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By F. C. Noyes

DAME Nature was in a generous mood when she distributed widely over the face of the globe numerous deposits of phosphate rock from which man can make phosphatic festiIizer to replace the phosphate re- moved from the soil by crops. The principal deposits are readily accessible to the world's greatest consuming areas and most of them are such that mining operations can be carried on at relatively low cost. The world's known reserves shown in Table 1 are sufficient to last well over 2000 gears at the present rate of consumption. Before giving a brief outline of the phosphate rock industry of foreign countries let us try to get a picture of the movement of phosphate rock throughout the world in 1938, the last full normal calendar year where it came from and where it was consumed. Table 2 shows the origin and finial destination of world shipments in 1938 by grand divisions. Table 3 (p. 499) shows shipment9 of phosphte rock to each country in Europe. Europe is seen to be by far the world's greatest market and the French North African mines the world's most important producers outside of the U. S. A.

Jan 1, 1944

By B. J. Scheiner, A. G. Smelley

The Bureau of Mines, US Department of the Interior, is conducting research on a dewatering technique for fine particles generated during the mineral beneficiation process that will recover a portion of the water now being lost using conventional waste disposal methods and significantly reduce the time required for land reclamation. The technique utilizes a flocculant, polyethylene oxide (PEO), that forms strong stable flocs that can be dewatered rapidly on static and/or rotary screens. Infield tests, phosphate clay waste has been dewatered from a nominal 2.5% solids to greater than 20% solids. In other field tests, coal-clay waste has been dewatered from a nominal 3% solids to greater than 55% solids. In addition, small-scale continuous tests have shown that bentonitic clays can be dewatered from 12% solids to 40% solids.

Jan 1, 1985

By Lewis Carroll

AS he contemplates the numerous good things the hard-working committees have evolved for the 140th Meeting of the Institute, the Editor knows just how the walrus felt when he uttered his memorable, if somewhat lugubrious lines. For there are the Annual Reception and Dinner at the Commodore, 'the Gold Supply Symposium, the luncheons, general and special, and the Annual Institute of Metals Lecture, a Round Table on Iron Ore and a wonderful Informal Dance at the Grand Central Art, Gallery, substantial general sessions, a Smoker-and many other things. -Old, friends and new, reminiscences and confidential chats, horizons pushed back by new information and adjusted perspectives, courage revived and ambitions stimulated-one with a flair for the modernistic might make something-or nothing-of the kaleidoscopic preview 'of the coming Annual Meeting.

Jan 1, 1931

By W. V. Kotlensky, H. E. Martens

In an earlier communication, Ref. 1, the authors presented the tensile properties and the changes in crystal structure and microstructure for pyrolytic graphite tested at 2750°C. It was suggested that changes in the structure may have an effect on the tensile properties of this material. Accordingly, tensile tests were run on a series of specimens, from one block of pyrolytic graphite, some of which were hot-worked by being strained at 2750°C, others of which were tested in the as-deposited condition. According to the manufacturer, General Electric Co., the polycrystalline material was deposited at 2100°C on a substrate of synthetic graphite by decomposition of a dilute natural gas mixture. The as-deposited material had a density of approximately 2.19 g per cc, and as shown in Fig. 1 had a structure of medium size growth cones which were regenera-tively nucleated. All specimens had a gage section 0.75 in. long by 0.06 in. wide by 0.1 in. thick with the thickness direction perpendicular to the basal planes. The testing method and equipment used have been previously described, Ref. 2 and 3. For both the hot-working and the testing the load was applied parallel to the basal planes; a cross-head speed of 1.5 x l04 in, per sec was used. All heating was done in an atmosphere of bottled helium.

