Search Documents

By C. E. Agnew

THE Eastern district, composed of New Jersey and eastern Pennsylvania, with its native ores, was the cradle of the iron industry of the United States The district attained and held the leadership in production of pig iron for over 100 years, from pre-Revolutionary days to approximately 1875 The first shipment of Lake hematite ore was made in 1853 It was a small shipment, transported by a sailing vessel and a canal barge, but it was the beginning of the end of the supremacy of the Eastern district, although at that time the ore was supposed to be too rich to be successfully smelted with the block coal then in use at western furnaces The iron made from the first shipment of Lake ore was worked into nails by the Sharon Iron Co , at Sharon, Pa The writer's great-grandfather, David Agnew, and his brother, John P Agnew, owners and operators of the Sharpsville furnace, Sharpsville, Pa , worked the shipment through a furnace Because of this, the writer feels some satisfaction in having been one of a group that solved the problem of making profitable an operation using Eastern district ores exclusively With the development of Lake mines, and the production and use of coke, the Middle West district gradually assumed the position of leadership in production, because, even though the ores were transported 1000 miles by water and rail, its cost figure on pig iron was better than that of the eastern producer whose furnace was next to his mine Such a cost figure was possible because the ore was naturally rich in iron and reduced easily It was possible to carry a heavy burden on the furnace, which resulted in large tonnage and low coke per ton of iron This paper is in no sense a technical one The purpose is to show that with the proper physical preparation of the Eastern magnetites they will reduce as easily as the Lake hematites, and because of the high iron concentration give the Eastern producer just as much advantage as formally he was at a disadvantage in comparison with the Middle West producer

Jan 1, 1938

By V. H. Gottschalk, R. S. Dean

In the theoretical study of metallurgical reactions, it is necessary to make certain assumptions concerning the nature of metal-gas systems. The assumption usually made is that the reaction in such systems takes place predominantly with gas that is in "solution" and that the amount of solution follows the rules which have been developed for aqueous solutions; namely, Henry's law. The purpose of this paper is to inquire whether these assumptions are the best ones that present knowledge of gas-metal systems permits us to make. In the first part the extent to which a gas will dissolve in a metal and still follow Henry's law is considered. The conclusion is believed justified that the number of molecules of gas that can dissolve in a metal and have the system follow Henry's law must be small indeed. It is therefore improbable that the first assumption concerning the predominance of these dissolved molecules in reaction is correct. It is suggested that some improvement in the correlation of the probabilities with the assumptions made in the mass law equations would be made by the use of the dp law of Sieverts in place of Henry's law. However, the amount of gas that may be held in a metal so that it follows either Henry's or Sieverts' law is considerably outweighed in most metallurgical reactions by that held in gas-metal systems of entirely different structures and concerning which little experimental evidence is available. Some speculation concerning the nature of these is offered. The conclusion is that attention should be given to the determining of the nature of gas-metal systems and that the really fruitful application of the mass law and its connected calculations will have to await a more complete knowledge of these systems than we now possess. DISCUSSION (Paul D. Merica presiding) P. D. Merica, New York, N. Y. (written discussion).—The solubility relations of gases in metals, in so far as they are known from the pioneer work of Sieverts and others, have from the first presented certain challenging peculiarities. The authors have emphasized the significance of these characteristics and suggest that they point

Jan 1, 1933

By C. E. Agnew

THE Eastern district, composed of New Jersey and eastern Pennsyl-vania, with its native ores, was the cradle of the iron industry of the United States. The district attained and held the leadership in produc-tion of pig iron for over 100 years, from pre-Revolutionary days to approximately 1875. The first shipment of Lake hematite ore was made in 1853. It was a small shipment, transported by a sailing vessel and a canal barge, but it was the beginning of the end of the supremacy of the Eastern district, although at that time the ore was supposed to be too rich to be successfully smelted with the block coal then in use at western furnaces. The iron made from the first shipment of Lake ore was worked into nails by the Sharon Iron Co., at Sharon, Pa. The writer's great-grandfather, David Agnew, and his brother, John P., Agnew, owners and-operators of the Sharpsville furnace, Sharpsville, Pa., worked the shipment through a furnace. Because of this, the writer feels some satisfaction in having been one of a group that solved the problem of making profitable an operation using Eastern district ores exclusively. With the development of Lake mines, and the production and use of coke, the Middle West district gradually assumed the position of leader-ship in production; because, even though the ores were transported 1000 miles by water and rail, its cost figure on pig iron was better than that of the eastern producer whose furnace was next to his mine. Such a cost figure was possible because the ore was naturally rich in iron and reduced easily. It was possible to carry a heavy burden on the furnace, which resulted in large tonnage and low coke per ton of iron. This paper is in no sense a technical one. The purpose is to show that with the proper physical preparation of the Eastern magnetites they will reduce as easily as the Lake hematites, and because of the high iron concentration give the Eastern producer just as much advantage as formally he was at a disadvantage in comparison with the Middle West producer.

