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By Colin M. Sargent

ALTHOUGH annealing twins are frequently observed in many fcc metals, their occurrence in aluminum is relatively rare. ~ahn' in his review of twinning has listed only a few references to observations of twins in aluminum, e.g., Refs. 2 and 3. They have also been shown to occur in evaporated aluminum layers.4 During the present work, several annealing twins were studied in aluminum. The specimens of 1099-grade aluminum had the following thermomechanical treatment: deformed 90 pct by rolling, partially re-crystallized, further deformed 60 pct to a final thickness of 100 p, then annealed for 24 hr at 120°C. This treatment produced several annealing twins—-about ten per electron microscope specimen. The specimens were produced by the window technique and examined in a Phillips E.M. 200 operating at 100 kv. A typical twin boundary is shown in Fig. 1. For several of the twins studied the twin plane could be tilted so that it was parallel to the electron beam, e.g., Fig. 2. The associated diffraction pattern, Fig. 3, shows the twinned relationship between the grains. The twinning plane in each case was (111). Use of a reflection common to both the twin and the matrix,* i.e., using reflecting planes parallel in the twin and the matrix, the coherent twin boundary becomes invisible and only the noncoherent segments of the stepped boundary are seen, e.g., Fig. 4. Trace analysis of the boundaries showed that the long straight portions were invariably the twin plane; i.e., these portions are coherent. The planes of the shorter segments are shown by Fig. 5 to be (551 1, (7111, and {211).

Jan 1, 1969

By Rudolph Emmel

THE mines operated by the South American Development Co. are located in the Zaruma mining district of southwestern Ecuador. They are near the old mining town of Zaruma, which is the only important city in the canton of the same name. The district is situated in the upper end of a valley lying between two spurs of the Cordillera, one of which may be considered the Coast Range and the other an intermediate range. The mining camp proper, known as Portovelo, and the plant are 2.4 km. south of Zaruma, on the north bank of the Amarillo River, a tributary of the Tumbes River, which flows southwestward through Peru to the Pacific. Portovelo is difficult of access; it is reached from Guayaquil by means of river steamers and muleback. Embarking at Guayaquil, the route is down the Guayas River, across the Jambeli Canal, and up the Santa Rosa River to Santa Rosa, a distance of 177 km. From Santa Rosa, the road or trail follows the Santa Rosa River, then across the summit of the Coast Range into Portovelo, a distance of 74 km.-a two-day trip on muleback. The mining property of the South American Development Co. comprises 297 lode claims and 142 placer claims. The combined lode claims cover an area, roughly rectangular in shape, 9000 m. long from north to south by 4000 m. wide; the northern edge of the rectangle is about 3000 m. north of the central plaza of Zaruma. Mineral lands in Ecuador are held by virtue of an annual tax per claim paid to the central government, no surface rights being included.

Jan 1, 1925

By Joseph Hyde Pratt, Douglas B. Sterrett

Monazite is one of the minerals which, for a long time, was considered somewhat rare in its occurrence, but, upon a commercial demand arising for it, prospectors and engineers soon located large deposits of it in the Carolinas arid Brazil, and the supply has always been able to meet the demand. During 1908 further sources of supply of monazite have been discovered and developed in Idaho. North and South Carolina, however, are the only States that have thus far put any monazite on the market. Monazite is essentially an anhydrous phosphate of the rare-earth metals,ceriunl, lanthanum, and didymium,(Ce,La,Di)PO,. There is nearly always present a varying but small percentage of thoria, Tho2, and silicic acid, SiO2,, which are very probably united in the form of a thorium silicate, ThSiO4. Some mona-zites contain but a fraction of a per cent. of thoria, while others have been recorded that showed the presence of from 18 to 32 per cent.; but the majority contain from 3 to 9 per cent. of this oxide. It is the presence of the thorium oxide that gives the monazite its commercial value. The analysis occasionally shows also the presence of other constituents, as the yttrium and erbium oxides, zirconia, alumina, magnesia, lime, iron oxides, manganese oxide, and titanium oxide. Monazite is light-yellow, honey-yellow, reddish-, brownish-, or greenish-yellop. in color, with a resinous to vitreous luster, and is translucent to subtransparent. It is brittle, with a con-choidal to uneven fracture, and is from 5 to 5.5 in hardness, and from 4.64 to 5.3 in specific gravity. It crystallizes in the monoclinic system, and some crystals have been observed that werc 6 in. in length. The more perfect crystals are,-however,