Jan 1, 1962

By R. Steinitz, J. L. Orehotsky

An analysis was made of the influence of floating molten zone traversal on the purification of tungsten rods and the effect of this purification on the brittle -to-ductile transition temperature. The major impurities detectable in the original rods, i.e., molybdenum and oxygen, were reduced by zone refining from 30 to 3 Ppm. Changes in the trace amounts of other impurities could not be quantitatively determined since they were below the limit of detection. Tensile tests on 3-mil wires, drawn from these rods and recrystallized to 17,000 grains per sq mm, showed a transition temperature of 60°C for the zone Purified and 175°C for the original material. 1 HE brittle-to-ductile transition temperature is manifest mainly in the bee metals, iron,' molybdenum, chromium,3 tungsten,4 and niobium. Since many of these metals cannot be fabricated at room temperature in a commercially pure annealed poly-crystalline state, a considerable amount of work has been done on evaluating the influence of purification on the transition temperature in order to determine indirectly whether the fabricability of these metals can be improved by removing impurities. Smith and Rutherford8 showed that the transition temperature of iron is lowered significantly by zone purification. Working with chromium, Edwards, Nish, and wain7 found also that purification appreciably lowered the transition temperature. A similar evaluation has so far not been reported for tungsten, probably because of the difficulties in obtaining tungsten in a purified polycrystalline state. carlson8 and, more recently, schadler9 have purified tungsten rods by floating zone traversal, but after zone traversal, their rods were single crystals. To obtain high-purity polycrystalline tungsten, a technique has to be round for transforming the zone-purified single crystal material into a suitable polycrystalline structure. The purpose of this investigation was to obtain zone-purified tungsten in a suitable polycrystalline state and then to evaluate the effect of zone purification on the transition temperature.

Jan 1, 1962

By R. C. Edwards, Will Mitchell, T. G. Kirkland

THREE years ago, when the Process Research Laboratory at Allis-Chalmers Manufacturing Co. sought a remedy for the increasing cost of disposing of great quantities of spent sands from foundries, R. C. Edwards developed a continuous inclined paddle scrubber which removed a substantial amount of the charred coatings from the grains with a surprisingly small amount of degradation of the sand itself.1 The satisfactory results obtained on foundry sand, using this piece of equipment in conjunction with classification, suggested that a similar procedure could probably be applied to the cleaning of other sands, such as those required by the glass and chemical industries. This paper describes the flowsheet and the results of tests performed on impure natural sands. The four materials tested were silica sands obtained from widely separated geographical areas. Three of the sands tested contained various amounts of iron oxide and the fourth an excessive amount of calcareous bonding material. The iron oxide was present predominantly in the form of grain coatings, which were scuffed by the paddle scrubber, and in all cases a product was manufactured which would meet one of the sets of specifications imposed by the glass industry' The Edwards paddle scrubber used in these tests consists of a rubber-lined steel cylinder 18 in. in diam and 48 in. long, mounted on a frame so that its slope can be varied 5 ° to 35º from horizontal. This variable slope permits controlled flow of material through the machine. Rubber paddles rotate inside the cylinder and are secured to a center shaft 2 in. square, which extends through the entire length and is turned at both ends so that it can be supported by sleeve bearings centrally fixed in the end plates of the shell. At the upper or feed end it extends through the bearing on the end plate into a sheave, to which the motor drive is connected by means of Texrope transmission. The four sets of paddles mounted on the shaft, two in each set, are made of rubber belting, 1/4 in. thick, 9 in. wide, and 16 in. long. The two paddles in each set are secured on opposite sides of the square shaft, but in the same longitudinal position along the shaft axis. In other words, the two paddles in the set operate 180° apart. Each successive set is mounted 90º from the preceding one. One end of each paddle is bolted to the square shaft and the other weighted by a steel bar, 1x1 ½ x9 in. long, which is attached about 1/ 2 in. from the outer tip of the paddle. By centrifugal force at proper shaft speed, these weights force the paddle surface to rub smoothly against the rubber lining of the cylinder. During operation, the sand forces its way between the paddle face and the surface of the cylinder, providing the necessary abrading action as the pulp flows by gravity down the length of the cylinder. The capacity of the machine is limited by the amount and the hardness of the coating material and by the quality of product desired. The degree of scrubbing is governed by the retention time in the scrubber, which in turn may be changed by varying the feed rate, water content of the feed, and