Jan 1, 1938

By Craig R. Smith, Warren Pfefferle

Tests were conducted utilizing large flat jack devices placed in a vertical slot for high pressure loading of rock to measure in-situ properties of a rock mass. The high pressure flat jack devices were used as a site investigation tool to obtain rock mass properties. Tests were conducted before and after a 100 ton surface high explosive detonation test to assess explosive effects on the rock. It was conclusively demonstrated by these tests that meaningful flat jack tests could be successfully accomplished; also, a significantly different response of the rock medium was measured as larger areas of rock were loaded. Surface jointing was severely disturbed by the explosion.

Jan 1, 1971

By Herbert Clark Hoover, Lou Henry Hoover

SINCE I have written of the varied work of pre- paring the ores, I will now write of the various methods of smelting them. Although those who bum, roast and calcinea the ore, take from it something which is mixed or combined with the metals ; and those who crush it with stamps take away much ; and those who wash, screen and sort it, take away still more; yet they cannot remove all which conceals the metal from the eye and renders it crude and unformed. Wherefore smelting is necessary, for by this means earths, solidified juices, and stones are separated from the metals so that they obtain their proper colour and become pure, and may be of great use to mankind in many ways. When the ore is smelted, those things which were mixed with the metal before it was melted are driven forth, because the metal is perfected by fire in this manner. Since metalliferous ores differ greatly amongst themselves, first as to the metals which they contain, then as to the quantity of the metal which is in them, and then by the fact that some are rapidly melted by fire and others slowly, there are, therefore, many methods of smelting. Constant practice has taught the

Jan 1, 1950

By William Kent

(Read at the Amenia Meeting, October, 1877.) IN a paper by Mr. Frank Firmstone, published in vol. iv, of the Transactions of the Institute, on "Comparison of Results from Open-topped and Closed-topped Furnaces," the regularity of the average grade of pig iron produced by the furnace under different conditions is expressed by means of a curve or diagram. The object of this note is to show that the graphic method, or that of representing variations by plotted curves or diagrams, is capable of a much more extended application to blast-furnace records, making a valuable auxiliary to the "furnace .book," and that by it the practical metallurgist may obtain at a glance information concerning the variations of the furnace during long periods, which could be found in the furnace book only after a tedious search. Plate XII is a graphic record of an anthracite blast furnace for one month. The table on page 554 gives the figures obtained from the furnace book, together with a record of temperature of the atmosphere, barometric pressure, and moisture in the air, which was obtained from a meteorological observatory not far from the furnace. In the records of a furnace, two of the variable qualities are final results, viz., the quantity of pig iron produced, and its grade; all the other variables are antecedent causes which produce the final results. Of these variable causes which contribute to the quantity of product and its grade, some are partially under the control of the furnace manager, others depend upon the state of the atmosphere, and still others are accidental. Of the first class are the character of the materials charged, and their relative proportions, their mechanical conditions, as wet or dry, large or small pieces, etc., the revolutions of the engine, the heat and pressure of blast, and the distribution of the charge. Of the second class are the number of pounds of air blown into the furnace for each stroke of the engine, the amount of moisture in the air, and the condition of the chimney draughts. These vary largely with the season of the year. Of the third. class is the leaking of a tuyere or a temporary stoppage. To keep a record of this kind for a whole year, it is only necessary to procure a sheet of common profile or cross section paper, about 38 inches long and 8 or 10 inches wide, with cross lines ruled about 0.1 of an inch apart. The vertical lines, or those in direction of the

Jan 1, 1878

By John B. Pearse

The works heretofore used in carrying out the Bessemer process have been constructed substantially as follows: The whole works or plant has been divided into three parts. 1. The division in which the metals for conversion are melted. 2. The division in which the metals are converted into steel and cast into ingots, or the converting department. 3. The engine and boiler department which supplies the hydraulic power required to move the machinery, and which furnishes the blast used for converting the crude metal into steel.

