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By B. Silliman

THE remarkable outflow of natural gas recently developed in Western Pennsylvania, and along the valley of the Ohio and its tributaries, has called attention to an important series of patents for improvements in glass-fnrnaces and the manufacture of glass, which the brothers Siemens have made since 1872. The basement-patent of this series, is No. 127,806 of the U. S. Patent office, and is of date June 11th, 1872. This has been followed by eleven other patents (including one re-issue), all for improvements in glass-furnaces, or methods of manufacture, of which the latest is of date July 11th, 1882. Nine of these patents were issued in 1880-82. The following is the list of these patents, in order of dates, viz.: 1872. June 11th. No. 127,806 (U. S. office), Improvement in glass-furnaces; 17 sheets drawings, 5 pages text. This is the basement-patent. 1877. April 17th. No. 139,800. Improvement in the manufacture of glass; 3 sheets drawings, 2 pages text. Boats and floating vessels swimming in the liquid glass of the tank-furnace. Re-issued in 1880. q. v. 1880. April 27th. No. 226,931. Furnace for annealing and tem pering glass. " July 13th. No. 220,846. Glass-melting-furnace. " August 3d. No. 230,668. Glass-melting-furnace; 4 sheets drawings, 2 pages text.

Jan 1, 1885

Electro-mechanical actuator, self-protected for mechanical and electrical overload, is developed by RACO. Tubular housing consists of squirrel cage motor with hollow rotor shaft and inner threads in the rotor. Features stroke distance of 2-72 in. and wide range of trust (20 lb-10 tons). (100) Agglomeration systems, offered by Ferro-Tech, incorporate pelletizing, briquetting and extrusion systems to agglomerate materials too fine to convey, load or feed to a process. Equipment includes disc and drum pelletizers, briquetter presses, compactors, extruders, pugmills and mixers, dryers, coolers, feeders and conveyors. (101)

Jan 9, 1973

By J. K. Brooke, F. A. Renninger

During 1966, crushed stone production in the United States totaled just over 811 million tons valued at almost $1.2 billion. This represented in- creases of 4 % in tonnage and 5 % in value over that for 1965. Excluding the crushed stone used for agricultural and certain industrial purposes (cement, lime and flux), crushed stone mineral aggregate production totaled 616.3 million tons valued at almost $910 million, also up roughly 4% in tonnage and 5% in value over the 1965 figures. Limestone was by far the most widely used rock variety, followed by basalt, granite and sandstone in that order. Concrete aggregate and roadstone continued as the main uses for stone, accounting for 63% of all tonnage produced in 1966 and 60% of total stone value. Sand and gravel production in 1966 increased 3% over that for 1965. Total 1966 output was just in excess of 934 million tons valued at almost $985 million as compared with 908 million tons at $957 million for the previous year. Excluding the higher valued industrial sands, 903.2 million tons of sand and gravel valued at $891.6 million were used directly as mineral aggregates, representing a 2.9% increase in tonnage and a 2.4% increase in value over 1965.

Jan 2, 1968

In introducing last year's Industrial Minerals Review, Stan Lefond accurately predicted that the 1974- 75 period would be quite difficult and frustrating. Although 1974 demand and prices for most industrial minerals were exceptionally strong, operating costs also rose rapidly-while shortages of supplies and equipment, symptomatic of an overheated economy, occurred from coast to coast. Thus, at the end of 1974 recessionary forces were accelerating-and the minerals industry will soon be facing falling demand as a consequence of sharp declines in auto production, housing, appliances, and other consumer goods. Moreover, when sales weaken, the high-volume, low-prices industrial minerals will incur sharply increased unit costs. To maintain adequate profit margins under these conditions will require cautious and perceptive management.

Jan 2, 1975

By C. K. Leith

In discussing the subject of mineral exploration, one is tempted to resort to reminiscence. I could tell of many missed opportunities, but I propose rather to outline certain changes in the methods and conditions of exploration which present new problems to the mineral explorers of today. Our subject might appropriately be called The Passing of the Old Time Prospector. The first question that presents itself is whether the job of mineral exploration is not already pretty well finished. The current market surplus of most minerals and the present overcapacity for production, with their attendant financial troubles, naturally raise the question whether the accumulation of reserves has not gone far enough for the present, and whether further exploration should not be left to some future time when consumption shall have caught up. Unquestionably we have gone far in the conquest of our physical environment, and the fear of shortage of minerals is less than formerly. For the time being there is no great need of further supplies for the world as a whole of many of the great essential minerals, coal, oil, copper, zinc, silver, and others. For a few minerals, such as gold and lead, the known future world supplies are not yet large enough. For all minerals the distribution is so unequal among the nations that exploration will continue in deficient areas in the attempt to make nations self-supporting.