Jan 1, 1910

By Zay Jeffries

HOSTILITIES in Europe, Asia, and northern Africa were responsible for dislocations in rare-metal supplies during 1940. Although the consumption of some of the rare metals is small the dislocations may be relatively large. In some cases these are advantageous to North America and in others they are disadvantageous. Specific instances will be cited later. Barium T HIN films of barium metal on special steel balls greatly improve the life and reduce the friction of rotating anodes in highly evacuated small X-ray tubes and make possible the operation of these anodes at relatively high temperatures. These remarkable results are described in an article by Atlee, Wilson, and Filmer in the Journal of Applied Physics for September, 1940. Oil could not be used because of the high temperatures on the one hand and its volatility on the other. Fig. 3 shows diagramatically the rotating anode and the method of coating the steel balls with barium. The letters K.I.C. refer to "Kemet Iron Clad." The K.I.C. wire was mounted so that the barium could be evaporated by direct passage of the electric current. At high temperatures the barium dif-

Jan 1, 1941

By H. R. Hanley

The characteristics of alloyed anodes and their influence on the products of electrolysis and power consumption have been noted previosly ously in the literature.' This paper presents data in continuation of the subject given in an earlier paper by the authors.2 As noted in the authors1 previous paper, the objectives of this work are the reduction in the cell voltage and the purity of the cathode product resulting from the use of alloyed lead anodes. The fundamental facts developed in the previous paper were: (I) that the presence of a small amount of calcium lowers the anode potential approximately 50 per cent. below that of pure lead; and (2) that thallium when present to the extent of 4 per cent. rendered the anode practically stable, thereby lowering the contamination of the cathode by lead to a very insignificant amount. The specific features determined in this recent work are as follows: 1. The lowest limit of calcium in the lead which will still give maximum lowering of the anode potential. 2. The characteristics of the thallium-calcium-lead anode. 3. The characteristics of the silver-calcium-lead anode. 4. The characteristics of the thallium-silver-calciurn-lead anode. It was determined that 0.1 per cent. calcium in the anode was sufficient to lower the anode potential approximately 50 per cent. Table 1 shows the characteristics of alloyed anodes tested. The anode composed of 0.1 per cent. calcium, 4 per cent. thallium, and 95.9 per cent. * Professor of Metsllurgy, Missouri School of Mines. t Professor of Metallurgy and Ore Dressing, Hea.d of Department, Missouri School of Mines. Assistant Professor of Metallurgy, Missouri School of Mines. 1 Among others, see C. G. Fink and Li Chi Pan: Insoluble .Anodes for the Electrol-ysis of Brine [Trans. Amer. Electrochem. Soc., (1926) 49, 83-1341 and other papers by these authors. U. CJ. Taintori, 8. G. Taylor arid H. P. Ehrlinger: Lead Alloys for Anodes in Electrolytic Production of Zinc of High Purity. Truns. A. I. M. E. (1929) 192-200. 2 H. R. Hanley, C. Y. Clayton, D. F. Walsh: Investigation of Anodes for Production of Electrolytic Zinc. Trans. A. I. M. E. (1930) 275

Jan 1, 1931

By C. G. Wilson

DURING the course of some experiments on the plastic deformation of gallium a standard stereo-graphic projection was prepared with (001) at the center and it was felt that this might be useful to others working with single crystals of gallium. The stereogram, given in Fig. 1, was made using the following crystallographic data (Bradley, 1935):

Jan 1, 1962

By G. Donald Emigh

WESTERN phosphate resources which lie in Ida- ho, Montana, Utah, and Wyoming, have seen great expansion of activity in recent years. Growth has been two-pronged: expansion in fertilizer use, and since 1949, into the elemental phosphorous industry. Elemental phosphorous, produced in the electric furnace, goes largely into chemical making. Phosphate ore was first recognized in the West about 1889. Production started in 1906, and for many years consisted of underground operations by small companies operating sporadically. In 1920 Anaconda Copper Mining Co. opened the underground Conda mine near Soda Springs in southeastern Idaho, and has maintained and increased its operations since then. About 1930 Montana Phosphate Products Co. began underground mining in Montana and has remained a steady producer. In 1945 San Francisco Chemical Co., one of the oldest companies in the western field, initiated strip mining at the Waterloo mine near Montpelier, Idaho, and later at Leefe mine near Sage Junction, Wyo. In1946 J. R. Simplot Co. began open pit mining at Gay mine near Fort Hall, Idaho. In 1950 Victor Chemical Works began underground development work in the area of Maiden Rock, south of Butte, Mont.: and has since mined there. Monsanto Chemical Co. began open pit mining near Soda Springs, Idaho, in 1951.