By Thomas C. Wilder

The activities of both components and the partial and integral molar thermodynamic properties of mixing for the liquid Al-Ge system at 1200°K and for the gertnanium-rich Al-Ge liquidus have been determined from data for eighteen alloys of compositions in the range 0.0593 < 0.880 using the reuersible gal-vanic. cell in the temperature interval 9320 to 1258°K. The liqui-dus compositions above 93 2 °K loere also ve determined by observing the discontinuities in the C us T plots for the high-melting alloys. This system shows moderate negative deviation from ideality throughout, the values for y° being 0.212 and 0.189 for aluminum and germanium, respectively, at 1200°K. Pavtial molar Properties of aluminum on the germanium-rich solidus and at infinite dilution in Ge(s) oboue 932°K were estimated from the foregozng measurements and the equlibrium data of previous investzgators. RECENT compilations of data1" have shown an increasing demand for knowledge of the thermodynamic properties of mixing of metallic alloy systems. In the case of binary-liquid systems where one of the components is a semiconductor this information is useful because, primarily, properties of the second (dopant) component on the liquidus, solidus, and at infinite dilution may be determined more accurately than from calculations based on the phase diagram. In this investigation a reversible galvanic cell was used to determine the chemical potential of aluminum in the two-phase region, liquid + [Ge], on the germanium-rich side of the A1-Ge system in the temperature range 932" to 1193°K. In addition, similar measurements for homogeneous liquid A1-Ge alloys for the entire composition range were obtained for the temperature interval 932" to 1258°K. The cell used was: The experimental technique and the treatment of the data were essentially the same as described earlier394 and are elaborated upon only briefly here. Each cell consisted of a liquid aluminum anode and three A1-Ge alloy cathodes of different composition which were held in Morganite alumina crucibles. The alloys were made up from aluminum and germanium weighed to the nearest 0.1 mg to a total weight of 5 to 10 g. Aluminum was a gift of Aluminum Co. of America and had a purity of 99.995+ pct. Germanium of transistor grade was a gift of Bell Telephone Laboratories. The four electrodes were contained in a larger alumina crucible which also held the prepurified fused chloride electrolyte. Contact to the electrodes was made by tantalum wire leads sheathed in alumina. The tantalum leads were centered in the electrodes by suitable positioning of an alumina radiation shield which fitted on the top of the - alulnina crucible. Two chrome l-alumel thermocouples, sheathed in quartz wells, completed the internal cell arrangement. The entire assembly was enclosed in an alumina tube, fitted with a water-cooled copper head so the system could be evacuated and then flushed with purified argon. *

Jan 1, 1967

By W. A. Stickney, J. W. Town

Tests demonstrated that aqueous solutions of sodiu~n sulfide would dissolve over 95 pct of the cinnabal- in 5 pct Hg flrotation concentrates and 60 to 90 pct of the cinnabav in low-grade ol-es. Double-leach tests showed that potassiutn sulfide would dissolve 90 pct of the avsenic sulfide in Hg-As satnples and only 1 to 10 pct of the Hg; the sodium sulfide would then dissolve 80 to 90 pct of the rernaining Hg and 30 to 70 pct of the vemaining As. 1 HIS paper describes the extraction, by alkaline sulfide solutions, of mercury from cinnabar-bear ing ores and flotation concentrates. Leaching time and solution temperature had minor effects on mercury extraction when compared to the effects of reagent quantity and ore type and grade. Cinnabar, although readily soluble in sodium sulfide, was only partially soluble in potassium sulfide and essentially insoluble in ammonium sulfide. A double leach process was developed to extract selectively the arsenic from Hg-As products with K2S and to treat the residue with sodium sulfide-hydroxide solutions to extract the mercury.&apos; Mercury was then recovered from the pregnant solutions either by precipitation with metallic aluminum or by electrodeposition. The solubility of HgS in alkaline sulfide solutions was first reported by Volhard in 1878.&apos; The first reported commercial application was made in 1915 when Thornhill applied the method to the treatment of an amalgamation tailing.3 Mullhollen, in 1911. described the chemical reaction of HgS with Na,S and alkaline hydrate to be:4 Most investigators have reported using a 4-pct sodium sulfide and a 1-pct sodium hydroxide soluti~n.3-4 An increase in temperature or excessive dilution of the solution causes the reaction to be reversed. Church Holmes described a similar process used for the extraction of antimony from silver concentrates at the Sunshine Mining Company&apos;s mill at Kellogg. Idaho.5 More recently. Erspamer and Wells reported the results of leaching studies on a Hg-Sb ore from Alaska.6 EXPERIMENTAL PROCEDURE Leaching tests were made on samples of mercury ore from eight deposits in Oregon, Washington, and Idaho. In addition. tests were made on flotation concentrates from seven of the samples as well as a flotation concentrate from an operating mill. Since previous investigators reported reagent requirements greatly in excess of that required by the equation HgS + Na2S = HgS . Na2S, initial studies were made on chemically pure HgS. Results showed that the reaction actually required about 1 g of Na,S per g of HgS in an aqueous solution rather than 0.338 g of Na,S as indicated by the equation. To check further the matter of reagent requirements, Na2S and HgS were mixed together in equal mole ratios. Water was then added, a drop at a time, until the components reacted; X-ray diffraction analyses showed no HgS nor Na,S present. The yellow hydrate compound which formed would not redissolve until about three additional mole equivalents of Na,S were added to the solution. This indicated that a stable solution would require at least 4 moles of Na2S for each mole of HgS. While these implications may be valid for pure HgS, the possibility of entirely different results caused by the existence of other elements present in ores and concentrates was recognized. Consequently, experiments of the same order were made on samples of a flotation concentrate from a producing mill. The concentrate, containing about 18 pct