Jan 1, 1932

By Charles Schwab

WHEN I leave this life, as an employer of labor there is no one thing that I want so much to be engraven upon my monument as the fact that I have been one of the men who have worked, whether with my brains or my hands, for the advance-ment of industry in the United States, and to be regarded, as I should like to be regarded by labor with love and kindly remembrance for our years of association. In my relationship with my employees, I have always contended that every man should be paid for what he does. I will not employ or be associated with any kind of labor of which the organization insists that a man shall receive a fixed sum of money for his day's wages, however poor or good his day's labor may be. What applies to the common laborer applies equally well to the management, the brains of an industrial establishment. I have always thought of industry as a three-legged stool, with capital, management and labor as the legs. All three legs of that stool must be there before that stool can stand up. If you take any one of those legs away, it is going to topple over. The. three must stand together for successful business accomplishment. I believe that a man who has his labor to sell, to put it plainly, has just as good a right to bargain for the best price for that labor as those who employ him. It is a perfect right for him to do so. If the government of our United States is right, our method of handling labor in our Bethlehem plants is right because it is representative and democratic. We have our labor elect delegates; elect representa-tives from their own ranks, who shall meet frequently. That constitutes, as. it were, the House of our great Congress in Washington, the industrial house. We have our management, who represent the Senate, who meet independently. Working men have learned to express their views freely as to whether they are treated fairly and whether conditions are right or wrong.

Jan 12, 1922

By Stanley J. LeFond, Langtry E. Lynd

Elemental titanium has become famous as a space age metal, because of its high strength/ weight ratio and resistance to corrosion. However, the major use is in the form of titanium dioxide pigment, which because of its whiteness, high refractive index, and resulting light-scattering ability, is unequaled for whitening paints, paper, rubber, plastics, and other materials. A relatively minor use is in welding rod coatings, in the form of the mineral rutile. United States consumption of titanium dioxide in concentrates for these applications in 1982 was as follows: pigments, 630,000 st; titanium metal, 31,000 st; and welding rod coatings, 5,000 st. The only commercially important titanium ore minerals at the present time are ilmenite and its alteration products, and rutile. Titanium was discovered by Gregor in 1790, as a white oxide which he recovered from menaccanite, a variety of ilmenite occurring as a black sand near Falmouth, Cornwall. Barksdale (1966) stated that the fundamental chemical reactions on which the present day titanium industry is based were known before 1800, although it was not until 1918 that these pigments were available commercially on the American market. Pings (1972) outlined the early history of the titanium industry in the United States, referring to the work of Guise (1964) and others: Mining of titanium minerals in the United States began sometime between 1880 and 1900, in Chester County, Pennsylvania. Small quantities of rutile were also produced during that time in North Carolina and Georgia. In 1901 rutile was mined from a deposit near Roseland, VA, and was used in making titanium chemicals and for coloring ceramics. Ilmenite in the deposit was produced as a separate item in 1913, and rutile and ilmenite were obtained from this deposit through 1921. The mining of titanium bearing beach sands began in 1916 near Mineral City and Pablo Beach, FL, for the purpose of making titanium tetrachloride to be used in tracer bullets, flares, and smokescreens. The titanium pigment industry was founded in 1918. By 1928 a large part of the domestic production of rutile, ilmenite, and zircon came from Florida. However production ceased in 1929 in Florida with the mining of newly discovered deposits in Virginia which were mined until 1968. The discovery of new deposits in Florida, and the development of better mining and concentrating methods for low-grade sands, led to a return of activities in this area. The large deposits near Tahawus, NY. were brought into production in 1942 by National Lead Co. (now NL Industries, Inc.), and by 1949 this company was the leading producer of ilmenite in the world. In 1948 the extensive deposits of ilmenite and ilmenite-bearing iron ores were discovered in eastern Quebec. The large Trail Ridge sand deposit in Florida was discovered by E. I. du Pont de Nemours & Co., Inc. geologists in cooperation with the US