Jan 1, 1952

By Milton Williams

IT is generally recognized that fluid is lost from rotary drilling mud s to permeable strata during normal drilling operations;1,2,3 but that this fluid is the filtrate from the mud, rather than the mud itself, has been shown by various workers.1,4,5 . The presence of this filtrate in oil-bearing or gas-bearing strata is undesirable and harmful. The decreased permeability of the stratum to oil effected by the presence of water has been pointed out by several investigators,6,7 and since, in the production of the reservoir fluid, the greatest pressure drop occurs immediately adjacent to the borehole, it follows that infiltered water is particularly objectionable in this region. Again, this filtrate tends to make electrical logs less reliable, since oil in the proximity of the borehole is probably flushed out to an appreciable ent by the water.8 Observation of side wall cores may be misleading for the same reason. Drill-stem tests in low-pressure areas may be of doubtful value where no oil is recovered, unless sufficient time is allowed for production of water lost from the mud. The infiltered water may hinder drilling operations by softening shales and causing sloughing; the "tight hole" occasioned by excessive deposition of filter cake in the hole is a common occurrence. The filter cake remaining on the face of the producing formation may itself sometimes be detrimental to production.9 In view of these implications of the importance of filtration of mud, an investigation was undertaken to determine the factors involved in the infiltration process, and to correlate these in such a manner that the values obtained in routine filter tests employing a conventional filter of the "wall-building tester" type,10 together with data on size of hole, drill pipe, and rate of mud circulation, could be used to estimate water loss and distance of penetration of the filtrate into strata.

Jan 1, 1939

By Madan M. Singh, William J. Courtney

Pneumatic stowing is commonly employed in European coal mines, but is not used in the United States. This paper reports a study conducted to analyze the conditions under which pneumatic stowing might be advantageously used and the techniques and costs involved in order to effect this. Although stowing may reduce the subsidence in a mining area, this does not entirely eliminate the surface damage. Besides, the cost of stowing will run about $1.50 to $3 per ton of coal mined not including the cost of fill material, if it has to be bought and transported to the mine. Stowing my, however, be economically viable under special circumstances such as in thick, steep, or contiguous seams.

Jan 1, 1976

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Jan 1, 1938

By Archer E. Wheeler, Milo W. Krejci

The Boston & Montana Reduction Works at Great Falls, Mont., was formerly the reduction works of the Boston & Montana Consolidated Copper & Silver Mining Co., and continued as the reduction plant for the independent company until June 1, 1910, when the consolidation of a large number of the operating companies of Butte was effected. It then became merged in the Anaconda Copper Mining Co. as the Boston & Montana Reduction Department of the Anaconda Copper Mining Co. The history of copper converting at this plant, while not covering the entire period of the commercial use of the process in this country, does cover by far the larger part of it, and as the operation of and appliances for the process have undergone many changes during the time, it may, perhaps, be of some interest to put the record of these changes into permanent form. The plan followed in the preparation of this paper has been to give first a brief chronological record of the principal events and changes and then, even at the risk of some repetitions, to give more detaild accounts of some of these changes under separate headings. The headings for the complete paper are as follows: 1. General. Chronological Review. 10. Development of Different Classes 2. Mechanical Manipulation. of Converters After Class I. 3. Casting of Finished Copper. 11. Basic Lining. 4. Tamping of Linings. 12. Number and Size of Tuyeres. 5. Early Acid Linings. 13. Cast Copper Tuyeres. 6. Acid Linings With the Use of Ore. 14. Efficiency of Air. 7. Introduction of Flux Through the 15. Size of Converter Mouth. Tuyeres. 16. Height of Converter. 8. Bottom Blast. 17. Summary. 9. Disposal of Converter Slag, General Chronological Review. Ground was broken for the general concentrating and smelting plant in the spring of 1,891. The first departments to start operations were the concentrator in March, 1892, and the Brückner roasting and reverbera-tory smelting departments in April, 1892. The converter department