Jan 1, 1962

By J. O. Whitely

IT is difficult to give a refining outline that may be followed for any and all combinations of the platinum metals; different combinations require different methods of attack. This paper does not pretend to go into all of the reactions of the metals of the platinum group, but will outline the commercial refining of platinum scrap. TYPICAL PLATINUM SCRAP As a concrete case, let us take 100 oz. of miscellaneous scrap, made up of jewelry scrap, dental scrap and laboratory ware. This lot will contain some platinum, palladium, iridium, ruthenium, rhodium, gold, silver and copper. The first problem is to get all of the metals in solution. If the scrap is principally platinum, palladium and gold, a treatment with aqua regia is the course to pursue; but if the scrap contains alloys high in iridium or ruthenium, aqua regia will act too slowly. In the case in hand, we are going to presume that we have scrap high in iridium and ruthenium, and proceed accordingly.

Jan 1, 1928

By S. R. Maloof, W. R. Mitchell, J. A. Mullendore

Preliminary experimental evidence is presented to show that the metallic impurities aluminum, iron, and silicon, and beryllium oxide as found in commercially pure hot-pressed beryllium powder can be reduced to lower Concentrations by Zone -Purification techniques. The reduction in the concentration of aluminum to extremely low levels (10 PPm) is noteworthy, since earlier work demonstrated that aluminum is a major factor contributing to the hot-tearing of beryllium during fusion welding. On the basis of present findings, a method is suggested for producing beryllium metal of improved weldability. EXPERIMENTAL research now being conducted on the purification of beryllium indicates that several of the metallic impurities and beryllium oxide can be reduced to lower concentrations by employing standard horizontal zone-refining techniques. For the preliminary work, commercially-pure hot-pressed beryllium having a purity of 97.84 pct was used. The chemical composition is given in Table I. The hot-pressed beryllium was machined into bars 5/8 by 5/8 by 4 to 6 in. in length. Beryllium-oxide boats which had been conditioned by prior heating in a vacuum of 10"5 mm of Hg at 1100°C for 3 hr were used to hold the beryllium while it was zone melted. The boat with its charge, along with a smaller beryllium-oxide boat containing scrap beryllium to be used for gettering purposes, was loaded into a quartz tube and evacuated to 10-6 mm of Hg. Alter alternately evacuating and flushing three times with purified argon, the furnace tube was backfilled to a pressure of 1/6 atm of A and sealed off by means of a vacuum-tight stopcock. It was then removed from the pumping equipment and mounted on the traveling carriage of the zone-refining apparatus. Heating was accomplished with a 10 kw 450 kc induc- tion heating unit using an induction coil consisting of two turns of 3/16-in. diam copper tubing. Before starting to zone melt, the atmosphere in the furnace tube was gettered by heating the scrap beryllium in the smaller boat to above its melting point and holding at temperature for several minutes. The carriage was then shifted so as to locate one end of the beryllium ingot in the large boat within the induction coil. A molten zone approximately 3/4 to 1 in. was established by loading directly into the ingot. The molten zone was moved very slowly along the length of the ingot. Before each pass was made the procedure for evacuating, flushing, and backfilling, and so forth was repeatedI&apos; Speeds of 1 1/2 and 3 in- per hr were used with up to twelve zone passes. The appearance of a typical zone-refined ingot is shown in Fig. 1. After zone refining, the grains in the ingot appear to be elongated in the direction of zone travel, whilst before, they are essentially equi-axed. A microexamination revealed the presence of a network in the beryllium grains as seen in Fig. 2. Laue spots in back reflection pictures taken of the sample were not sharp, indicating the presence of subgrains in the structure. As can be seen, however, many of the network boundaries cross beryllium grain boundaries. It has been shown by Martin and Moore1 that beryllium solidifies as a bcc structure which then transforms to the hexagonal structure at about 1250oC.It is believed that the observed network is merely the outline of the bcc structure which formed from the melt and are not subgrain boundaries. In order to eliminate surface contaminants, approximately 1/16 of an inch of material was removed from the outer skin of each ingot after zone refining.

Jan 1, 1962

By J. L. Whitlock

An attached growth aerobic biological treatment process has been developed at Homestake Mining Co.&apos;s Lead operation which not only oxidizes free and complexed cyanides, including the stable iron complexed cyanides, but also thiocyanate, and the oxidation byproduct ammonia. Through the employment of a mutant strain of bacteria which has been gradually and specifically acclimated to the waste, these potential pollutants are mineralized to relatively harmless sulfates, carbonates, and nitrates. The resultant effluent, through toxicological testing, has been shown compatible with the receiving stream, which serves as a cold water marginal trout fishery.