Jan 1, 1983

By N. P. Goss

ASTERISM appearing in X-ray Laue dia-grams is an extremely sensitive index of changes in the internal structures of indi-vidual grains of polycrystalline metals. It indicates the existence of various forms of subboundary structure or subdivision within the grain. The present viewpoint is that the grain is made up of lattice blocks having substantially the same size and shape.1-4 When these blocks all assume exactly the same orientation, the crystal is perfect and asterism is absent. Cleaves and Thompson5 observed that the hardness of iron is virtually constant over a range of grain sizes. It is quite possible that the subboundary structure caused this, and that the latter is just as important as grain size itself. While the experiments reported here are not con-clusive, they do support this viewpoint. Metals can, under certain conditions, be prepared entirely free from asterism, but this preparation does not necessarily require long heating or slow cooling, as will be shown here. In this paper a distinction is made be-tween mosaic and distorted grain struc-tures but the difference is only a matter of degree. In a previous paper9 it was shown that the grains can become distorted even during heat-treatment. The block structure exists inherently, even in a perfect crystal; the size and shape of these crystallites, or lattice blocks, varies, depending upon a number of factors. Goetz, for example,7 has shown that a metal before crystallizing from the molten state must go through a paracrystalline phase with oriented groups of atoms about 10-14 to 10-15 c.c., or 10 5 cm. in size.

Jan 1, 1940

Jan 1, 1966

By Ian Wark

IT has been shown1 that in the absence of heavy metal salts, the nature of the alkali used to promote differential flotation-whether caustic soda, lime or sodium carbonate-is unimportant. The hydroxyl ion is the active depressant upon which differentiation depends, and the pH value determines whether a film of collector forms on any given mineral surface. Even when sodium cyanide is used in conjunction with alkalies, it is the pH value and not the nature of the alkali or its concentration that is important, for upon the pH value alone depends the fraction of the added sodium cyanide that is present as cyanide ion, which is the true depressant. When heavy metal salts become dissolved from partly oxidized ores, or are added intentionally as activators, conditions are different, and metallurgists have found that lime and sodium carbonate do not give identical results, even when added in amounts sufficient to produce the same pH value. In the few instances in which we had attempted to confirm this view, we had failed to do so, for, with nothing to guide us, we had inadvertently chosen solutions that gave contact curves of a "stand-ard type," which correspond to conditions of ready floatability. Now, however, we find that, in the presence of copper salts, and within a restricted range of reagent concentrations, the nature of the anions present is important, and that sodium carbonate does influence the results, apart from the usual effect due to its influence on pH value. With the recognition of this anion effect, and with the control of temperature already introduced,' it appears that the factors of major importance in connection with this set of reagents have been taken into consideration, and that the results obtained and the conclusions drawn from contact tests will be of more immediate value to the operator.

Jan 1, 1939

By John Wulff, David A. Stevenson

The rates of solution of copper, nickel, and three copper-nickel alloys in liquid lead were studied at 527° and 727°C under dynamic conditions. The relative velocity at the solid-liquid interface was varied from 8.65 to 125 cm per sec. Analysis of the data for the pure metals indicates that the solution rate is transport corztrolled at lower velocities, but a transition to mixed control occurs at higher velocities, higher temperatures, and higher percent saturation. 1 HE present work concerns the effect of relative velocity at a solid-liquid interface on the dissolution kinetics of pure solid materials in liquid metals. This general problem is of interest in electrode kinetics, in electrolytic processes, and more recently in the field of liquid metal corrosion. Considerable work has been done on dissolution kinetics in aqueous environments because of the obvious importance to electrolytic processes.1,2 In purely metallic systems investigation has been more limited. There are, of course, extensive data from loop tests which are used in an engineering evaluation of liq- uid metal corrosion. Here, however, the dissolution process is complicated by several interdependent processes. In general, one of two factors is considered to be rate limiting in the dissolution process: the transport of material from the solid-liquid interface into the bulk liquid, or an activation process directly at the interface. A number of studies of the dissolution rates of solid metals in liquid metals under static conditions have been published.3- Since the attendant hydrodynamic conditions imposed by thermal gradient convection and concentration gradient convection are difficult to analyze, it is doubtful if a clear interpretation of the experimental findings of these papers in terms of the mechanism involved in the dissolution process can be made. A clearer picture of the dissolution process is provided by