Jan 11, 1954

By R. V. Sara

Determination of the Hf-C phase diagram was conducted primarily by metallographic and X-ray diffraction studies on appropriate alloys. The only intermediate phase observed in this binary system was HfC. This phase was found to be homogeneous between 34.0 and 48.0 at. pct C at 2200°c and between 36.0 and 49.3 at. pct C at 3150°C. The lattice-parameter variation was also determined for HfCI-, compositions prepared at 2200° and 3150°C. The most most refractory composition, with a melting point of 3830°c, was established at 47.5 at. pct C from melting-point data. Solidus temperatures of 2240' and 3150°C occur on the high-kafnium and high-carbon sides of the monocarbide, respectively. The invariant point between HfC and carbon is located at 66.0 at. pct C, whereas the 2240°C solidus corresponds to the peritectic temperature at which hafnium is formed from HfC and hafnium-rick liquid. Hafnium has a melting temperature of 2208°C and is capable of taking carbon into solution to the extent of 10.5 at. pct at this temperature. ALTHOUGH the Hf-C phase diagram has not been previously evaluated experimentally in its entirety, the belief has been that the general configuration would resemble the chemically similar Group rV carbide systems, Ti-C and Zr-c.' These binaries are characterized by a single carbide phase with a simple NaC1-type structure which is maintained over wide compositional ranges. This family of carbides has high thermal stability that increases substantially as the atomic number of the metal component increases. This trend characterizes HfC as one of the highest melting materials. According to Agte and Alterthum,2 the melting point for this monocarbide is 3890°C, a value that has been quoted quite extensively for the past several decades. Recently, in repeating the work of Agte and Alter-thum, Adams and Beall3 determined the melting point of HfC to be 3895°C. A significant departure from the commonly accepted version of the Hf-C system was reported by Avarbe and his coworkers,4 who proposed that there is an extreme stabilization of a hafnium in a narrow field to 2820°C, above which it melts peritectically to form HfC and liquid. Their study was also concerned with the melting temperature of various HfCI-, compositions, but the peak melting point was taken from the work of Agte and Alterthum. Avarbe and his associates were not concerned with the high-carbon region of the system. However, three widely varying temperatures have been reported for the HfC-C solidus by other investigators. Cotter and Kohn5 observed approximately 2800°C; Portnoy et al.' reported 3260°C; and, more recently, Krikorian7 indicated 2915°C. Equally as uncertain is the solidus between hafnium and HfC. As noted above, Avarbe et al. report a peritectic temperature of 2820°C, Krikorian7 measured 2150°C, and Benesovsky and Rudy' estimated 2000°C on their diagram. I) EXPERIMENTAL PROCEDURE The starting materials for this study consisted of reactor-grade hafnium hydride obtained from Fair-mount Chemical Co., Newark, N.J., hafnium carbide supplied by Wah Chang Corp., Albany, Ore., and Union Carbide spectroscopic-grade graphite, SP-1. The graphite analysis indicated impurities at levels of only 0.5 ppm or less. According to the suppliers, the hydride and carbide contained the typical impurities listed in Table I. The samples required for these studies were prepared by dry blending either graphite and hafnium hydride or hafnium hydride and hafnium carbide powders for approximately 5 min in a "Spex Mixer Mill". The latter combination was used only for preparing several samples in the HfC1-, melting-point studies. Small pellets, varying between 3/16

Jan 1, 1965

By C.P. Clingerman

The recent iastallation of a combination dust catcher, gas washer and precipitator at Carrie blast furnaces of the Homestead Steel Works has given very satisfactory results. The following description of the gas-cleaning installation is based on actual operating experience. When Carrie blast furnace No. 3 was rebuilt the decision was made to fine-clean all the gas produced by the furnace, because the management wanted fine-cleaned gas for fuel in the stoves and boilers. In order to keep the installation cost as low as possible, the gas-cleaning system was streamlined. All by-pass lines and goggle valves for bypass lines were eliminated from the system. A radical departure from the use of 8-in. tubes in the Cottrell-type precipitators was made by using 12-in. diameter tubes in a single compartment, the single compartment being divided into two units by a single partition wall in the top header. The Furnace Proper A few of the characteristic points and dimensions of the furnace proper are: Hearth diameter.............. 26 ft. o in. Bosh diameter............... 29 ft. 1 3/4 in. Stock-line diameter........... 20 ft. o in. Large-bell diameter........... 14 ft. 8 in. Small-bell diameter........... 6 ft. 6 in. Height of furnace from center of iron notch to bottom of large bell, closed............ 94 ft. 4 in. Height of furnace from center of iron notch to main platform ...................... 105 ft. o in. The furnace top is equipped with a MC-Kee revolving distributor, the operation of which is electrically interlocked with the skips, bell hoists, and coke-weighing and charging apparatus through a Freyn automatic charging control. The gas leaves the furnace first through four offtakes, 5 ft. 9 in. in diameter, then through uptakes that, are approximately 85 ft. high, which feed into a single down-comer that is 9 ft. in diameter. Dust Catcher The primary dust catcher installed (Fig. I) may be described as a single-cone type. The inlet pipe at the top of the dust catchei is 9 ft. in diameter; it is flared to a conical shape as it extends down inside the dust-catcher shell, which is 35 ft. in diameter, 37 ft. high on the straight side, and has a conical top and bottom. The slope of the bottom is so0 with the horizontal. The cone-shaped pipe inside the dust-catcher shell is 42 ft. high and is 19 ft. 7 in. in diameter at its bottom lip where it releases the gas inside the dust catcher. The ratio of the area of the inside cone at its bottom lip to the