Jan 1, 1985

By R. W. Hertzberg, R. W. Kraft

A study of the fracture behavior of unidirectwn-ally solidified Cu-Cr eutectic alloy was performed. Fractured whiskers, grain boundaries, and the interface between proeutectic Cr dendrites and the Cu matrix were the predominant failure initiation sites where grain size was larger. Strain induced void formation was restricted at lower solidification rates. This was attributed to a lack of adequate plastic constraint and a probable preferred orientation. A modification of the Crussard et al. model is presented to explain the appearance of "elongated dimples" on the shear fracture surface. A Cu-Cr alloy containing about 1.8 at. pct Cr solidifies by a eutectic reaction forming filamentary crystals of chromium within a continuous copper solid solution matrix.&apos; Webb and Forgeng2 have shown by bend tests that the extracted chromium filaments, which are ordinarily curved and branched (due to random solidification), have the high strengths associated with whiskers. If an ingot of the eutectic alloy is unidirectionally solidified and appropriate control exercised over the thermal gradient, growth rate, and impurity level, the chromium fibers can be forced to solidify as fibers which are substantially parallel to the growth direction, Fig. 1. Uniaxial tensile tests on these straight chromium fibers extracted from controlled ingots3 have confirmed the earlier bend test results on curved fibers. Combining the facts that the strength and modulus of the chromium filaments are higher than the more ductile copper matrix and assuming that a "good bond" exists between the two phases, the Cu-Cr controlled eutectic system fulfills the requirements for effective fiber reinforcement of ductile matrices as established by studies on fiber glass reinforced plastics and other two-phase systems.4 Therefore, it was decided to study the fracture characteristics of morphologically simple specimens of chromium fiber reinforced copper (i.e., specimens of the controlled eutectic with substantially parallel reinforcing fibers) with the objective of establishing the dominant aspects of fracture. PREVIOUS WORK Comparatively little work has been done to understand the manner in which ductile alloys fail be- cause of the limited demand for this kind of information. Ordinarily ductility is specified for safety or similar reasons and when a part deforms plastically its useful life is terminated. In recent years, however, a number of investigators have begun to

Jan 1, 1963

The oil production in Bahrein for the year 1937 was 7,762,264 bbl., a monthly average of 646,855 barrels. Sufficient potential production had been developed in the Second Pay (Main Pay) at Bahrein by the end of 1936 to supply the anticipated crude demand, and the drilling program was changed from straight development to partial exploration during 1937. Two nonproductive wells were drilled to test the Third Pay at a depth of about 2900 ft., or some 900 ft. below the top of Second Pay. As a result of this exploratory work, the normal drilling program was slowed down and only eight new wells were completed in the Second Pay during 1937, making a total of 45 producers from the Second Pay. The deep test was drilling at 5081 ft. at the end of the year. A 550-ft. section (termed Fourth Pay) of porous limestone interbedded with anhydrite was topped at about 4150 ft. Numerous drill-stem tests indicated that the limestone was very permeable and that it carried large volumes of natural gas under high pressure together with a small amount of high-gravity oil or condensate. Drill-stem tests also indicated that the bottom 50 ft. of the 550-ft. section carried an encouraging amount of heavier oil, gravity about 37" A.P.I., with characteristics similar to the oil produced from the Second Pay. A well was started somewhat down-structure from the deep test to better determine the oil-producing possibilities of the Fourth Pay. Some refinements in drilling technique were adopted during the year. All wells started to the Second Pay were drilled with rotary from the surface. The top 1500 ft. of porous limestone section, formerly drilled with cable tools, is now drilled with rotary without circulation, using water to wash the cuttings into cavities. The shale section from this point to the top of the oil horizons is drilled with natural mud circulation. The productive horizons are drilled with oil circulation under pressure control. A second satisfactory method of completing wells was developed when the two Third Pay test wells were plugged back and gun-perforated through cemented casing opposite the Second Pay, with good results.