Jan 1, 1914

By J. B. Morrow

AMONG the most notable of Canada's many contributions to the personnel of the mining industry in the United States is J. B. Morrow, born in Halifax, Nova Scotia, April 9, 1886. Soon after completing his schooling at Dalhousie University in 1906 he emigrated to Arizona and Kew Mexico, via Cobalt and Larder Lake, Ontario. After preliminary experience in sampling and mucking he was employed by the Phelps Dodge Corp., first as chemist at the Copper Queen smelter, then, in 1908, with the Corporation's Stag Canyon coal branch at Dawson, N. M., in various capacities fro111 chemist to coke oven and coke department superintendent, and finally as general outside superintendent. While with Phelps he had some contact with the late Dr. Douglas, of whose industrial methods he has always been a great admirer.

Jan 1, 1937

By O. F. Kammerer, W. E. Miller, D. H. Gurinsky, J. Sadofsky, J. R. Weeks

Zirconium and titanium inhibit solution mass transfer of steels by liquid bismuth, mercury, and lead. It is shown that in bismuth and mercury, these adsorb on the surface of the steels and subsequently react with nitrogen and possibly carbon from the steels to form inert, adherent surface layers of ZrN, TiN, or TiN + Tic. Data are presented which describe the condition under which thase deposits form. These inhibitors decrease the solution rate of iron into bismuth, and require a higher supersaturation for precipitation of iron from bismuth. USE of the low-melting heavy metals (bismuth, lead, mercury, and their alloys) as coolants has been limited because solution mass transfer of steels occurs in these liquids; i. e., iron dissolves in the hot sections of the heat transfer circuit and deposits in the colder sections. The rate of solution of iron and the temperature coefficient of solubility are sufficiently great to cause complete or partial stoppage by the deposition in the coldest section of a closed circuit in finite time, even though the actual solubilities are extremely low. In the development of the mercury vapor turbine by the General Electric Co., Nerad and his associates1 discovered that the addition of as little as 1 ppm Ti or Zr to magnesium-deoxidized mercury reduced the mass transfer of ferrous alloys by mercury to a negligible amount. Reid2 reported that titanium was detected chemically on the surface of steels contacted with this mercury alloy in amounts varying from 2.0 to 2.6 mg per sq in., the greatest amount being found in the hottest portion of the circuit. Reid stated that the titanium forms the intermetallic compound Fe2Ti by reaction with iron on the surface of the steels. This compound was presumed to be highly insoluble in mercury. More recently, El-gert and Egan3 have reported a greater than 100-fold reduction in the rate of mass transfer of a 5 pet Cr steel by liquid bismuth upon the addition of titanium (in excess of 50 ppm) and magnesium (350 ppm) in the liquid metal, during experiments performed in thermal convection loops* over the temperature differential 700° to 615° C. Also, Shep-ard and his associates' have reported that the addition of titanium to liquid bismuth and Pb-Bi eutec-tic produced a marked decrease in the rates of solution of both iron and chromium from type 410 steel capsules under static conditions. This inhibiting effect increased with repeated reuse of the capsules. Tests performed in this laboratory under carefully controlled conditions have shown that the addition of zirconium and magnesium, or titanium and magnesium, to liquid bismuth or lead greatly reduces the rate of mass transfer of chromium alloy steels and carbon steels in thermal convection loops with a maximum temperature of 550°C.5-9 The present paper will review the data obtained to date at this laboratory on the behavior of iron and steels in contact with liquid bismuth alloys containing titanium or zirconium, and will attempt to explain the role of the above additives in reducing solution mass transfer. Reaction between the Zirconium or Titanium Dissolved In Liquid Bismuth and an Iron or Steel Surface Reaction between Zirconium Dissolved in Bismuth and the Surface of Pure Iron-—A small pure iron crucible (analyzed by the supplier to contain 0.8 ppm N was contacted with bismuth containing approximately 0.1 pet Mg and varying amounts of a radioactive zirconium tracer. The crucible was then inverted at the temperature of contact. The thin residual layer of adherent bismuth was dissolved in cold, concentrated nitric acid. The crucible surface and the solidified bismuth were then analyzed for radioactive zirconium. An analysis of the activity loss on the crucible surface and the weight loss of the crucible during the nitric acid treatment showed that the acid treatment removed the zirconium that had originally been dissolved in the adherent bismuth, but not any zirconium that may have reacted with the crucible surface. The crucible was then pickled in warm aqua regia to remove all surface activity, hydrogen-fired at 600°C, and recontacted with a new liquid alloy. The results of the experiments contacted 1 hr at 450°C show, Fig. 1, a Langmuir-type adsorption with an adsorption free energy of approximately 17 keal per g atom Zr.5 This deposit was estimated to contain 1 atom of zirconium for each 7 to 8 iron atoms on the crucible surface, assuming a surface roughness factor of the pickled crucibles to be five. Increasing the temperature to 520°C caused consi-