Jan 1, 1943

By C. P. Clingerman

The recent iastallation of a combination dust catcher, gas washer and precipitator at Carrie blast furnaces of the Homestead Steel Works has given very satisfactory results. The following description of the gas-cleaning installation is based on actual operating experience. When Carrie blast furnace No. 3 was rebuilt the decision was made to fine-clean all the gas produced by the furnace, because the management wanted fine-cleaned gas for fuel in the stoves and boilers. In order to keep the installation cost as low as possible, the gas-cleaning system was streamlined. All by-pass lines and goggle valves for bypass lines were eliminated from the system. A radical departure from the use of 8-in. tubes in the Cottrell-type precipitators was made by using 12-in. diameter tubes in a single compartment, the single compartment being divided into two units by a single partition wall in the top header. The Furnace Proper A few of the characteristic points and dimensions of the furnace proper are: Hearth diameter.............. 26 ft. o in. Bosh diameter............... 29 ft. 1 3/4 in. Stock-line diameter........... 20 ft. o in. Large-bell diameter........... 14 ft. 8 in. Small-bell diameter........... 6 ft. 6 in. Height of furnace from center of iron notch to bottom of large bell, closed............ 94 ft. 4 in. Height of furnace from center of iron notch to main platform ...................... 105 ft. o in. The furnace top is equipped with a MC-Kee revolving distributor, the operation of which is electrically interlocked with the skips, bell hoists, and coke-weighing and charging apparatus through a Freyn automatic charging control. The gas leaves the furnace first through four offtakes, 5 ft. 9 in. in diameter, then through uptakes that, are approximately 85 ft. high, which feed into a single down-comer that is 9 ft. in diameter. Dust Catcher The primary dust catcher installed (Fig. I) may be described as a single-cone type. The inlet pipe at the top of the dust catchei is 9 ft. in diameter; it is flared to a conical shape as it extends down inside the dust-catcher shell, which is 35 ft. in diameter, 37 ft. high on the straight side, and has a conical top and bottom. The slope of the bottom is so0 with the horizontal. The cone-shaped pipe inside the dust-catcher shell is 42 ft. high and is 19 ft. 7 in. in diameter at its bottom lip where it releases the gas inside the dust catcher. The ratio of the area of the inside cone at its bottom lip to the

Jan 1, 1943

Jan 1, 1967

Jan 1, 1967

By C. J. Fleisch, C. P. Clingerman

THE recent installation of a combination dust catcher, gas washer and precipitator at Carrie blast furnaces of the Homestead Steel Works has given very satisfactory results. The following description of the gas-cleaning installation is based on actual operating experience. When Carrie blast furnace No. 3 was rebuilt the decision was made to fine-clean all the gas produced by the furnace, because the management wanted fine-cleaned gas for fuel in the stoves and boilers. In order to keep the installation cost as low as possible, the gas-cleaning system was streamlined. All by-pass lines and goggle valves for bypass lines were eliminated from the system. A radical departure from the use of 8-in. tubes in the Cottrell-type precipitators was made by using 12-in. diameter tubes in a single compartment, the single compartment being divided into two units by a single partition wall in the top header. THE FURNACE PROPER A few of the characteristic points and dimensions of the furnace proper are: [Hearth diameter 26 ft. o in. Bosh diameter 29 ft. 1 3/4 in. Stock-line diameter 20 ft. o in. Large-bell diameter 114 ft. 8 in. Small-bell diameter 6 ft. 6 in. Height of furnace from center of iron notch to bottom of large bell, closed 94 ft. 4 in. Height of furnace from center of iron notch to main platform 105 ft. o in.] The furnace top is equipped with a McKee revolving distributor, the operation of which is electrically interlocked with the skips, bell hoists, and coke-weighing and charging apparatus through a Freyn automatic charging control. The gas leaves the furnace first through four offtakes, 5 ft. g in. in diameter, then through uptakes that are approximately 85 ft. high, which feed into a single down-comer that is 9 ft. in diameter. DUST CATCHER The primary dust catcher installed (Fig. I) may be described as a single-cone type. The inlet pipe at the top of the dust catcher is g ft. in diameter; it is flared to a conical shape as it extends down inside the dust-catcher shell, which is 35 ft. in diameter, 37 ft. high on the straight side, and has a conical top and bottom. The slope of the bottom is 50° with the horizontal. The cone-shaped pipe inside the dust-catcher shell is 42 ft. high and is 19 ft. 7 in. in diameter at its bottom lip where it releases the gas in-

