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By Kehsin Kuo

DIE steel with 1.47 pct C, 0.42 pct Mn, and 8.22 pct W contains Fe,C and WC in the annealed state and WC embedded in a martensitic matrix in the hardened state (quenched from 800°C). The presence of a large amount of undissolved angular WC carbide particles makes this steel extremely wear-resistant. However, the WC carbide begins to dissolve in the austenite when the heating temperature is raised above 1000°C, but this solution process is still not complete at 1250°C although partial melting has already taken place at the austenite grain boundaries. At 1325 C, this steel contains austenite and liquid metal but no WC carbide, Fig. 1. On quenching into brine, the liquid metal solidifies into a constituent which etches differently from the austenite-martensite matrix. This constituent appears lighter than the matrix at the 1250°C stage when etched with 2 pct nital but darker in Fig. 1 when etched with Murakami's reagent. Such a constituent has also been found in burnt tungsten high speed steels. This constituent has been isolated from the matrix by anodic dissolution in a 5 pct HC1 electrolyte and was found by the X-ray powder method to be iso-morphous with &manganese, Table I. The agreement in line intensity between these two phases indicates that there is no ordering in this new phase. The calculated cube edge of this phase is 6.395A, somewhat larger than that of ß-manganese (6.30A). Besides this phase, the anodic residue also contains free carbon from the matrix and amorphous WO,, although the X-ray powder pattern of the residue shows the presence of only this phase. This makes it impossible to determine directly the composition of this phase from the residue. Attempts to prepare an alloy containing only this phase have hitherto been fruitless. The following experiments serve to show that this phase can only be obtained by drastic quenching from the liquid state and that its tungsten and carbon contents must be lower than those in the Fe,W,C carbide. On air cooling from 1325oC, the liquid metal solidifies into a eutectic consisting of austenite and the Fe3W3C carbide. The nature of this dark-etching Fe3W3C has also been ascertained by X-rays. This eutectic becomes coarser on furnace cooling. The solidification of a specimen cooled for 5 min from 1325" to 1200°C and water quenched is still not complete and the fine eutectic is formed during the quenching. Since this new phase can be replaced by a eutectic of austenite and the Fe,W,C carbide, its composition must lie somewhere between the latter two phases. The special features of this phase are: 1—it can only form directly from the liquid state by drastic quenching and 2—it is a ternary phase of iron, tungsten, and carbon. The ß-manganese structure of this phase is also interesting. In the Periodic Table, iron and tungsten lie on opposite sides of manganese; a certain combination of these two elements, in the presence of carbon, may have average properties similar to those of manganese. It has already been established that the x phase, a ternary one of iron, chromium, and molybdenum, has the a-manganese structure."' A similar phase has also been found in the ternary system Fe-Cr-W and in the following binary systems: Re-Cb, Re-Ta, Re-Mo, and Re-W.6 References 1 G. D. Preston: Philosovhical Magazine 11928) 5. 7th Series, p. 1207. - K. W. Andres: Nature (1949) 164, p. 1015. 35. G. McMullin, S. F. Reiter, and D. G. Eberling: Trans. ASM 11954) 46, p. 799. ' J. S. Kasuer: Acta Metallurgica (19541 2, p. 456. • H. J. Goldschmidt: Trans. ASM (19541 46, p. 807. P. Greenfield and P. A. Beck: Private communication.