Jan 1, 1962

By Klaus Detert

Fifteen and 18 pct Ni maraging steel and several binavy and ternary alloys of the iron-rich corner of the Fe-Co-Ni system have been studied. After annealing in the austenite range, these alloys were deformed slightly by cold rolling and subsequently aged. Compavison of experimental measurements at various processing stages indicates that small degrees of deforn~ation (5 to 10 pct reduction in thickness) do not influence hardness and strength or the aging kinetics. Electrical resistivity and ductility are somewhat redu]ced and the coercive force is substantially lower when compared to identical samples which were not deformed. The results are explained in terms of retained austenite which transforms into martensite with the small amount of deformation. RECENTLY there has been increasing interest in maraging steel for applications in electric power generators requiring a high ratio of power to weight.' Fifteen pct Ni maraging steel has been investigated to evaluate its properties and performance for application as high-strength magnetic rotor steel,' and a thorough investigation of the precipitation and transformation processes in this alloy has been conducted in this laboratory.3 The influence of deformation, which preceded the aging treatment, was also studied. It was found that a small deformation in the order of 5 pct has a rather striking effect in reducing the coercive force. Other interesting effects on the properties caused by such deformation have led to the more detailed studies reported herein. EXPERIMENTAL METHOD The methods used to produce the samples from 15 pct Ni maraging steel have been described elsewhere.3 The general procedure of hot forging and cold rolling to sheet has been followed. The composition is included in Table I which also contains the composition of the 18 pct Ni maraging steel grade 250 studied. More data about the material and the processing of the 18 pct Ni maraging steel have been recently reported.4 The experimental alloys of binary and ternary Fe-Ni-Co alloys were made by levitation melting in an argon atmosphere and casting into rod-shaped ingots 7 mm thick weighing 20 g. From these ingots 25-mm-long rods were machined to study the phase transformation by a dilatometer. These rods were then cold-rolled to strips, 2.4 mm thick. Annealing for austenitizing was done in tube furnaces in an argon or helium atmosphere followed by cooling in the water-cooled portion of the tube. Aging was done in a salt bath containing a neutral blend of Alkali nitrates and nitrites. Vickers hardness was measured using a load of 50 kg for 15 sec. Tensile tests were carried out on a hard beam tensile tester at a strain rate of 5 X lo-' per sec using flat samples with a gage length of 37.5 mm and a cross section of 1.25 by 6.25 mm. Estimated sensitivity was 5 K x strain and 0.35 kg per sq mm stress. Magnetic saturation was determined on small cylindrical samples, 2.5 mm in length and diameter, by measuring the force exerted by the gradient of a magnetic field of 1000 oe per cm in a mean field of 11,500 oe. The measured values could be reproduced within *1 pct. Coercive force was measured by a precision-type magnetic field probe in a magnetic coil as described by Foerster.5 The magnetizing field was 1300 oe. The samples were 5 cm long, 1 cm wide, and 2.4 mm thick. he coercive force was measured to within +0.1 oe. Electrical resistivity was measured by using a potentiometer on flat strips with a gage length of 100 mm and a cross section of 2.5 by 0.5 mm. The accuracy of the measurement was 0.1 pct but the reproducibility of the measured specific resistivity among different samples was in the order of 1 pct. The method used to prepare the samples for electron transmission has been reported elsewhere.3 RESULTS Fig. 1 shows the influence of deformation after annealing on the resistivity, hardness, and coercivity. The samples were annealed for 30 min at 1000"C,