Jan 1, 1943

By T. D. Parris

Within a 30-mile radius of Sudbury, Ontario, the Ontario division of the International Nickel Co. of Canada, Ltd., operates nine underground mines and two open pits. Prior to 1966, ore removal from the underground workings was mainly by scraping, using 125-hp electric slushers in blasthole and caving mining, and 30-hp or less air-operated slushers for fill- method mining. The development and evaluation of low-profile, diesel-powered front-end loaders, designed specifically for underground operations, was followed with keen interest during the period 1964-1965.

Jan 6, 1969

By B. D. Cullity

GOLD and beryllium form an intermediate phase composed of the two metals in equal atomic proportions and having the formula AuBe. According to Winkler,1 this phase probably exists in two modifications: beta, stable below about 600°C, and alpha, stable between 600°C and the melting point, about 740°C. Only the low- temperature beta form will be considered in this paper. EXPERIMENTAL PROCEDURE The gold used had a fineness of 999.75 to 999.85, balance mainly silver, and the beryllium purity was better than 99.8 pct. AuBe was prepared by melting the constituents in a beryllia crucible in an evacuated induction furnace. After melting and thorough mixing, the alloy was allowed to solidify in the crucible. No difficulty was encountered in obtaining a homogeneous ingot. Both chemical analysis and microscopic examination of the ingot showed that the alloy was essentially one phase, containing 50 at. pct gold. The alloy was quite brittle and powder samples could easily be pre- pared by grinding in an agate mortar. The X-ray diffraction patterns were made with CuK-alpha radiation in a Debye-Scherrer powder camera 57.3 mm in diameter. The film was placed unsymmetrically in the camera in order to afford a basis for am-shrinkage corrections. A sample homogenized at 5o0°C gave the same diffraction pattern as a sample taken from the as-melted ingot. GENERAL RESULTS The diffraction pattern of AuBe was readily indexed on the basis of a simple cubic lattice with ao = 4.659 ± 0.001kX. If the unit cell is assumed to contain four AuBe "molecules," the calculated X-ray density is 13.46 grams per cc as compared with the measured density of 13.55 gm per cc. The only missing reflections in the dsraction pattern are (100) and (220) (see Table I). Since these missing reflections are not those characteristic of body or face centering, the lattice of AuBe must be simple cubic. To locate the positions of the atoms within the unit cell, two possibilities had to be considered: I. The structure was disordered and there were eight positions to be filled by an "average" gold-beryllium atom. That the structure was disordered seemed unlikely since the lattice parameter did not vary with composition in alloys containing some- what more and somewhat less than 50 at. pct gold, indicating a fixed composition for AuBe.