Jan 1, 1938

By F. F. Schmidt, H. R. Ogden, E. S. Bartlett

Continuing tantalum alloy development studies have been concerned with a more detailed investigation of promising binary, ternary, and more complex tantalum alloys containing Groups IV-A, V-A, VI -A. VII-A, and VII-A metal additions. A primary objective of these studies was to improve the elevated temperature strength of tantalum with minimum degradation of fabricability and low-temperature ductility by alloying. Several alloys were found to exhibit hot tensile strengths in the excess of 25, 15, and 10 ksi at 2700°, 3000°, and 3500°F, respectively, combined with excellent cryogenic toughness and ductility. Particularly outstanding in this respect are alloys in the system Ta-Mo-W. Ternary parameter curves describing hot-strength, low-temperature ductility, recrystallization temperature, weld ductility, and fabricability are presented for the Ta-Cb-V, Ta-Hf-W, Ta-Mo-Hf, Ta-Mo-V, Ta-Mo-W, and Ta-V-W systems. At present, only four metals qualify for large scale structural applications at temperatures above about 1800°F. These are tungsten, tantalum, molybdenum, and columbium. Research and development work on these refractory metals has progressed to the point where efforts are now primarily directed toward the improvement of high- and low-temperature mechanical properties through alloying. High melting point combined with excellent low-temperature ductility, fabricability, toughness, weldability, and high solubility and tolerance for both substitutional and interstitial solutes are important attributes of tantalum. Conversely, its high density and relative scarcity compared with other refractory metals are the major deterrents to the use of tantalum. Early studies in the Battelle alloy development program established base line data on the mechanical and metallurgical properties of high-purity tantalum.&apos; These studies were extended to include a preliminary investigation of the effects of various alloying elements on the established base properties.2,3 Recent studies involved a more detailed investigation of promising binary alloys containing Cb, Hf, Mo, Os, Re, Ru, and W, and ternary Ta-Cb-V, Ta-Hf-W, Ta-Mo-Hf, Ta-Mo-V, Ta-Mo-W, and Ta-V-W alloys. Results of major importance obtained are given in this article. EXPERIMENTAL PROCEDURES Electron-beam-melted tantalum (Wah Chang) and high-purity alloying elements were consolidated as 150-g ingots by multiple nonconsumable arc melting under a partial atmosphere of helium. Homogeneity of the button ingots was checked radiographically. Alloy buttons measured about 1-1/2 to 1-3/4 in. in diam by about 0.35 and 0.50 in. thick. Nominal alloy compositions were checked on each alloy button by weighing after arc melting. In most instances, weight losses were within 3 pct of the total weight charged. Subsequent chemical analyses on a number of selected alloys showed interstitial contents to range as shown below: Range of Interstitial Content, ppm 0 C N H 25-75 50-100 10-50 1-5 Metallic alloying additions were found to agree well with nominal compositions based on weight change data. Fabrication directly from the cast button to sheet was conducted at low (75° to 900°F), intermediate (1800° to 2000°F), or high (3000°F) temperatures, depending upon alloy content and hardness. Evacuated stainless steel or molybdenum packs were used for fabrication at intermediate and high temperatures, respectively. The temperature required to complete recrystal-lization in one hour was determined by hardness measurements and metallographic observations (longitudinal test sections) after vacuum annealing at 180°F intervals in the range 2010° to 2910°F. All mechanical property evaluations were conducted on recrystallized sheet, nominally 0.04 in. thick. Weldability of the various alloys was screened using manual TIG welding techniques. Bend ductility (bend axis perpendicular to weld axis) was the criterion used for evaluation. Tensile specimens employed 0.200 by 1 in. gage lengths, and bend test specimens measured about 1 by 1/4 in. Low-temperature tensile tests were conducted using a crosshead speed of 0.02 in. per min up to the point of yielding, and 0.05 in. per min to fracture. High-temperature tensile tests were conducted in vacuum using a crosshead speed of 0.01 in. per min

Jan 1, 1963

By F. C. Kelley, L. L. Wyman

In order to clarify and amplify the existing data concerning the action of the cementing material in cemented tungsten carbide alloys, the authors have initiated this investigation of the entire range of cobalt-tungsten carbide alloys. Inasmuch as the ultimate objective is relative to what actually goes on during the sintering of cemented tungsten carbide materials, this work was necessarily restricted to heat treatments similar to those used in actual production of these materials. In the course of numerous experiments, the authors have noted several conditions that indicated that there was a solubility to be considered. Among these factors are the following: 1. Many of the alloys showed a much larger amount of binding constituent to be present than could possibly be accounted for by the cobalt content. 2. In many areas, grains of the carbide constituent are much larger than the particles of carbide originally added. In addition, these grains are of very regular contour. 2a. In samples of cemented tungsten carbide which had been fused in the atomic hydrogen torch in the presence of excess binder constituent, immense grains are formed, and their shapes are very regular. This is also true when the cemented tungsten carbide of 13 per cent. Co content is fused alone in the atomic hydrogen torch. Contrary to general expectation, chemical analysis of this material, after fusion in the atomic hydrogen torch, checks the analysis of unfused material. 3. In making the cemented tungsten carbide materials by the process of exerting the pressure at the time of heating a certain portion of the &apos; contents squeezed out of the mold. Chemical analysis has shown that this material contains approximately 12 to 20 per cent. of tungsten. The microstructure shows a cored dendritic structure interlaced with eutectic network, and some graphite, as shown in Fig. 1. 4. Thermal analysis of these materials has consistently indicated an arrest point close to 1350" C.