Jan 1, 1968

By C. H. North, L. E. Lynd, W. W. Anderson, H. Sicurdson

D. R. Grantham (Institute of Mining and Metallurgy, London, England)—This paper is a very valuable contribution to our knowledge of ilmenite and its alteration products. Two aspects are not treated in the paper and further information would be valuable. How far are the alteration processes described influenced by the original composition of the ilmenite? The word gangue is used but it is not clear whether this refers to other chemical constituents in the ilmenite, e.g., magnesia, or to other minerals loose or in composite grains. Has the work described been related to specific gravities? Pure ilmenite is stated to have a specific gravity of 4.79. Some varieties range up to over 5.0, while high magnesic varieties have a specific gravity ranging to below 4.2. Alteration to hematite might lower the specific gravity and a porous texture due to the removal of iron and the formation of rutile might also lower it. As specific gravity is a quick method which often gives an approximate indication of composition, data on the above would be valuable. L. E. Lynd (authors' reply)—Because of the way in which beach sand deposits were formed, it is impossible to tell exactly what the original composition of the parent ilmenites might have been. Information on the influence of original composition on the alteration processes must be derived from other sources, perhaps by comparing the alteration products formed from ilmenite in place in a variety of rock deposits, where parent ilmenite and its alteration product can be recognized. No information of this type has yet been brought to our attention. The material referred to as gangue includes all constituents other than oxides of titanium and iron. Nearly all of this was present as separate grains of garnet, augite, hornblende, quartz, feldspar, spinel, or other gangue minerals. Inclusions of gangue minerals within ore grains were rare, and we believe there is little MgO (1 pct or less) or other impurity actually held in the ilmenite structure in any of the concentrates studied. No specific gravity measurements were made on the samples studied. However, the suggestion that alteration involving loss of iron would lower the specific gravity is a very reasonable one, and is in accord with the findings of Creitz and McVay (Ref. 9 of our paper) who reported two magnetic opaque fractions from Trail Ridge, Fla., to have the following specific gravities and pompositions: The specific gravity of this porous, high TiO² alteration product of ilmenite is closer to that of rutile (4.25) than to that of ilmenite. Due to the porosity, it may even be less dense than rutile, although lower in TiO² and higher in iron.

Jan 1, 1955

By Hans W. Brodbeck

The main problem in tunneling without the use of explosives lies in the development of tools capable of continuous mechanical destruction of rock, resulting in a fragmentation which lends itself to a smooth, uninterrupted transportation of the broken rock away from the tunnel face. While all moles of U.S. design mainly achieve this by crushing the rock by means of "disk cutters" or "roller bits," a boring system based on the principle of cutting the rock came into being in Europe, whereby the rock is worked in a manner very similar to the milling of metals. For tunneling purposes, this principle was first developed by the late Austrian engineer Wohlmeyer. Between late 1962 and the spring of 1965, the first experimental machine was tested in a German coal mine, working in coal and shale over a distance of some 3000 ft, divided over two runs separated by a period of time to allow for equipment modifications. In 1964, a collaboration was started between Wohlmeyer and the Habegger engineering firm of Thun in Switzerland. The normal Habegger range of equipment consists of aerial ropeways, ski lifts, and certain tool machines, to which in later years have been added monorail passenger-transport systems. One of these was installed as the main mode of transport at the 1967 World Fair in Montreal. After taking over the Wohlmeyer patents, Habegger further developed the original cutting principle, aiming at more robust machines in order to be able to tackle harder rock. A first machine was built and tested at a site near Thun in sandstone averaging 17,000 psi compressive strength and limestone of 25,000 psi. In May 1966 this machine was delivered to Japan for the boring of a pilot tunnel for the Honshu-Hokkaido railway connection under the sea. A second machine, incorporating many improvements based on experience gained with this first mole, was built during 1966 and tested in the same limestone as mentioned previously (25,000 psi), before being installed to bore the head race tunnel of the Julia hydroelectric power scheme near St. Moritz, Switzerland, in the early summer of 1967 (Fig. 1 ) .

Jan 1, 1970

By Charles Baker

THE district of Catorce, San Luis Potosi, ranks among the first half-dozen silver-producing camps f Mexico. Mining has been more or less continuous there for 150 years. The large producing mines, Mapum, Mazapil, Palomas, Musquiz, Minas Virjas, now for the most part idle or abandoned, are grouped around the head of two valleys: one, which drains to the west, falls 2000 ft. (609.6 m.) in 4 1/2 mi. (7.2 km.) between the main Catorce and the western foot of the range and is characterized by steep canon walls; the other, east of the main town of Catorce from which it is separated by a high divide, heads in a number of steep tributaries above the basin in which lies the town of Potrero and flows nearly north for 10 mi. (16 km.) to the northern base of the range; below Potrero, it has for the most part gently sloping valley walls and a broad valley floor. The Sierra Catorce is the highest range of the region, the summits reaching altitudes of over 11,000 ft. With the exception of a few cliffs of the erosion escarpment of the lower limestone and the canon walls below the main town of Catorce, which is the highest town in Mexico, the gently rounded slopes are characteristic of a maturely eroded mountain range composed of folded sedimentary rocks. As is usual in desert regions, the heavy-bedded limestones are the most resistant to erosive forces. Folded into anticlines, they form the mountain ranges; and the intermontane valleys and basins, originally carved out of less resistant shales, clays, marls and sandstones, are covered by debris forming a mantle with surface gradually rising upwards toward the hills. In time, the debris buries, in deposits formed from their own ruins, all but the highest summits of the original mountains; some f this region has already nearly reached this stage. Most of the debris is firmly cemented by calcium carbonate (caliche). Solution f the limestone by meteoric waters afforded the supply of lime carbonate, which has been redeposited upon evaporation of the waters as a cement binding the boulders, pebbles, and finer detritus.