Jan 1, 1959

By I. Milton LeBaron

OPERATION of the phosphate flotation plant at the Peace Valley mine of the International Minerals and Chemical Corporation, Florida, began in the summer of [ ] 1942. Since that time several changes have been made in the flowsheet, with resultant increases in metallurgical results. Three flowsheets, together with the comparative plant results, are given in this paper, together with a discussion of the desliming circuit used for preliminary washing of the flotation feed. FIRST FLOWSHEET CHANGES Fig. I lists the essential units in the original flowsheet at the Peace Valley plant. The figures for tonnage and grade are average for a period of two months. Mineral Separation Airflow cells are used for both the fatty acid and the amine float. Three immediate difficulties presented themselves in the use of this flow sheet: I. Floating a maximum amount of phosphate in the rougher section to give good recovery sent a low-grade concentrate to the silica float, resulting in high costs for amine reagent in that section.

Jan 1, 1946

By James E. Harding

The usual method of sampling mineral deposits is to drill holes and assay the sludge or core. Though the results thus obtained may not represent the true average value of the deposit, it is on these results that estimates of practically all large orebodies are made. In a large number of cases, the results of exploitation fall far short of the estimated value of the orebody. The standard method of making these estimates is to find the cubic contents of triangular prisms, in the apexes of which the drill holes are placed, by. multiplying the surface area by the average depth of the ore in the three drill holes and then multiplying the cubic contents by the specific gravity of the ore or rock to find the tonnage. The assay value is found by dividing the sum of the products of the depth of ore in each hole and the corresponding assay value by the sum of the depths of the ore in the three holes. As the latter part of this method is subject to many mathematical errors, it should not be depended on. Some engineers, therefore, use a discount factor, but as this factor is either arbitrarily selected or is obtained by obscure methods, the results are no better than guesswork. The standard method is correct when the drill holes are so laid out that the triangular prisms are equilateral in cross-section. But as ore deposits cannot always be drilled into at regular intervals and because of the human factor, if many holes are drilled, triangular prisms of all degrees of angularity are produced. In such cases it is necessary to assume that the influence of the different holes is not the same in all directions, which assumption of course is absurd. The area of the triangular prism is usually found by scaling; an ore-body of sufficient size to justify churn drilling is too large to be handled conveniently on maps having a scale larger than from 1000 to 1 to 1,500 to 1 and maps of such scales cannot be accurately measured. A variable is thus introduced in the first operation. In addition, the scaling is frequently done from blueprints, which sometimes shrink as much as 4 per cent. between printing, washing, and drying. The error due to scaling may be eliminated by surveying the location of each hole and