Jan 1, 1947

By J. L. Lytton

The flow-stress recovery of high-purity aluminurn following a 10 pct tensile prestrain was studied in terms of a fractional flow-stress recovery parameter fr. The flow-stress recovery behavior was related to the dislocation arrangements using transmissiort electron rnicvoscopy. During recovery at 120° and 160°C, nearly stable strength levels were attained, the strength level for 120°C recovery being greater than that for 160°C. This stabilization of flow stress was related to the formation of meta-stable dislocation networks bounding nearly perfect cells. Both network formation and the annealing of dislocation loops were found to be recovery mechanisms, and the stronger metastable strength level joy 120°C recovery was related to a smaller average cell size. Analysis of the networks was consistent with the reaction of sets of dislocations with a/2 (110) Burgers vector to give product Burgers DURING isothermal annealing of cold-worked metals, a degree of softening occurs without re-crystallization, and the processes responsible for this change are termed recovery processes. During recovery annealing, the dislocations generated during cold work become rearranged into low-energy configurations, and as much as 50 pct of the stored energy is released."' The relationship between this rearrangement of dislocations and mechanical behavior is of considerable importance, since the dislocation substructures formed during recovery provide a significant degree of low-temperature strength3j4 and can favorably alter the course of primary creep at high temperatures.4 The purpose of the present study was to relate the flow-stress recovery behavior of high-purity aluminum to the substructural modifications that occur. Electron transmission microscopy was therefore employed for direct observation of dislocation substructures at various stages of recovery following 10 pct prestrain. Several investigators5-' have proposed that dislocations can become rearranged or lost during the preparation of thin foils. It was found early in the present study that the dislocation structures in the thicker regions of the foils changed in a systematic way during the course of recovery. Therefore, it is unlikely that substantial losses or rearrangements occurred during thinning. This point will be discussed in more detail later. The results of various investigators indicate that recovery processes in fcc metals can result in release of 50 pct or more of the total energy stored in the as-prestrained metal, this percentage decreasing with increasing prestrain.' Alloying elements or impurities tend to increase this percentage. The release of stored energy of fcc metals during recovery appears to occur by 1) annealing of point defects if the deformation occurred at sufficiently low temperaturesg and 2) rearrangement of dislocations into low-energy Configurations.1,2In bcc metals, the annealing of dislocation loops has also been observed during recovery after prestrain,10-12 and it has been proposed that this is a recovery mechanism for unidirectionally strained fcc metals.' The density of dislocations in bcc metals has not been observed to decrease appreciably during recovery,10 although the formation of regular dislocation networks has been observed. has shown that the formation of such networks can result in elimination of long-range stresses and can lead to significant release of stored energy without dislocation annihilation. It might thus be expected that network formation is a significant recovery mechanism in fcc metals, although extensive network formation has apparently not been reported in controlled recovery experiments. The formation of sub-boundaries in aluminum has been observed by various investigators13'17 during recovery studies of aluminum, but the structure of these boundaries was not resolved. In this regard, it is significant to note that Bailey and Hirsch,' using transmission electron microscopy, detected no network or sub-boundary formation during recovery of 99.99 pct Ag. Furthermore, Clarebrough et al.2 found no such rearrangements during recovery of copper. EXPERIMENTAL PROCEDURE The high-purity aluminum used in this investigation was obtained in the form of 0.125-in.-thick sheet. Spectrographic analysis revealed that the sheet was 99.995 pct A1 with the following weight-percent impurities: 0.001 Cu, 0.002 Fe, 0.001 Si, and 0.0004 Mg. The as-received sheet was in the heavily cold-rolled condition. The as-received sheet was cold-rolled at room temperature to 0.040-in.-thick sheet in the longitudinal direction, which was the original rolling

Jan 1, 1965

By F. Habashi

Conclusive evidence is given showing that the dissolution of gold in cyanide solution follows mainly the over-all equation A similar equation can also be written for the dissolution of silver. Theoretical derivation of the velocity equation for this reaction has been obtained, which describes quantitatively the experimental facts. The equation is as follows: where [CN-] and [O2] = the concentrations (in moles/ml) of cyanide and dissolved oxygen, respectively. DcN- and Do2 = the diffusion coefficients of cyanide and dissolved oxygen; 1.83 x 10-5 and 2.76 x 10-5 cm2 sec-1, respectively. A = the surface area of the metal in contact with the aqueous phase, in cm S = the thickness of the boundary layer; varies between 2 and 9 x 10-3 cm, depending on the speed and method of agitation. Rate being expressed in g. equiv. sec-1. INTRODUCTION During recent years a number of papers have been published on the kinetics of dissolution of gold and silver in cyanide solution.1,6 The authors agree that the rate of dissolution is diffusion-controlled, but disagree regarding the mechanism of the reaction. Some authors'-3 support the Bodlander equations: The apparently conflicting results, when critically reviewed, are concordant and lead to the conclusion that the proper equation for the dissolution reaction should be only Eq. 1. This conclusion is based on the following facts: 1) For every 2.2 equivalents of metal dissolved one mole O2 was consumed. 2) For every 1 equivalent of metal dissolved, 2 moles of cyanide were consumed.' 3) Hydrogen peroxide is formed during the dissolution of gold or silver, and for every 2.2 equivalents of metal dissolved, one mole H2O2 was produced.1,2 The fact that Kudryk and Kellogg4 did not detect H2O2 during the dissolution of gold should not throw doubt on the many affirmative reports of other investigators. Lund2 has shown that depending on the crystalline nature of the silver surface, (e.g. method of etching the sample) H2O2 may undergo catalytic decomposition heterogeneously according to: Further Kudryk and Kellogg4 carried out their experiments in the presence of 0.5% KC1 to achieve a greater electrolytic conductivity, and Matsudaira7 has shown that H2O2 is catalytically decomposed (homogeneously) in the presence of C1- ion in alkaline solution. 4) Experiments carried out by Boonstra8 and Lund2 showed that the dissolution of gold and silver respectively in KCN + H2O2 in the absence of oxygen was a slow process. Thus the reaction takes place to a minor extent only. Further kinetic studies showed that: 1) The rate of dissolution depends on the surface area of the metal in contact with the liquid phase, thus indicating that the process of dissolution is a heterogeneous process. 2) The rate of dissolution depends on the speed of stirring,5,6 thus indicating that the process is controlled by a physical phenomenon.