Jan 9, 1921

Jan 1, 1901

Jan 1, 1944

By D. S. Flett, A. W. Fletcher

Equilibrium studies on the extraction of nickel and cobalt with kerosine solutions of naphthenic acid have shown that an exchange extraction reaction occurs at pH 5.5. The nickel/cobalt separation factor is constant at 1.8 for constant total metal molarity and varying nickel/cobalt ratios. The separation factor decreases with increasing total metal molarity in the organic phase beyond 0.2 M and also decreases with increasing temperature. From the equilibrium data, it has been possible to derive a mathematical model for the separation of nickel from cobalt by exchange extraction in multistage systems. Experimental data from a continuously operated multistage mixer/settler apparatus has shown a reasonable correspondence with computer-calculated data. The effective separation of nickel and cobalt in sulfate solution remains a problem in hydrometallurgy and the hope that this would be solved by solvent extraction has not yet been fulfilled. With chloride solutions, advantage may be taken of the ability of cobalt to form anionic complexes with the chloride ion. It can then be readily separated from nickel, which does not form stable chloro complexes, by extraction with a suitable long chain amine. However, in hydro metallurgical operations, sulfate solutions are generally obtained in which no extractable anionic species are present. Thus, the possibility of using cationic extractants must be considered, and in this paper attention is directed to the use of carboxylic acids. The method of separation studied has been termed exchange extraction, which involves replacement of a metal in the organic phase with a more acidic metal in the aqueous phase. Thus, (BR2).+ (Az+)aqt=(AR,).+ (B2+)aq (I) where metal A is more acidic than metal B, R represents the acidic radical derived from the acid RH, and the subscripts e and aq refer to the organic and aqueous phases, respectively. Ashbrook and Ritcey' have used this method for the separation of cobalt from nickel using the sodium salt of di-2 ethyl hexyl phosphoric acid, which preferentially extracts cobalt. Some nickel is coextracted, and this is removed by exchange with cobalt ions in the feed solution by suitable countercurrent operation in a pulsed column. Much work has been carried out by a number of workers in Russia on the general use of exchange extraction for the separation of metal ions using car-boxylic acids. Gindin et aL a have demonstrated that this technique could be applied to the separation of nickel from cobalt using a C--C. carboxylic acid and have applied the technique to the production of high purity cobalt solutions for electrolysis. Further worka was concerned with the development of a process for the separation of nickel from cobalt in a pulsed column. This system permitted the separation of iron and copper from nickel and cobalt in one system. The procedure involved center feeding with acid backwashing at the top and alkali addition lower down the column. Thus the system operated under a pH gradient and the metals were distributed in the column in the order of their basicities. A similar application was studied by Gel'perin et al,4,5 for the removal of copper and iron impurities from a nickel anolyte by means of a C10-C,12 fatty acid fraction. Ginden et al,' and Fletcher and Wilson' have studied the effect of pH on the extraction of a number of metals with carboxylic acids. These studies showed that metals such as iron, copper, lead, zinc, nickel cobalt, and manganese are extracted at pH values close to the pH of hydroxide precipitation. Nickel is extracted at a slightly lower pH than cobalt and thus the nickel/cobalt separation factor has a value not much greater than 1. More basic work on complex identification has been reported by Fletcher and Flett: by Tanaka; and Jay-cock and Jones." These studies have suggested that at low loadings in the organic phase, the nickel and cobalt carboxylates appear to be dimeric and solvated by free carboxylic acid molecules. As the concentration of metal in the organic phase increases, the complex changes and larger polymeric species are formed. In order to permit assessment of the potential of carboxylic acids as extraction reagents for separation of