Jan 1, 1922

By J. A. Capp

For certain classes of electric railways a steel conductor is preferable to the oldcr atld more commonly used overhead trolley-wire. The third-rail presents a rather better appearance, because of the absence of an overhead structure; it is easily installed, cheaply maintai~ied, presents s large area for conducting and collecting the current, and is therefore particularly suitable for high speed and heavy service. With costs calculated on the basis of equal coilductirity in rail aud trollej-wire, the third-rail constrrictiol~ is cl~caper than thc overhead trolley. But the average interurban road will lise a trolley-wire of considerably less conductivity than would be obtained with the smallest size steel rail (about 60 lb. per pard) that mould ordinarily be used, and here the first clost of trolley construction would generally be less thau that of the third-rail. While no third-rail installation has jet bee11 in operation long enough to give figurcs of value, it ~vould appear that the cost of maintenance of the thirdrail construction should be less than that of the overhead trolley. This consideration, together with that of sightliness and adaptability (particularly in the case of terminals, yards and very heavy or high-speed service), will frequently off'set the higher cost of the third-rail construction and make it the preferable means of' conducting the current from thc generator to the car-motor. For the first third-rail installations, old track rails were used when obtainable, and these old rails were supple~rlented with new rails of standard T-section and composition. With the coming of the very heavy, high-speed service during the past few years, the resistance of these old and new standard T-rails was found to be so high that they mould not carry the high currents necessary without too great a drop in the line-potential. The rails would, therefore, have to be suppleme~~ted with addi-

Jan 1, 1904

By Roger G. Rowe

In late 1980, Exxon Minerals Company performed rock mechanics testing on oriented 150 mm drill core from their 75Fi tonne massive sulfide deposit near Crandon, Wisconsin. Instrumented samples from depths of 300 meters indicate premining horizontal stresses in a north-south direction (parallel to pillar faces) to average 12,300 kPa, with the perpendicular plane yielding an average stress of 14,630 kPa. Rock strength versus sample size was compared using uniaxial compressive strengths from 47 mm, 95 mm and 150 mm core. Massive sulfide averaged 153,300 kPa, 139,845 kPa and 75,330 kPa respectively, while the hanging wall and foot- wall averaged 92,000 kPa, 76,560 kPa and 57,960 kPa respectively. Point load compressive strengths were calculated using formula suggested by both Hassani et al., 1980 and Broch et al., 1972. Values calculated using the Hassani formula closely resembled pre- existing point load and uniaxial compressive strengths, while values calculated using the Broch formula were 50 percent low.

Jan 1, 1982

By M. A. Steinberg, J. Wulff, R. Kamm

In a previous paper1 from this laboratory, the development of a lead grid method for exploring the distribution of strain and density within metal powder compacts was described. In that work thin lead foil with rectangular holes cut at regular intervals was inserted with the powder fill, the arrangement pressed and then radiographed to permit measurement of the deformation of the lead grid. Densities at each grid element obtained in this manner were plotted as a function of the die dimensions. From such plots it was found that the densest part of a compact pressed from one side (the top) is at the top outer region and the least dense at the bottom outer region of the specimen. The axial density maximum occurs more often nearer the bottom than at the top. As a result of such exploratory measurements, it appeared reasonable to conclude that variations in density could be attributed in the main to die wall friction. Thus compacts of large diameter appeared relatively uniform in density except where the die fill had been uneven. Finally it was found that lubrication of the finely finished die cavity contributed more to magnitude and uniformity of density within the compact than interparticle lubrication. Since publication of the above results, it was found that circular-hole grids could be more accurately made and, when deformed within the powder, more readily measured and analyzed. Much of the former work was repeated and new results which include the effect of lubrication, compact height, pressure, speed of pressing and vacuum pressing are reported in the present paper. Circular-hole Grids and Analyses OF Radiographs Commercial lead sheet 0.008 in. in thickness was used in all the work reported. The 0.0938-in. diam holes were punched in the sheet on 1/8-in. centers to an accuracy of 0.001 in. The finished grid used contained eight or more holes in a row and from I to 24 rows. The lead sheet was clamped between two pairs of brass strips bolted to a small milling machine table which was itself bolted to a bench in correct position near a vise which held the punch. Travel of the lead grid in two dimensions was controlled by two steel lead screws calibrated in 0.001-in. divisions. A stripper plate was used on the punch to avoid distortion of the lead foil. A high carbon-high chromium (chrocar) one-piece steel die was used throughout the work. The die cavity was 1.125 in. in diam and the clearance between plungers and die wall was 0.001 in. The die was also used for pressing from both ends with two long plungers. Finally, lapping of die and plungers gave a surface whose rms value On an Abbot profilometer was 5 micro-in. The die walls and plungers were, except where otherwise noted, lubricated with a stearic acid suspension in benzene. This was put on in multiple layers and allowed to dry before filling the die.