Jan 1, 1957

By D. L. Martin

THAT small amounts of impurities have a harm-J- ful effect on the malleability of metals and alloys is well-known. One common type of em-brittlement involves the formation of a small quantity of eutectic at the grain boundaries, and is typified by sulfur embrittlement of nickel. Another example of eutectic embrittlement—sulfur embrittlement of cobalt—is described in this report. In the preparation of specimens for a study of Co-Pt alloys, it was observed that the hot swagabil-ity of the alloys appeared to be influenced by the grade of cobalt used as melting stock. The cause of the hot-shortness was not traced to any particular impurity, although sulfur was suspected.' The damaging action of sulfur on the malleability of cobalt has not been generally recognized,'; in spite of the fact that the Co-S phase diagram8 eveals the same basic conditions—low solubility and eutectic formation—responsible for sulfur embrittlement of iron and nickel.7, 8 Apparently sulfur embrittlement has not been a serious problem in the fabrication of cobalt alloys. One related factor is likely the limited commercial experience with high cobalt alloys, since the predominant use of cobalt has been in alloys containing less than 75 pet Co. A series of Co-S alloys was prepared and studied to establish the effect of sulfur on the hot working characteristics of cobalt. Specimens, 5/8 in. diam by 4 in. long, were prepared by vacuum melting in magnesium oxide crucibles and casting in a copper mold. Two grades of low sulfur electrolytic cobalt were used as the basic material for the study, one from Johnson, Matthey and Co. and the other from the International Nickel Co. Each contained about 99.5 pet Co and had a nominal sulfur content under 0.005 pet. The sulfur was added initially as cobalt sulfide powder. Later, some low sulfur alloys were prepared by diluting the high sulfur alloys with cobalt. Trouble was experienced in controlling the sulfur content. Apparently much of the cobalt sulfide powder was lost during melting, as most of the samples contained a lower sulfur content than was added. The alloys were evaluated for hot brittleness by heating to 1000°C in a hydrogen furnace and swaging in air. The results of these tests are summarized in Table I. All the alloys containing less than 0.008 pet S were successfully hot swaged to 1/4 in. diam. The bars containing more than 0.015 pet S could not be swaged because of the formation of intercrystal-line cracks similar to those illustrated in Fig. 1. Examination of the microstructure of the cast bars revealed cobalt sulfide eutectic at the grain boundaries, Fig. 2. The sulfide was not always continuous at grain boundaries in bars that were hot embrittled but, in general, the particles did form a network that could account for the brittleness above the eutectic temperature, 880°C. There is no question about the brittle nature of a specimen exhibiting a continuous sulfide network such as is shown in Fig. 2b, though a sulfide distribution similar to that in Fig. 2a is marginal. This particular bar cracked when hot-swaged. However, other bars with lower sulfur content but with some sulfide phase at grain boundaries were successfully worked. The reduction of area of a hot tensile test specimen was also found to be a sensitive indicator of sulfur embrittlement. The variation of reduction of area with sulfur content is shown in Fig. 3 for specimens fractured at 900°C in an evacuated capsule. The ductility of cobalt is greatly reduced when the sulfur content exceeds 0.005 pet. Similar results were obtained for alloys tested at 800°C, below the eutectic temperature. The upper sulfur embrittlement limit of 0.015 pet, Table I, agrees with the observation of Kalmus8 hat

Jan 1, 1957

By A. D. Schwope, L. R. Jackson, A. M. Hall

IN the course of an extensive investigation of the comparative properties of several types of copper, data were obtained on the cold working and subsequent recovery and recrystallization of the copper. In this paper, relations between the degree of cold work and the course of recrystallization are developed. In particular, it is shown that the course of recrystallization over long periods of time and at low temperatures can be predicted with reasonable accuracy from short-time high-temperature recrystallization data. MATERIALS USED IN THE INVESTIGATION Three types of copper were used in this investigation; these were tough pitch, OFHC, and OFHC copper with 15 oz per ton of silver added identified herein as Lots C, D, and F, respectively. The material was supplied by the American Metal Co. Ltd., and processed by the Rome Cable Co. The analyses of the three types of copper are given in Table 1. Originally, it started as wire bars 4 X 4 X 54 in. These bars were heated to 871°C in air and hot rolled to 3/8 in. rod. This rod was cold drawn to 0.204 in. rod (70 pct reduction) in three passes and annealed at 427°C for 4 hrs. A portion of the 3/8 in. rod was saved for more detailed cold-drawing experiments. Starting with the annealed 0.204 in. rod, hard-drawn wires were produced by cold drawing to 0.081 in. wire in 7 passes (84.4 pct reduction in area). Half-hard wires were made by cold drawing the 0.204 in. rod to 0.102 in. wire, (75 pct reduction) in 6 passes and annealing at 427°C for 4 hrs. This annealed wire was then drawn to 0.081 in. wire, (37.1 pct reduction) in 2 passes. Square rod was made by hot rolling wire bars to 9/16 in, rod in 8 passes. This rod was then cold drawn to 0.445 in.-diam rod and annealed for 3 1/2 hrs at 538°C. It was then cold drawn to 0.325 in. rod and again annealed at 538°C for 3 1/2 hrs. Hard square rods were then made by cold rolling this material to 0.257 X 0.257 in. rod, a reduction in area of 20.5 pct. Half-hard square rods were made by cold rolling to 0.268 X 0.268 in. square, annealing for 332 hrs at 538°C and cold rolling to 0.257 X 0.257 in., a reduction of 8.5 pct. Soft wire or rod was made from all types of copper by annealing the hard-drawn material at 343°C for 3 hrs in steam. The grain size of the annealed 0.081 in. wire varied slightly among the three lots: from 0.015-0.025 mm in the silver-bearing OFHC to 0.035-0.045 mm in the OFHC copper. The annealed 0.257 in. wires were more uniform in grain size, averaging about 0.035-0.045 mm. Representative structures are shown in Fig I. EFFECT OF COLD DRAWING AND TENSILE STRAIN ON STRENGTH OF COPPER Conventional tensile tests were performed on the three types of copper in the various degrees of hardness described above. Results of these tests are tabulated in Table 2. The results in Table 2 are