Jan 1, 1971

By R. H. Schnitzel

Internal-friction peaks have been observed in tungsten single crystals at about 300° and 400°C. The characteristics of these peaks are similar to interstitial peaks observed in other bee metals; therefore, the origin of these peaks appears to he the Snoek mechanism. The interstitial responsible for the peak at about 300°C has not been identified. Carburizing increases the magnitude of the peak at about 400°C; consequently, it appears reasonable to suppose that the specific interstitial associated with this peak is carbon. The activation energies associated with the 300° and 400°Cpeaks are about 35,000 and 45,000 cal per mole, respectively. INTERNAL - friction peaks resulting from the stress-induced diffusion of interstitials (Snoek relaxation peaks) have been frequently observed in bee metals.1-5 Attempts to detect Snoek relaxation peaks in tungsten have, however, not been fruitful.' Failure to find Snoek peaks in sintered tungsten can perhaps be attributed to one or more of the following difficulties: a) the relatively low purity of the sintered tungsten; b) the lack of extensive metallurgical knowledge about tungsten-interstitial alloys, such as suitable interstitial dosing and quenching procedures; and c) the inconsistency of some of the interstitial analyses of tungsten, which reflects itself in one's inability to be sure of the nature of the specimens. This present investigation did not overcome all of these difficulties for successful tungsten internal-friction measurements. Some of these difficulties still persist and new difficulties were encountered during the course of this investigation. Nevertheless, the use of electron-beam tungsten single crystals having somewhat greater purity levels than sintered tungsten combined with appropriate carburizing and quenching procedures permitted a reasonable attempt to be made. As a consequence, internal-friction peaks were observed in these tungsten single crystals at about 300° and 400°C. These peaks were found to be unstable, since they annealed rapidly away during a sequence of internal-friction measurements. Hence, it was necessary to construct an apparatus having a faster heating rate to study some of the details of these peaks. From the behavior of these peaks as well as our knowledge of similar peaks in other bee metals, one can reasonably conclude that these peaks are caused by residual interstitial impurities within these crystals. Further investigation of these peaks after the application of various metallurgical treatments lent credence to this supposition. EXPERIMENTAL TECHNIQUE The internal friction of tungsten single crystals was measured using two different pieces of apparatus both of which are of essentially the same conventional design, namely the KE type of torsion pendulum. The important difference between these two types of apparatus was in the attainable heating rate and method of protection of the specimen from atmospheric contamination. The apparatus designated "number 1" was enclosed in a vacuum chamber which was heated by an externally mounted furnace. It had a slow rate of heating which was estimated to be about 4°C per min from room temperature to about 350°C and then about 1°C per min to 600°C. The internal friction of tantalum was measured with this apparatus and the established Snoek peaks were found.' These tantalum peaks in the temperature range from room temperature to 400° C served as a check for the apparatus. The apparatus designated "number 2" having a faster heating rate than number 1 was not elaborate. It consisted of a mounted nickel tube to which split heating elements were attached. Argon was used as the protective atmosphere. The measured heating rate was about 12° to 15°C per min whereas the cooling rate was somewhat slower at about 10° C per min because of the increased difficulty encountered in stabilizing the temperature. No surface oxidation of the specimen was noted after any test. This apparatus was also checked with the known peaks of tantalum.1 The preparation of the single-crystal specimens for internal-friction measurements consisted of centerless grinding the crystals from an approximate 0.200 in. diameter to 0.030 to 0.040 in. in diameter, and then electropolishing them to about 0.020 in. in diameter. Single crystals processed in this manner are designated as being in the virgin condition. Since the length of crystal varied from 3 to 9 in., the test frequency varied from about 1 to 2 cps. The frequencies of measurement, axial orientations, and chemical analyses for the various crystals are listed in Table I. The controlled addition of carbon into tungsten is a difficult problem. Attempts to find the critical conditions necessary for an equilibrium treatment were not fruitful. Therefore, a simple nonequi-librium method was used. The addition of carbon to these crystals consisted of appropriately combining three treatments—carburizing to achieve a case, annealing to partially dissolve the carbon into the

Jan 1, 1965