Jan 1, 1931

By W. H. Smith

IN connection with some recent work on the effect of impurities on the ductility of chromium, it appeared desirable to know the solid solubility of carbon in chromium. A literature survey indicated that this information was not available. Although considerable work has been done on the Cr-C phase diagram,&apos;.&apos; previous investigators have been more concerned with the structure and phase boundaries of the carbide phases than with the terminal solid solution. The phase diagram shown in Fig. 1 is taken from the work of Bloom and Grant&apos; and represents the most recent determination. As indicated by the dashed line, the a solid-solubility limit was not determined. Experimental Procedure Alloys of chromium were prepared from hydrogen-treated and vacuum-degassed electrolytic chromium plus spectrographic grade carbon. The oxygen and nitrogen content of the alloys was <0.002 pct. After melting, analysis of the alloys showed them to contain 0.02, 0.08, 0.15, and 0.55 pct C. Pieces of the alloys were heated in a protective atmosphere to various temperatures and then quenched after holding for a time sufficient to insure equilibrium. Microscopic examination of the as-quenched alloys for the presence of a second phase was used as a measure of the solubility limit. The heats were made in a multiple hearth arc-furnace using a zirconium-gettered static argon atmosphere. A zirconium melt was made before each Cr-C heat. Triple melting was used to insure ingot homogeneity as shown by microscopic examination. The alloys were prepared by adding portions of a 4.5 pct C-Cr master alloy to high purity chromium. The carbon contents listed previously were those obtained by analysis. The nitrogen and oxygen contents after arc melting were both <0.002 pct. Sections 1/8X1/4X1/2 in. were cut from the 100-g ingots and a hole drilled in one end in order to suspend the sample from a molybdenum wire. After the surface was carefully cleaned, a sample of each melt was hung in a mullite tube heated externally by a platinum resistance furnace connected to a vacuum system. The lower portion of the mullite tube was sealed to Pyrex and closed off several inches below the furnace. This was filled with sili-cone oil kept cold by circulating cold water around the outside of the Pyrex. Quenching into the oil bath was achieved by melting a fuse wire supporting the sample. It required about 4 sec for the sample to cool from 1400" to 600°C. This severity of quench was considered satisfactory to freeze-in the high temperature equilibrium. For tests made at temperatures of 900" to 1200°C, heating was done in vacuum; for tests above 1200°C, an argon atmosphere was used. The holding time employed ranged from 12 hr at 900°C to 6 hr at 1400°C. Experiments were performed at temperatures of 900°, 1000°, 1100°, 1200°, 1300°, and 1400°C. Microscopic examination for evidence of a second phase was done at X1500. Experimental Result The microstructures of a 0.08 pct C-Cr alloy as-cast and after quenching from 1300°C are shown in Figs. 2 and 3. A 0.15 pct C-Cr alloy quenched from 1300°C is shown in Fig. 4. The data obtained from the quenching experiments is shown graphically in Fig. 5. If the Van&apos;t Hoff equation is obeyed, a plot on a logarithmic scale of the mol fraction of solute vs the reciprocal of the absolute temperature should give a straight line. For dilute solutions the weight percentage can be substituted for the mol fraction without introducing any appreciable error. The Van&apos;t Hoff equation can then be written as where H is the heat of solution in calories per mol. The slope of the straight line on the log pct C vs 1/T plot gives the value of AH. Assuming that the Van&apos;t Hoff equation is obeyed, which is probably justified for the dilute solution of carbon in chromium, the heavy straight line shown on Fig. 5 represents the best fit of the data. This line was obtained as follows. On Fig. 5 the results of the microscopic examination of all alloys following quenching were plotted and designated as to whether one or two phases were seen. Below 1100°C all alloys showed a second phase on quenching. The heavy vertical lines shown in Fig. 5 therefore represent the possible range of the ter-