Jan 1, 1947

By E. A. Anderson

THIS seems to be the year for superlatives in A.I.M.E. meetings. The programs of the various Divisions and Institute committees offered an abundance of interesting and valuable information in the form of technical papers, symposia. and lectures to large and interested audiences. The Institute of Metals Division may hold up its head with pride for its own program. With six technical sessions, three full-day symposia, and the annual I.M.D. dinner, four meeting days were not enough and many simultaneous sessions were required. The quantity and quality of the paper were equaled by the numbers and interest of those attending.

Jan 1, 1944

By G. Gabra

The kinetics of acidified thiourea leaching of pyrite concentrate was investigated at temperature ranging form 20 °C to a 60 °C. The effect of various parameters on the dissolution rates are discussed. The gold extraction was found to be zero and first orders with respect to Fe (111) and thiourea concentration, respectively. The order of the reaction with respect to sulfuric acid was found to be zero. The activation energy was determined from the Arrhenius plot as 2,039 kcal mole -1 (for a freshly prepared acidic solution containing Fe (111) as the oxidant and at 800 rpm stirring speed. This relatively low activation energy value suggests that the gold extraction is controlled by a-physical phenomenon. Under optimum conditions, more than 90% of gold has been dissolved in about 30 min. and 95% in 60 min. Attempt to recover gold from thiourea solution using active carbon is also discussed.

Jan 1, 1984

By L. W. Rowe, S. S. Cole

A laboratory bench scale unit is described whereby finely divided chlorinatable residues are held for a short period by a restraining bed of a coarse-grained ore of comparable composition to permit 'flash' chlorination of the high surface area powder. Results on chlorinating a finely divicled titania residue using rutile sand as the restraining bed showed that 92 pct utilization of chlorine and equivalent conversion of TiO2 in the fine residue to Ticl4 were attained with a dust loss of about 3 to 4 pct and an equivalent amount of ch1om'nation of the titanium values in the restraining bed. THE chlorination of coarse grain titaniferous ores; i.e., 20 to 150 mesh sizes in fluidized beds is practiced commercially.' One effective method found for the chlorination of a very fine material in a fluidized bed is the "flash" chlorination technique.' By charging the finely divided charge material into the bottom of an established bed of optimum sized rutile, ilmenite, titanium beneficiate, or even an inert material such as sand, chlorination occurs before the dust can pass through the bed. The major requirement is that the bed be less chlorinatable than the charge. In this process, the charge consists of a finely divided (between one and 50 µ) titania residue obtained from a titaniferous ore beneficiation process. The charge is blended with a 20 pct wt basis addition of 20 to 60 .mesh size low volatile coke (to minimize hydrogen chloride formation) and fed to the bottom of the bed with the chlorine gas stream. A ball check device is used to permit entry of the charge and prevent the bed from discharging when the gas flow is cut off. The coarse pieces of coke serve to reduce compaction in the charge mixture and permit sat]sfactory feeding without plugging or jamming. Feed and gas rates are adjusted to provide for complete reaction of the charge material, with 90 to 95 pct chlorine efficiency, and maintain a gas flow in the range of 0.4 to 0.6 ft per sec. The equipment consisted of a 3-in. diam mullite tube enclosed in an electric furnace. A bow-shaped 3/4 in. Saran tube fed the charge from an air lock type of feed hopper (to prevent the escape of the chlorine gas into feed bin) to the bottom of the bed. The charge rate was set by providing a small awiliary hopper below the feed hopper where a weighed portion of the charge could be discharged in a specified time interval into the main chlorine stream. The chlorine rate was measured by a flowmeter. The reaction tube was filled with a bed of Australian rutile ore, this restraining bed serving two purposes; i.e., it rapidly heated the fresh charge to the reaction temperature and retained the particles in the bed for a sufficient time for selective chlorination to proceed. Due to the fine particle size and open, porous structure of the charge, this reaction was almost instantaneous, and, with proper adjustment of feed and gas rates, very little fine material passed through the bed without reacting and only a very small fraction of the restraining bed was chlorinated. A typical reaction procedure was to fill the bench scale fluidized bed unit with a 1 kg charge of Australian rutile ore analyzing 95.5 pct TiO2, 0.6 pct FeO, a beach sand deposit 40 to 150 mesh size. When fluidized, the bed was approximately 2 ft in depth. The ore was fluidized with a 1:l mixture of chlorine and nitrogen at a rate of 0.40 ft per sec. This gas mixture was necessitated by the comparatively short bed depth; a larger unit, with a deeper bed, could be fluidized with chlorine alone without significant free chlorine loss. Feed rate was 8.0 g per min of beneficiated ilmenite analyzing 85.0 pct TiO2, 2.6 pct FeO plus 1.6 g per min of 20 to 60 mesh petroleum coke. The

