sample-container reaction at the high temperatures involved. This paper reports on the development of a technique for containing Nb-Sn alloys under pressure high enough to prevent tin losses at temperatures in excess of the liquidus. Using this technique, melts of known composition were made and a phase diagram near the liquidus is proposed based on the microstructures resulting when these melts were quenched. EXPERIMENTAL The Nb-Sn alloys weighing 0.7 g each were prepared in the form of cylinders. Niobium powder, -200, +325 mesh, and tin shavings with a minute amount of tin powder for a binder were mixed in the desired proportions and cold-pressed at 50,000 psi in a 0.150-in. die. This cylinder was then enclosed as shown in Fig. 1, and the entire arrangement mounted in a 2.6-in. pyrophyllite tetrahedron.' The desired temperatures (-2500°C) presented several problems in high-pressure container materials. Boron nitride, the usual sample holder, was found to react with niobium to form the nitride. However, MgO cans and plugs machined from refractory rods did not melt nor react with the sample. Thick tantalum contact disks were used to carry the large currents (~450 amps) to the graphite heater, since tantalum did not melt and had enough strength to prevent extrusion of the sample. It was further observed that the graphite heater and tantalum disks could not be in direct contact with the pyrophyllite because it melts and decomposes at these temperatures to kyanite and coesite (SiO2),2 the former reacting with graphite and the latter with tantalum to form the silicide. The use of a MgO outer sleeve

Jan 1, 1965

By F. W. Glaser

Iron-silicon alloys have had a great influence, in many ways, in modern industry. Silicon steels have been used almost exclusively for the construction of electrical machinery, but have also become an important material for structures which benefit by the high tensile and yield strengths of this material. In elaborating on the early history of work done on iron-silicon alloys, Greiner, Marsh and Stoughton1 went back as far as 1808, and pointed to Berzelius as the first producer of ferrosilicon. During the last twenty years some very important contributions in the form of studies of the iron-silicon system, as well as of the physical properties of these alloys, have been published. In consideration of the brit-tleness and poor machinability of alloys containing more than 5-6 pct Si, commercial interests have stimulated the research done on iron-silicon alloys, but mainly in the range of 0 to 6 pct Si. Yensen2 has shown the influence of im- purities, such as carbon, sulphur and phosphorus on the magnetic properties of 2, 4, and 6 pct Si alloys. Corson3 extended his investigation of physical properties to approximately 32 pct Si, and attributed the brittleness of the high-silicon material to the particular constitutional features of the alloys. Though mentioned earlier in the literature, the effect of nitrogen on crystal growth and magnetic permeability of iron-silicon alloys has been demonstrated recently by Morrill4 and Rostoker,5 respectively. In all the above quoted investigations, except that of Rostoker,5 sand or chill casting processes were employed for the preparation of samples. A major advantage of the powder metallurgy process is that it does away with time-consuming machining in many applications. The powder metal industry is always interested in pro- ducing a finished product employing a material which has presented considerably greater difficulties in manufacture by other methods. Steinit26 described preparation and testing of various Fe-Si alloys which were produced by the powder metallurgy process for the manufacture of armatures for small electric motors or generators. While Steinitz investigated alloys up to 6 pct Si, Rostoker5 went as high as 9 pct Si. The author7 previously discussed the diffusion of iron-silicon compacts containing 6 and 10 pct silicon. It is the object of this paper to study the progress of diffusion occurring in iron-silicon alloys by electrical resistivity measurements. All samples were prepared by pressing and sintering of compacts. Iron, silicon, and Fe-Si powders of various mesh size and compositions were employed to obtain test samples. It was assumed that complete diffusion had been obtained when the electrical resistivity reached a constant value characteristic for that particular alloy. To this end, electrical resistance measurements were used to follow the progress of alloying under various conditions.