Jan 1, 1958

By Margaret V. Doyle, R. W. Powers

INTERNAL friction measurements, carried out as functions of temperature, have been used extensively to obtain data on the mobility of interstitial impurities in the Group V metals, vanadium, colum-bium, and tantalum. For a given frequency of vibration, the internal friction peaks at a temperature which depends principally on the particular metal and interstitial impurity. Relaxation times and corresponding activation energies are determined from a knowledge of such peak temperatures for various vibration frequencies. These experimentally determined relaxation times are related to the average jump frequencies of the interstitial impurity atoms using the model of Snoek1 and can be related to macroscopic diffusion coefficients as shown by Polder.2 In these Group V elements, the impurity whose diffusion rate has been the hardest to pin down by the internal friction technique has been carbon. The experimental difficulties associated with carbon in these metals were not evident in the earliest investigation carried out by Ke on tantalum.3 The carbon peak was thought to occur near 140°C at 1 cps on the basis of the enhancement of the height of this peak measured on specimens which had been coated with colloidal carbon and heated in vacuo at 1200°C. Presumably on the basis of similar evidence, Wert identified a peak also near 140°C at 1 cps in columbium with the diffusion of carbon in that element." Later, the difficulties of admitting carbon into these metals without simultaneously introducing oxygen were pointed out by Ang and Wert- nd by Marx, Baker, and Sivertsen.6 The latter suggested that the peaks attributed to carbon in tantalum and columbium might arise from the presence of traces of oxygen, adventitiously absorbed during the carburization. Such suspicion was confirmed, at least in tantalum, when it was found possible to prepare C-Ta specimens without contamination by oxygen. Specimens sci prepared, aitnough high in carbon content, gave no evidence of a damping peak near 140°C.7 Recently, the authors were able to Show that carbon diffuses in tantalum at a rate only slightly slower than that for nitrogen.8 At 1 cps, the carbon peak lies at 34g °C, only a few degrees above the nitrogen peak at 341 °C. However, the two could be distinguished by a different stability with respect to aging at 400 °C and by a different dependence of peak height on solute concentration. On the basis of this experience with tantalum, it appeared worthwhile to search also for a carbon peak in columbium in the vicinity of the nitrogen peak." In this report, the location of the carbon peak in columbium is made known and its position relative to the nitrogen peak is compared with the authors&apos; previous findings in tantalum. In addition, a second source of internal friction seen only in specimens of very high purity is discussed. Columbium was obtained from the Fansteel Metallurgical Corp. as either 30 or 40 mil diam stock. The manufacturer gives the following analysis as typical of this material: 99.4 pct minimum Cb, 0.10 pct maximum C, 0.5 pct Ta, 0.04 pct Ti, 0.02 pct maximum Si, and 0.01 pct maximum Fe. Wires 13 in. long were degassed near 2200°C for 4 to 16 hr in an ultimate vacuum better than 2.10" mm Hg in an apparatus described previously.8 This treatment reduced the oxygen and nitrogen damping peaks observed in the as-received material to less than 0.0001 in Q-1 above background. The latter value varied somewhat from specimen to specimen in the range 0.0004 to 0.0008, depending chiefly on the wire diameter and the frequency of vibration. The high temperature evacuation left the specimen in a rather soft condition, the Vhn being reduced to 40 from a value near 121 in the as-received conGi~iur~. The gram size was about the diameter of the specimen. After outgassing, specimens were loaded with carbon by absorption of such hydracarbons as methane or ethylene. Carbon was also added to a few speclrnens by heating them at

Jan 1, 1958

By C. H. Mathewson

MICROSCOPIC rnetallography has been exploited quite well enough to bring about a very general understanding that the typical metal or alloy is composed of minute crystalline particles blended into a coherent microstructural mosaic. One does not have to be a specialist in metallography to realize that the properties of such an aggregate are essentially a summation in appropriate form of individual effects derived from the shape, size, placement or orientation and cohesive characteristics of the component particles. It is clearly of great importance to consider the various forms of discontinuity which may occur at the boundaries between these crystalline particles. When a number of particles each possessing the same orderly arrangement of atoms are brought together into a close-fitting system of purely haphazard contacts, not unlike a handful of snowflakes compacted into a snowball, the particles are said to possess random orientation. There are no generally accepted views concerning the arrangement of the atomis or the constitutional reaction between atoms where one crystal meets another, but these contact regions are characterized by strength rather than weakness and it is customary to require the presence of many rather than few boundaries in preparing metal for useful service. Under certain circumstances all of the particles in a metal may be nearly alike in orientation. Other general tendencies of orientation may be associated with particular forms of mechanical and thermal treatment. In contrast with these cases of fortuitous or statistical diversity of orientation, we often find adjacent particles united along a plane which possesses a grouping of atoms belonging equally well to both structures. This, of course, determines a fixed relationship between the two orientations and it is always possible to derive one from the other by some form of rotation or reflection prescribed by the symmetry of the crystal structure under consideration. Particles united in this manner are known as twin crystals although the term refers to the form of association rather than the number of individuals concerned.

By G. K. Williams

The continuous process of lead refining as at present operated at the Port Piric plant of The Broken Hill Associated Smelters Proprietary Ltd. was a development from investigations conducted in connection with the ordinary Parkes desilverizing process. It is not proposed here to discuss the theoretical considerations involved in continuous desilverizing because this aspect has already been dealt with in previous publications.1 Continuous Softening Process For economical desilverization of lead bullion, the bullion must first be subjected to refining processes for the removal of such impurities as copper, sulphur, arsenic, antimony and tin. This refining is effected by first drossing to remove copper and sulphur and then preferentially oxidizing the arsenic, antimony and tin from the bullion in the softening process. The theoretical basis of the continuous softening process is illustrated by the portion of the Pb-Sb-O ternary equilibrium diagram shown in Fig. 1. Under conditions of complete liquefaction, metal of the composition of softened bullion is in equilibrium with an oxide slag containing about 9 per cent antimony. In practice, of course, arsenic also is always present, and while the 0Pb-Sb-As-O quaternary system has not been worked out in detail, it has been found that in softening drossed smelter bullion of the composition produced at Port Pirie, arsenic is always reduced to 0.001 per cent or less when the antimony in the bullion is reduced to a satisfactory figure. In the operation of the continuous softening process, a two-phase system of a bullion low in arsenic and antimony and an oxide slag relatively high in those components exists in equilibrium. To this system is added continuously a bullion containing 0.2 per cent As and 0.8 per

Jan 1, 1937