Jan 1, 1962

By H. E. Wilborg

This chapter deals with those sands employed by the foundries for the manufacture of cores and molds used in the casting of such common metals as steel, gray iron, ductile iron, aluminum-based alloys, and copper-based alloys. Most metal is cast in "green sand" molds in which the sand mixture, consisting primarily of silica, clay, and water, forms a plastic material. This plastic material is rammed around a pattern in a split box called a flask, then the box is separated, the pattern is withdrawn, and the metal poured. These green sand molds are broken apart when the metal has solidified. The sand is then remixed and a new mold made for the next casting. To a lesser extent silica sand is mixed with resins or oils and, after forming, the mixture is hardened either by heat or chemical reaction. In any case, the foundry mold or core is used just once before being broken up and remixed for manufacturing another core or mold. By far the greatest consumption in the foundry is of those types of sand high in silica, low in clay (under 0.5%) and occurring in numerous locations thoughout the United States.

Jan 1, 1975

By R. M. Fowler, H. L. Hamner

DURING the last 25 years, there appeared in the literature a number of papers describing equipment and operating techniques for the determination of total oxygen in iron and steel. In the early papers, comparatively little attention was paid to side reactions that occur when iron is saturated with carbon at a high temperature in a high vacuum. As more experience was gained with the new method, the limitations appeared. Metals, with a boiling point lower than iron, distilled out of the crucible, condensed in the cooler part of the furnace, and subsequently reacted with carbon monoxide to form oxides and carbon. Aluminum, manganese, and the alkaline earth metals proved troublesome in this respect. Modifications have been devised to overcome the difficulties due to aluminum and manganese, while the alkaline earth metals are not of too much concern as yet to the steel chemist. The reactions of sulphur have received less attention, although it is generally recognized that some carbon disulphide is probably formed. Liquid air traps have been used in some cases to prevent any carbon disulphide from entering the analytical train. Sulphur was not a particular problem at the Union Carbide and Carbon Research Laboratories until the analysis of the irons of higher than usual sulphur contents became necessary. In order to describe the procedure developed for such irons, it will be necessary to first describe the type of vacuum-fusion equipment employed because the operation of vacuum-fusion equipment is an art to a considerable extent. At the Laboratories, vacuum-fusion equipment has been in daily operation since about 1930. Over the years, the evolution of this apparatus has been governed by the versatility required to analyze a wide variety of materials. Since all types of materials from high purity metals to slags are analyzed and, since seldom more than a few samples of one type are analyzed in succession, the apparatus was designed for accuracy and flexibility rather than for speed. A general view of the equipment is shown in Fig. 1, while Fig. 2 shows the relationship of the various parts. In Fig. 2, A is a vertical double-glazed 24X27/8 in. OD silica tube heated with a 20 kva mercury-arc high frequency generator. The tube is closed with a water-cooled brass head attached with de Khotinsky cement. A turret cap fits on this head and is sealed with a 1/8x3 in. "0" ring. The head contains a sight glass and two 8 in. horizontal glass tubes, for sample storage, cemented in with de Khotinsky cement. B is a four-stage Gaede mercury diffusion pump connected to the water-cooled head with a 11/2 in. copper tube through a flange with an "0" ring. The output of the vacuum pump feeds into an automatic Toepler F pump which compresses the gas sample over mercury in the measuring burettes, G and H. There are bypasses in this line for a McLeod gage C and a Piranni gage D, a manometer E, and for initial pumping out of the system with a Cenco Megavac backing-up pump. The reduction crucible shown in Fig. 3 is machined of Tungar Bulb quality (A.G.K.T.E.-2) graphite. The sample is guided into the crucible with the graphite funnel depicted on this figure. The arrangement of the crucible, radiation screens, etc. in the furnace is as follows: A 1 15/16x61/2 in. Alundum thimble, porosity RA-84, with two 1/8 in. holes near the top and opposite each other which take a pair of special tongs used for lowering it in place, is prepared. A 3/4 in. layer of powdered graphite is placed in this Alundum thimble, and the graphite crucible containing 20 g of ingot iron and 0.5 g of carbon is carefully centered on this bed of graphite powder and graphite powder is packed around it to the top of the graphite cru-