Jan 1, 1950

By J. F Haseman, J. E. Davenport

In the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1,2 results in inadequate beneficiation. Investigation of Flotation Methods Flotation has been used in 'Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate. 3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P2O5 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P2O5, 20; SiO2, 40; CaO, 29; Fe2O3, 2; Al2O3, 3; F, 2.3. The particle-

Jan 1, 1948

By Maria I. De Rosa

The major fire and fire injury findings for all metal/nonmetal mining categories for 1990-2001 are shown in tables 64-65. Table 66, partly illustrated in figure 22, shows the number of fires, fire injuries, fire fatalities, risk rates, employees' working hours, and lost workdays for all metal/nonmetal mining categories by time period. For all metal/nonmetal operations (including stone and sand and gravel), a total of 518 fires occurred during 1990-2001; 296 of those fires caused 308 injuries and 4 fatalities (Ewhr = 4,012 x 106 hr, In = 0.015, LWD = 36,204). Thirty fires and 26 injuries involved contractors. The greatest number of fires and fire injuries occurred at surface operations; the highest risk rate values were also calculated for surface operations. The number of fires increased during the first four 2-year time periods (1990-1991, 1992-1993, 1994-1995, and 1996-1997), then decreased during the last two periods (1998-1999 and 2000-2001). The number of injuries showed a decrease throughout the periods, accompanied by an increase in employees' working hours. Twenty-five firefighting interventions by mine rescue teams in underground mines and at least 30 interventions at surface operations were required to combat these fires. However, 45 fires destroyed or heavily damaged facilities and equipment (including 19 pieces of mobile equipment) because of failure of firefighting methods, late fire detection, undetected fires, or fire size. Ninety-seven fires were detected late, and 30 fires were undetected. The ignition sources that caused the greatest number of fires were flame cutting/welding spark/slag/flame (169 fires or 33% with 137 injuries), hydraulic fluid/fuel sprayed onto equipment hot surfaces (89 fires or 17% with 46 injuries and 3 fatalities), heat source/explosion and flammable liquids/ gas/refueling fuel on hot surfaces (98 fires or 19% with 73 injuries), electrical short/arcing (51 fires or 10% with 16 injuries), and spontaneous combustion/hot material (46 fires or 9% with 17 injuries). The flame cutting/welding spark/slag/flame source caused fires usually involving welders' clothing or oxyfuel/grease and other materials (including chute and dust collector liners, flammable liquids, belt material, crusher, hopper and shaker deck materials, washer plants, equipment mechanical components, stampler breaker, hydraulic fluid, rubber tires and hoses, gear boxes, bin feeder, dump rope cables, screen liner and screen panel, kiln and shaft material, pipelines, liquor pumps, wood pallets, electrical junction boxes, handrails, grease, refuse, shop and wood). The spontaneous combustion/hot material and electrical fires were usually detected late due to lack of combustion gas/smoke detection systems. At least 55 of the 89 mobile equipment hydraulic fluid/fuel fires became large fires (requiring 12 mine rescue team interventions in underground

Jan 1, 2004

By L. B. Herring, Harold Decker

The area under discussion includes districts 2 and 4, so designated by the Texas Railroad Commission,‡ and comprises the following 26 counties: Bee, Brooks, Calhoun, Cameron, De Witt, Duval, Goliad, Gonzales, Hidalgo, Jackson, Jim Hogg, Jim Wells, Karnes, Kenedy, Kleburg, Lavaca, Live Oak, Nueces, Refu-gio, San Patricia, Starr, Victoria, Webb, Willacy, Wilson and Zapata. Drilling and Production The total number of wells drilled in this district during 1944 is shown in Table 5. This indicates a 41 per cent increase in all drilling over 1943. In spite of every handicap created by the war, the oil industry more than met the crisis in its drilling program in this district. Last year we thought it would be impossible to add to the total number of wells drilled in the previous yea;, but in spite of the lack of manpower and materials this large increase was shown. During 1944 this district produced 124,201,978 bbl. of oil from 11,607 producing wells, whereas in 1943 it produced 88,421,693 bbl. from 11,211 producing wells. This is an increase of 35,780,285 bbl. of oil. Some decline has been shown in the older fields arid undoubtedly the majority of wells in the district are producing at too high a rate. However, this district has been able to meet any demands made on it by the Petroleum Administration for War for increased production. Discoveries and Extensions There was a slight decline over the preceding year in the number of wildcats drilled, but the number of discoveries increased. In most instances subsequent development has not been sufficient to arrive at preliminary valuations but it appears that the over-all oil discoveries were below normal and that the gas discovcrics were relatively more important. The Canolis and Tijerina pools, Jim Wells County, and the Dan Sullivan pool, Brooks County, appear to be the outstanding oil discoveries of the year. No important oil reserve was discovered or developed in the Wilcox horizons, although considerable wildcatting was done. Important extensions were made at Agua Dulce and Stratton in Nueces and Teleberg Counties. Production was increased appreciably at Willimar, Willacy County, and Seeligson, Jim Wells County, in sands and areas which were apparently productive at the beginning of the year. Refining Most of the major work in the changing and completing of refineries was finished this past year. Some of the most modern refineries in the industry are now located in the Corpus Christi area. Gas and Condensate No new recycling projects were commenced during the year, nor were there any important additions to the old operations. No major gas reserve was developed, although several new discoveries suggest potentid possibilities.