Jan 1, 1949

By Evan Just

DIRECT subsidies for mine production in this country began as an outgrowth of wartime 'price regulation. The price-fixing authorities realized that the volume of production to be required from domestic copper, lead, and zinc mines would invoke costs of production considerably higher than the established ceiling prices. Accordingly, beginning Feb. 1, 1942 the Premium Price Plan was set up, which undertook to pay premiums to mines for production in excess of quota, of 5¢ per lb of copper and 2Y4¢ per lb of zinc or lead. Quotas, except for small mines, were initially established at the average rate of production in 1941, but were later reduced arbitrarily on an individual basis. Subsequently, additional "B" premiums were set for lead and zinc of 2Y40 per lb and a further "C" zinc premium of 2%¢. Additional copper premiums were negotiated on an individual basis, mainly with small mines. Quotas under each of these successive categories were the production obtained at the next lower premium level. In other words, under ceiling prices of 12¢ for copper, 6,14¢ for lead, and 83¢ for zinc, it was possible for high-cost operations to receive prices plus premiums of 17¢ or more for copper, 12¢ for lead, and 16% 0 for zinc on a portion of their production. On the other hand, some of the larger operators received only slight premiums and in at least one instance none at all. The average price plus premium for copper was 12.25¢ in 1942 and rose to 13.65¢ in 1945. That for lead was 6.99¢ in 1942 and 8.73¢ in 1945, and for zinc it was 9.06¢ in 1942 and 11.200 in 1945.

Jan 1, 1948

By J. Nutting, D. H. Kirkwood

The oxidation of lead sulfide in air between 200° and 350°C has been investigated by electron diffraction from thick sulfide films and from galena surfnces. It has been demonstrated that sulfate is the stable reaction product up to 570°C. Sulfate is HAGIHARA has investigated' single crystals of galena roasted in air by the reflection electron-diffraction technique, which owing to the very limited penetration of the beam into the crystal gives information of the nature of the surface only. He has shown that up to 280°C the first oxidation product is lead sulfate, followed by lead mono-oxysulfate (PbO . PbS04). At longer times and higher temperatures more complex patterns appeared which could not be analyzed. All of these patterns were of streaks or spots arising from crystals oriented on the galena surface, and it is probable that these crystals are lead compounds whose structures have not been determined, such as the other oxysulfates (2Pb0 • PbS04 and 4Pb0 . PbS04) or a number of oxides. Certain lead sulfide films, formed chemically, give ring patterns in transmission electron diffraction2 because they are polycrystalline, and should also give ring patterns of the products after oxidation. It was thought that a diffraction study would reveal the sequence of phases produced in the reactions at different temperatures, since X-ray powder patterns are available for many lead compounds. PREPARATION OF FILMS The films were prepared by passing H2S over a saturated solution of lead nitrate in water. Once a silvery film had formed on the solution surface, no further thickening was apparent. The films were transferred by a gauze to a bath of distilled water for washing and pieces of film were caught on small discs on which they were dried. The discs were formed initially on galena up to temperatures of 300°C, followed by oxide and oxysulfates in turn at longer times. The appearance of- these phases is believed to result from an inadequate rate of supply of sulfur to the top surface 01. the crystal. standard Siemens mounts, made of platinum alloy, and had seven 20-p apertures drilled through them. The parts of the film which had dried onto the disc surface were light blue in color, which is the interference color of a film about 600A in thickness. A strong pattern of lead sulfide was obtained in transmission electron diffraction through the apertures but slight broadening indicated a crystallite size of around 200A. Tilting a sulfide film in the beam produced arcing of the rings, increasing the intensities of the (Ill), (3111, and (222) rings and reducing (200) and (220). This arises from preferred orientation in the film, a [loo] direction of the crystallites being normal to the plane of the film. These specimens were oxidized in an oven maintained at the required temperature. The reported times include that taken to heat the film to the reaction temperature. STABLE PHASES FORMED IN OXIDATION The conditions in which various oxidation products of lead sulfide are stable have been considered by the authors in a previous paper.3 It was shown that in a normal atmosphere, taken as containing lo-' atm of SOs, lead sulfate would be stable up lo about 570°C. This was confirmed by oxidizing thin films of sulfide for several days, and the analysis of the transmission-diffraction pattern is given in Table 1. The fit with the patt$rn from X-rays is good, except for the missing 3.62A ring. Some disagreement in intensities of reflections given by X-rays and electrons is to be expected. Up to 570°C a spotty pattern of sulfate was still obtained, indicating grain growth, but above this temperature the film disintegrated. Probably this is associated with the decomposition to PbO . PbS04. It needs to be emphasized that the atmosphere