Jan 1, 1953

By Robert E. Brand, Strathmore R. B. Cooke

For a study of the bonding that occurs in magnetite pellets during oxidation, cubes of magnetite, hematite, and quartz were prepared, each with one surface polished and nearly optically plane. These faces were fired together under pressure and at various temperatures to determine whether bonding would occur. Sections of surfaces that bonded were examined microscopically. An attempt was made to measure the strength effected by this treatment. EARLIER work1,2 has shown that the strength developed by fired magnetite pellets containing silica or silicates is due to three separate effects. Two of these are associated with the formation of slag in the interior of each pellet at temperatures above 1000°C, where the atmosphere is substantially though temporarily neutral. The third is independent of the silica content and is responsible for the development of a hard shell around the pellet during the initial stages of firing, a condition which permits the pellet to assume the increasing load of the overlying burden and prevents extrusion of the slagged and semi-liquid interior. Pellets made from hematite concentrates do not show these effects unless specific additives are incorporated, and it is these differences in behavior which in large part account for the difficulty in producing satisfactory pellets from such concentrates. Elsewhere it has been stated that "the most important factor responsible for the development of strength in fired magnetite pellets containing no additive is the oxidation of magnetite to hematite and the subsequent recrystallization and grain growth of this constituent."' The object of the investigation reported in the present paper was to study in detail the mechanism described above and to evaluate its contribution to the strength of the fired pellet compared with other possible mechanisms, excluding slag bonding. This was effected by placing together polished faces of two cubes prepared from specific minerals and then heating them under constant pressure at different temperatures both in air and in nitrogen. The materials used were magnetite, hematite, and quartz. The magnetite was coarsely crystalline material from western Montana, the hematite was Itabira ore from Brazil, and the quartz was of optical grade but of unknown origin. A high-grade Lebanon (Pennsylvania) magnetite concentrate was used to prepare briquets for the investigation of bonding strength. Analyses of the iron oxide materials are given in Table I. The specimens for furnace treatment were prepared with a carborundum cut-off wheel, which cut the minerals into cubes approximating % in. along each edge. Care was taken to make the sides as parallel as possible. The edges of the faces to be polished were beveled, and the cubes were mounted in brass rings with sealing wax, this being essential to prevent the specimens from rocking during polishing. To prevent excessive friction, the wax was recessed so that only the brass ring and the face of each specimen would be in contact with the polishing lap. Each specimen was then ground with No. 600 carborundum to produce a level surface before polishing. The Graton-Vanderwilt process was not used for polishing because of the long time required by this method, but several other methods were tried. Cloth laps using levigated alumina or chromium oxide did not produce the desired polish. Satisfactory results were obtained by means of a pitch lap: which was used for all the mineral cubes, with levigated alumina as the polishing medium. The lap was operated in a machine similar to those used in the preparation of single optical surfaces. It was run at low speeds and moderate pressures, and polishing was stopped occasionally to prevent overheating of the lap. A good polish with flat surfaces could be obtained in about 5 min. After polishing the sealing wax was removed either in hot water or in a solvent such as turpentine.