Jan 1, 1945

By J. F. Haseman, J. E. Davenport

In the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1,2 results in inadequate beneficiation. Investigation of Flotation Methods Flotation has been used in 'Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate. 3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P2O5 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P2O5, 20; SiO2, 40; CaO, 29; Fe2O3, 2; Al2O3, 3; F, 2.3. The particle-

Jan 1, 1948

Objective To identify techniques to reduce the probability of gob gas explosions. Background In the last 6 years, seven explosions of methane and/or coal dust occurred within worked-out, sealed areas (gobs) of underground U.S. coal mines. These explosions, believed to have been started by lightning, destroyed many mine seals and caused much damage external to the sealed area. Three of these gob gas explosions occurred in one mine in Alabama over a 3-year period. Fortunately, the explosion forces and the toxic gases that vented from the sealed gob area did not cause fatalities or injuries, but they destroyed several large seals. If miners had been inspecting or working near these areas, the potential for serious injury and/or death would have been high. The United Mine Workers of America and the Mine Safety and Health Administration (MSHA) requested that the National Institute for Occupational Safety and Health (NIOSH) help identify the mechanisms for lightning penetration into the gob and recommend ways to reduce the probability of occurrence of future explosions from such lightning penetrations into sealed areas of underground coal mines. Because three of the explosions occurred in a single mine, special attention was focused on these particular explosions. The first occurred in April 1994 in a sealed area, which enclosed about 1.35square miles of abandoned workings (gob). This explosion destroyed 3 of the 38 seals that surrounded the gob. These seals were less than 2,000 ft away from three 4.5-in-diam steel-cased test wells that extended from the surface into the mine entry. At the time of the explosion, the National Lightning Detection Network (NLDN)verified 12 lightning strikes within 10 miles of the mine, including several above the gob. After the 1994 explosion, the damaged seals were rebuilt using an acceptable seal design capable of with standing a 20-psi explosion, as required by 30 CFR 75.335. On January 26,1996, a second gob explosion destroyed five more cementitious pumpable seals less than 2,000 ft away from those destroyed in 1994and even closer to the steel-cased wells. The NLDN verified72 lightning strikes in the area of this second gob explosion. Compressive strength analyses of fragments from the destroyed seals showed that strengths ranged from 11 to 138 psi, with an average of83 psi. This is over 100 psi below the minimum 200-psi compressive strength requirement for cementitious pumpable seals. These seals were again replaced. On July 9, 1997, the third and most violent explosion occurred in the same vicinity of the last two explosions. Three more cementitious pumpable seals were destroyed, including one newer seal that exceeded the minimum 200-psi compressive strength requirement. The NLDN verified 695 lightning strikes above the mine during the time in which the explosion occurred. MSHA's