Jan 1, 1967

By Subhas G. Malghan

Feldspathic deposits occur widely throughout the United States, but North Carolina, California, Connecticut, and South Carolina accounted for over 80% of the total domestic feldspar output for the year 1973.1 Pegmatites and granites constitute the major feldspar reserves of the United States, 2 and in addition, feldspar is produced as a byproduct by firms whose major products are spodumene and mica. 3 Feldspar flotation is practiced in the United States, Mexico, Finland, Norway, West Germany, Japan, and the USSR. According to the US Bureau of Mines estimates, the production of feldspar in the United States and rest of the world were 704,000 and 2,514,000 t, respectively. Feldspar is principally used as a flux in making glass, pottery, porcelain, enamel, tile, and other ceramic products. In recent years, the domestic feldspar industry is faced with a number of problems. As a result of increased cost of energy and the introduction in 1972 of new legislative programs relating to air, water, and noise pollution, land-use restrictions, and mined-land rehabilitation, the production costs have increased. Apart from the increased cost of operation, an operational problem exists with the feldspar producers in North Carolina, especially those in the Spruce Pine area. This problem is concerned with the use of hydrofluoric acid in the feldspar flotation. Feldspar producers in Spruce Pine, NC, have been discharging process waste water into the North Toe River. The mill waste water contains active fluoride ions. Fluoride in excessive concentrations is undesirable in waters used for drinking. It is stated that water containing 0.9-1.0 ppm fluoride will seldom cause mottled enamel on children's teeth; and for adults, concentrations less than 3-4 are not likely to cause endemic cumulative fluorosis and skeletal effect. Although the literature on this subject is rather confusing and inconclusive, the inference that concentrations over 4 ppm may affect bone structure is clear. According to the recent Federal Register,4 maximum fluoride level of 1.4 ppm at 79°-98°F is considered to be adequate and safe for the protection of health of the consumers. The EPA and state environmental agencies have accelerated their drive to reduce water pollution on a faster schedule. By 1977, the EPA specifications for maximum contaminant level of fluoride ions in the discharge waters of feldspar milling operatins is expected to be reduced to 2.0 ppm. The other problems of using hydrofluoric acid are the following: toxicity, hazards of handling and storage, and high cost as compared to other inorganic acids (almost 16 times the cost of sulfuric acid). In order to reduce fluoride levels in mill discharge waters, mining companies have taken the following steps: I) Recirculating a part of their mill water. Even though recirculation of mill water seems to be a novel method of reducing fluoride contamination of the discharge water, there are certain operational and handling problems. 2) Conducting research on the treatment of fluorides in mill waste water. The technology of treatment of fluoride ions has received considerable interest in the recent years. A recent research report5 estimates that the cost of fluoride ion removal to meet the present specifications in the feldspar industry is approximately $0.25/t of ore processed, and about $0.50/t of feldspar produced. At the request of the feldspar producing industries in North Carolina, the North Carolina State University (NCSU) Minerals Research Laboratory has taken up a research program directed towards overcoming the fluoride ion pollution problem. After a close study of the operational, technical, and economic aspects of feldspar flotation, it was decided to attempt to replace the conventional hydrofluoric acid process. Conventional Feldspar Flotatin Using Hydrofluoric Acid Since the inception of the feldspar flotation process using hydrofluoric acid by O'Meara2,6 the process has achieved a great commercial success. In the conventional flotation separation of feldspar-quartz, hydrofluoric acid is used to suppress quartz and activate feldspar, and a long chain amine salt (acetate or chloride) is used as a collector. The bulk of amine collectors used in current feldspar operations are applied as the water-soluble acetates of the free-base amines. These products are pastes or waxy solids which are available in a range of acetic acid neutralization levels generally 50 to 100% neutralized. In spite of the problems mentioned in connection with the use of hydrofluoric acid, this process is extremely stable with respect to changes in the process variables. With the exception of a few operations, alaskite and pegmatite are the major sources of feldspar.7 In the flotation treatment of a pegmatite that contains iron-bearing minerals (heavy minerals), mica, feldspar, and silica, a logical order of removal presents itself considering the following:8 1) Mica is readily floated by an amine collector in a pulp pH 3.5. Some iron-bearing minerals will usually respond to amine collector in acid circuit with the mica concentrate. 2) Since iron minerals tend to occur invariably in the feldspar concentrate, it is desirable to remove most of these prior to feldspar flotation. A fatty acid or a petroleum sulfonate collector used in this flotation step in acid circuit will float iron-bearing minerals. 3) Using hydrofluoric acid to maintain pH of 2.5, an amine collector employed in a final step will float feldspar away from silica, usually leaving the latter in the tailing as a high-grade silica concentrate. The problems connected with the flotation separation of feldspar-quartz arise due to the similarities in their chemical structure. Therefore, any reagent system that is likely to succeed in feldspar-quartz separation should have adsorption affinity towards one of the minerals and depression effect towards the other mineral.