Jan 1, 1955

By T. Vasilos, J. T. Smith

THE mechanism of pressure sintering, or hot pressing, for ceramic materials, has been investigated by several researchers.1-8 Plastic flow has been suggested as the rate-determining mech-anism1,2 while grain boundary sliding3,4 and fragmentation processess have been found controlling in other studies. Vasilos and Spriggs5,6 have reported that pressure sintering occurs by a diffusion-controlled mechanism. For the pressure sintering of metals, investigations with lead7 and with tin6 have not identified the operative mechanism during consolidation of these powders. This note reports the results of a pressure sintering study initiated to determine the mechanism controlling the densification of spherical copper powder. Temperatures of 300°, 400°, 500°, and 600°C at 2500, 5000, 7500, and 10,000 psi pressures were investigated. The copper powder for this study was obtained from Metals Disintegrating Co., Elizabeth, N.J. The minimum purity was reported to be 99.9 pct. The powder size was -325 mesh and a lineal analysis showed the average size to be less than 1 p. An alumina die body and punches were employed. Graphite spacers were placed between the copper powder and the punches before pressing. It was expected that the graphite would form carbon monoxide with any entrapped air and form a reducing atmosphere within the die cavity. This condition was generally realized during pressing although a minor amount of oxidation occurred at 500" and 600°C. The oxide particles were located randomly in the pressed samples and were not considered to influence the densification process. Calibration tests showed the temperature of the copper pellet to be about 20°C less than the die wall temperature, probably resulting from heat losses through the punches. This difference was compensated during the experimental pressing operations. The hot pressing equipment employed for this work has been described by Spriggs et a1.9 and was calibrated with a Baldwin-Lima-Hamilton load cell. Travel of the punches was monitored with a dial indicator showing increments of travel to 0.0005 in. Relative density was calculated at selected time intervals for a known copper weight, punch travel, and die diameter. The accuracy of this calculation was *1 pct. Average grain size after hot pressing was obtained by lineal analysis. Typical densification curves are presented in Fig. 1 and Fig. 2 where relative density is plotted vs log time as a function of applied pressure for the 300" and 600°C pressure sintering temperatures, respectively. The curves for 400" and 500°C were similar to those at 300°C and consequently are not shown. The curves at 300°C as well as 400" and 500°C do not show an end-point or limiting density for a particular applied pressure. At 600°C, a density in excess of 95 pct of theoretical has been reached such that further densification is extremely slow for the 5000, 7500, and 10,000 psi pressures. It is suggested that further densification at these pressure levels may be retarded or prevented by discontinuous grain growth, by entrapped gases, and by other microstructural limitations as described by Cob1e.10 The curve for 2500 psi hot pressing pressure is a straight line over the time interval although a slight change in slope may be occurring at the last time intervals. The plastic flow models,1,2 derived for hot pressing, predict the existence of an end-point (or limiting) density dependent on the yield point of the material at the temperature of interest. The yield stress of copper at a 0.005 strain level has been