Jan 1, 1965

By Noel Jarrett, Allen S. Russell, Bernard M. Starner, Stanley C. Jacobs

A process has been developed to refine high-grade commercial aluminum to 99.99 pct purity. This enzploys precipitating titanium, vanadium, and zirconiu~ as borides. The upgraded liquid is partially crystallized under conditions that prevent massive freezing. The resulting crystals are compacted and washed free of adhernig impure liquid aluminum by melting the top crystals while draining off the liquid. Finally, the bottorn portion of the crystal bed is melted and removed as the pure product. Leakage from the crystallizat~on vessel is prevented by a layer of alumina granules that are not wetted by the aluminum. ALUMINUM of 99.99 pct purity is desired in a variety of applications. These include electrolytic capacitors, catalyst carriers, decorative trim for automobiles, aluminum powder, and high-strength alloys. This market was for many years filled by refining commercial-purity aluminum in a three-liquid-layer electrolytic cell of the type originally proposed by Hoopes. To meet the expanding need for lower-cost high-purity aluminum, a refining process based on chemical precipitation and fractional crystallization was developed. The availability of this super-purity metal was announced in November 1961, and three patents1-3 relating to the process were issued in 1965. An alternate process, comprising continuous fractional crystallization of a portion of a liquid-aluminum feed stream under conditions of strong agitation at the surface of the growing crystals, was published by Dewey4 in 1965. Earlier proposals by Larsen 5 and by Regner6 also emphasized the advantage of rapid agitation of the melt in the region of the crystallization zone. johnson 7 more recently proposed extracting purified aluminum from an alloy by mixing crystals of pure aluminum into the molten alloy, allowing them to grow, and removing the pure aluminum as by casting. Aamot's 8 recent patent describes a freeze refining process that involves controlled partial freezing against cooled moving retort walls. The Alcoa process to produce high-purity aluminum is schematically described in Fig. 1. Relatively pure aluminum is treated with boron in a furnace (a) to precipitate high melting point impurities, the supernatant liquid is transferred to a crystallization vessel (b), the liquid is partially crystallized with mechanized "tamping" (c), the remaining impure liquid is tapped out and the crystal bed partially and directionally re-melted to wash the underlying crystals (d), and the balance of the crystals is melted and withdrawn as high-purity aluminum (e). PRINCIPLES OF FRACTIONAL CRYSTALLIZATION Commonly encountered impurity elements form two types of systems with aluminum. Titanium, vanadium, and some other transition elements in periodic groups IV, V, and VI are the high melting point impurities. Initial solidification of aluminum containing small percentages of these elements will produce solid markedly enriched in them at temperatures slightly above the freezing point of high-purity aluminum. Most other elements, such as silicon and iron, produce eutectic type reactions with aluminum. In this case the first solid formed on initial solidification at temperatures slightly below the freezing point for high-purity aluminum is markedly depleted while the remaining liquid is enriched in these elements. The equilibrium change in composition during solidification of aluminum contaminated with silicon, iron, or titanium is illustrated in Fig. 2. Here, for clarity, the temperature scale is expanded beyond the

Jan 1, 1968