Jan 1, 1979

[Chairman ZAY JEFFRIES, Vice-chairman S. SKOWRONSKI, Chairman WILLIAM M, CORSE, Secretary Executive Committee J. R. FREEMAN, JR., Local Section G. E. JOHNSON R. S. ARCHER, Non-ferrous Data Sheets P. D. MERICA EDGAR C. BAIN, Journal Committee L. W. SPRING SAM TOUR, Papers Committee F. L. WOLF H. C. JENNISON, Membership Committee Local Section Committee J. R. FREEMAN, JR., Chairman R. J. ANDERSON, Cincinnati R L. DOWDELL, Minneapolis R. S. WILLIAMS, Boston G. H. CLAMER, Philadelphia W. A. SCHEUCH, Chicago R. F, Woon, New York Papers Committee S. SKOWRONSKI, Chairman F. H. DIx, JR.-Aluminum E. R. DARBY-Bronze C. S. WITH ERELL-Copper H. A. BEDWORTH-Brass W. K. FRANK-BRONZE F. W. HARRIS-Copper R. L. SUHL-Nickel H. M. ST. JOHN--Foundry Metallurgy R. S. DEAN-Theoretical Metallurgy]

Jan 1, 1928

By C. F. Weinaug, R. W. Farley, J. F. Wolfe

A rapid, accurate method for predicting the dew points of gas condensate systems and their subsequent normal and retrograde phase behavior with pressure decline has been developed. The method predicts dewpoint pressure, volume percent liquid, condensate content of produced gas, and the liquid and gas compositions at pressures below the dewpoint pressure. Use of a modified form of the BWR equation of state, which was established by regression calculations on experimental data from several gas condensates, provides depletion behavior predictions that are significantly improved over predictions using K-values based on convergence pressures and Standing's correlation for density. INTRODUCTION Prediction of complex hydrocarbon-mixture thermodynamics is fundamental to reservoir and gas process engineering. In particular, accurate descriptions of phase behavior are needed to plan production operations for gas-condensate reservoirs. Although analysis of reservoir behavior during producing and cycling operations can be made for simple reservoir models, extensions of these studies to more complex reservoir systems are still difficult, both with regard to numerical techniques and the phase behavior of the fluids. This report presents a mathematical method for handling the complex phase relationships encountered in retrograde condensates; it represents an advance in reservoir behavior technology in that it will aid the development of closed-form mathematical representations of total production systems. A typical phase diagram for a complex hydrocarbon mixture is shown in Fig. 1. When the reservoir temperature T, is higher than the critical temperature Tc, and lower than the critical-condensation temperature Tct' the mixture is a gas condensate. Decreasing the pressure on a condensate while maintaining nearly constant temperature will result in two phases forming at the dew point. Further decrease in pressure will cause additional liquids to be formed. This phenomenon is called retrograde condensation. As pressure continues to decrease, normal phase behavior regions are encountered (liquid vaporizes as the pressure decreases) until the low-pressure dew point is encountered. When a gas-condensate reservoir is produced, gas is withdrawn and the volume of fluids in the reservoir remains nearly constant as the pressure declines. Heavier components tend to accumulate in the liquid phase as a result of retrograde condensation, while lighter components tend to concentrate in the vapor phase. Thus, as the gas is produced the composition of the gas and the condensate

Jan 1, 1970