Jan 1, 1965

By Robert E. Ogilvie, Zvonimir Ban

Oxidation experiments were conducted above 600°C to investigate the oxidation products formed on the surface of MoSi2. Results are presented which indicate that minor iron impurities play a key role in the oxidation behavior of MoSi2 above 600 °C. Based on considerations of the crystal chemistry of the oxidation products, MoSi2 with rhenium and iron additions was found to be resistant to oxidation in the pesting temperature range. AS early as 1914, Honigschmidtl observed that some silicides of molybdenum exhibited high resistance to oxidation at elevated temperatures. This fact did not arouse much interest until 1950, when Kieffer and cerwenka2 examined this property in more detail. They found that Mo-Si alloys with approximately 70 pct Mo (by weight) could be heated to 1600°C in an oxidizing atmosphere without any significant damage. The surface was found to be protected by the formation of an extremely thin silica glass layer which had no tendency to spa11 during subsequent thermal cycling. In 1955, Fitzer3 discovered that even solid bodies made of MoSi2 completely oxidized within a relatively short time when exposed to the air in the temperature range from 300° to 600°C. To describe this phenomenon he proposed the name "molybdenum disilicide 'pest' ", clearly analogous to the previously observed "tin plague" ("tin pest") which, however, arises as the result of a phase transformation. Studies performed by Fitzer and, in particular, one published recently by Berkowitz, Blackburn, and Fel-ten,' comprise the most extensive research to date on the pest phenomenon in MoSi2, as far as the fundamen- tal mechanism of the process is concerned. The first of these studies revealed the existence of a crystalline phase which appeared at the surface at 750°C and dissolved in the glassy silica layer at 1150°C. The logical assumption was that this phase was some reaction product of MOO3 and SiO2. The formation of a reaction product of this type seemed probable since it had been mentioned by Glemser and Lutz6 in a paper describing their studies of molybdenum oxides; however, this assumption was later disproved.8 It is our belief that information concerning the exact nature of this crystalline phase may be important for a better understanding of both pesting and the protection mechanism. Therefore, since the only available general description of the pest phenomenon was that of Fitzer, it was decided to reproduce his experiments. These experiments established that, in addition to the "pest" and "nonpest" temperature range, an intermediate region exists between 600" and approximately 650°C. This region is characterized by the appearance of a variable amount of yellow to orange colored crystals. The electron-beam microanalyzer was used to qualitatively determine their composition. Iron and molybdenum were found to be major constituents. This result can be explained based on the following facts: 1) iron, according to literature data,* is the most common impurity in molybdenum powder, and its content can be as high as 0.25 pct; 2) technical silicon powder usually contains iron; 3) steel ball mills are often used for the crushing and grinding of MoSi2. In order to clarify the exact role of iron, it was deliberately added to a stoichiometric mixture of molybdenum and silicon. The observed results corroborated the previous experiment, proving that iron (probably as some silicide phase) concentrates along the grain boundaries. I) EXPERIMENTAL PROCEDURE A) Oxidation of MoSi2 with Iron Additions. 1) Specimen Preparation. Specimens were prepared by both

Jan 1, 1967

Only the coal of the Sunnyside district in Carbon county is coked. Two companies, the Utah Fuel Company and the Columbia Steel Corporation, operating adjoining mines at Sunnyside and Columbia, produce coke. The Utah Fuel Company has 81 9 beehive coke ovens at Sunnyside. Only 350 ovens are being operated at the present time, largely because the smelters which had been using Sunnyside coke changed their equipment from blast furnaces to reverberatory furnaces

Jan 1, 1925

WHEN geologists began probing the grayish rock mass, natives of Adams County, Pa., called soapstone, they were paid scant attention. However, the soapstone, at first misidentified as pyrophyllite, was in reality sericite schist, a hydrous aluminum silicate whose chemical analysis resembles pyrophyllite, except that it has a slightly higher iron and potash content. In addition to its grayish color, sericite schist is foliated and has a greasy feeling much like that of talc.

Jan 10, 1953

By Lewis Stockett

During the year 1903, a building having machinery corresponding to ail anthracite-coal breaker was erected at the town of Stockett, Cascade county, Mont., for the purpose of breaking-up and cleaning bituminous coal. The coal is mined from a vein of the Kootenai group of the Lower Cretaceous measures having the following section: The vein is nearly horizontal in position, and each bench differs in quality as shown in Table I.

Jan 1, 1905

By Edwin B. Douglas

The Blackbird mine is owned by Calera Mining Co., subsidiary of Howe Sound Co. The mine is located in the Salmon National Forest, Lemhi County, Idaho, about 22 miles west of Salmon and 220 miles north of Pocatello. The thought of producing cobalt from a prospect that offered excellent opportunities stimulated everyone connected with this project. But as time went on, it was found that every phase of the development presented unusual difficulties.