May 1, 2001

Limnological processes are often overlooked when trying to assess the long-term water quality of pit lakes. It is essential to deal with these aspects, since they determine the geochemical and redox conditions around the submerged reactive rocks. Underground mining at East Sullivan (northwestern Quebec, Canada) stopped in 1966. Two adjacent stopes, 91 and 106 m deep, were left open to the surface, with roughly circular apertures of about 7700 and 18 000 m2. Water filling of the two glory holes went on over three decades and overflow began in 1999. Surface water pHs values were near neutrality as late as 1994 (6.3 - 7.0) but had become acidic by 1999 (2.6 - 3.5). Limnological processes were investigated in late-1999 and early-2000, with temperature measurements at 1 m intervals and sampling of the water columns before and after the late fall density inversions. A strong chemocline-thermocline was observed at 15 m. Above the chemocline, the water had low pH (3.2), no alkalinity, and low Na, Ca and sulfate. Below the chemocline, the concentrations of these parameters and the pH increased, with pH at 5.5 - 6. Consistent with the low pH values present in the upper 15 m, the concentrations of Al, Cd, Cu, and Zn were high near surface, and decreased below the chemocline. Dissolved oxygen concentrations as well as Eh decreased with increasing depth. Alkalinity integrated over the entire water column below the chemocline was at least six times larger than the acidity inferred from Fe2+ and Fe3+ concentrations. The temperature survey showed that seasonal density inversions do occur in the water column. The inversions do not involve the entire water body, since the surface to depth ratio is too small for a complete overturn. Oxygen from surface waters is carried to the bottom where it oxidises sulfides, until its depletion. Residual Fe2+, stable under anoxic conditions, is displaced upward by the next dense water incursion. It eventually reaches the thermocline, but only after many successive incursions. There, its oxidation to Fe3+ allows hydrolysis, which consumes dissolved and wall-rock alkalinity. It is only in 1999 that alkalinity was finally exhausted and that the pH shifts to acid values. The low pHs in the surface waters allow a build up of Fe3+ and Al3+, and desorption of metals from colloids. Buffering is assumed to be controlled by wall-rock oxyhydroxides in surface waters, and by carbonate minerals in the bottom waters. Because the seasonal overturns are far from being complete, the large amounts of alkalinity acquired from the wall-rock in the bottom waters cannot balance the acidity of near surface waters. Hence the surface water is acidic.

Jan 1, 2003

By W. David Menzie

An inventory of the mineral resources of a region is a most desirable basis for planning their systematic development. In the absence of appropriate samples upon which to base a reliable estimate of this inventory, investigators have resorted to a number of indirect approaches; the unit regional value concept forms the basis for one such approach. The produced resources of a region are a function of the inventory multiplied by the degree of intensity (some fraction between zero and one) of development of the resources. A convenient means of expressing this amount is to accumulate the weight and value of resource and to prorate the totals over the area represented by the unit sampled; i.e., weight and value per unit area or tonnes/km.2 and U.S. 1967 $/km.2. When this approach is used for the U.S.A., South Africa and Rhodesia the average value of (log.) U.S. 67$/km.2 for the states of the U.S.A. and South Africa are similar ($55,176 U.S.$67/km.2 and $52,538/km.2 respectively); whereas, Rhodesia is relatively underdeveloped (10,301 U.S.67$/km.2). On the other hand if the individual commodities are used as a basis for comparison, the U.S.A. shows the greatest diversity (67 commodities out of a possible total of 75) with South Africa next (50 commodities) and Rhodesia last with only 26 commodities. Since it is known that area and value are not simply related perhaps diversity is directly related to area. Again the kinds of commodities which have contributed the greatest value to the totals differs, with fuels (petroleum, coal and natural gas) predominating in the U.S.A. totals; whereas, South Africa and Rhodesia obtain their greatest contributions from gold, diamonds (S. Africa) coal and asbestos. In each case the greatest value of resources is produced from sedimentary rocks. As a somewhat different kind of example, consider a single resource (petroleum, the most valuable in the U.S.A.) over a large area (number of sampling units) the U.S.A. by state. Furthermore, assume that the model frequency distribution of the amount of petroleum (tonnes/km.2) is log normal. Then the present production fails to match the model first because 17 states (34% out of 50) have not produced petroleum. Of the remaining 33 states, Louisiana has produced the most (15,177 tonnes/km.2) and the frequency histogram is still skew. A spatial analysis of the distribution of the amount of petroleum by state shows that the samples (i.e., states) are not random; the non-producers and producers tend to cluster. It remains to be seen if this is indeed a true representation of the incidence of petroleum or is a function of the exploration philosophy currently in vogue.

Jan 1, 1977