Mar 1, 1956

By F. X. Tartaron

The comparison of actual energy of comminution with theoretical surface energy presents a wide gap. On the other hand, Solid State Theory presents a viewpoint that places actual energy of breakage in understandable relationship with the theoretical strength of materials. Therefore the physical background of comminution theory favors Kick's Law. A11 discussions of comminution theory appear farfetched when comparison is made of the actual energy of crushing with the energy input called for by thermodynamic theory. Quoting Taggart:' "The work required to crush halite was of the general order of 0.10 kg cm per sq cm of new surface produced (based on air percolation) whereas the theoretical energy of this new surface, based on thermodynamic calculation by a number of investigators is 1 x 10'4 kg cm per sq cm or the work expended was 1000 times the new surface energy — an indicated crushing efficiency of 0.10 pct." It is frustrating to probe into comminution theory with the prospect that the energy one is measuring is 99.9 pct waste energy. Do the laws of comminution deal with energy consumed by mineral breakage or with waste heat energy? There seems to be something wrong. Solid State Theory may provide the answer. The following statement is particularly apt to the situation: "The fundamental fact about metals and indeed all materials, is that they are much weaker than they should be. By this, we mean that if the stress required to cause a given plane of atoms to slip past a neighboring plane is calculated from basic atomic and Solid State Theory, the resulting number is some 1000 times too large to be accounted for by errors in approximations or assumptions. We know now that this is due to dislocations, and we even have a fair understanding of the details of the process by which dislocations make a crystal weak. An intriguing possibility which suggests itself, results from the discovery of very minute metallic crystals which are apparently free of dislocations and which have a strength approaching the ideal value for a perfect crystal." Here we have an extraordinary reversal of the situation. The actual energy for breakage is only one-thousandth the theoretical instead of 1000 times as given by Taggart. But the theoretical energy presented by Solid State Theory is the binding energy between atoms (or ions) in a crystal lattice. This is the kind of energy envisaged by Kick's law. The surface energy or the other hand corresponds to Rittinger's law. Comparison of theoretical with actual, on the basis of surface or on the basis of Rittinger's law, seems to present an absurdity; yet Rittinger's law is confirmed by an impressive array of experimental evidence. Comparison of theoretical and actual on the basis of Solid State Theory or, in other words, on the basis of Kick's law seems reasonable; yet there is not a scrap of evidence to verify Kick's law. The situation appears paradoxical, but the developments in the next section of this paper show that the paradox is a hint to a strange turn of events. ENERGY-WEIGHT FRACTION FUNCTION charles3 has presented a final equation showing the relation of energy consumed in comminution to size of product n{-1) a-n + 1 E is energy, C is proportionality constant, a and n are constants and k is the coarsest size in the ground product (size modulus). In the course of study of a large amount of experimental evidence, Charles discovered that in the general case, a-n + 1 approximated zero. For some reason, a and n differed only by unity. But if a—n + 1 = 0 within experimental error, then it is obvious that Eq. 1 states that it requires an infinite amount of energy to grind any sample to any size. This is a case where nature gives an absurd answer to a man-made mathematical equation, hence something is wrong with the equation. An adjustment must be made to fit the equation with experience. TO reveal the nature of the adjustment, the differential equation preceding the second integration in Charles' group of equations is given When Charles integrated the quantity xa-n it was almost impossible for him to realize that he was dealing with a special case of integration and that

Jan 1, 1962

By Arnulf Muan, R. W. Taylor

Activities of iron in Fe-Pt alloys have been dctermined by equilibrating mixtures of platinum metal and iron oxide at known oxygen Pressures in a thermobalance at 1300°C. Conzpositions and iron activities of the oxide phase at equilibrium are known from previous work, and compositions of the Fe-Pt alloy phase formed at equilibrium were detcvt?zined from the observed weight changes of the samples. The activity curve obtained shows a strow negative deviation from Raoult's law. THE present investigation was undertaken as part of a research program dealing with phase equilibrium relations existing among the oxides of iron and titanium at 1300°C. At low oxygen pressures of the gas phase in equilibrium with these oxides, the iron activity of the system is high, and considerable alloying of iron with the platinum used as a container material takes place. Thermodynamic data for Fe-Pt alloys at 1300°C are needed in order to evaluate quantitatively the extent of such reactions. Larson and chipmanlhave determined activities of iron in Fe-Pt alloys at 1550°C by equilibrating platinum metal with CaO-iron oxide-SiOzmelts in which the iron activities were known. Compositions of the resulting Fe-Pt alloys were determined by chemical analysis. Mundiath and Gerassimov2 have studied thermodynamic properties of Fe-Pt alloys by electromotive force measurements in the temperature range 550" to 1000°C. The experimental method used in the present investigation is a slight modification of that used by Grube and Ratsch3 in studies of NiCr-alloys. 1) EXPERIMENTAL METHOD 1) General. Mixtures of platinum metal and iron oxide were equilibrated at 1300°C in atmospheres of known oxygzn przssures, and the course of the reactions was followed by measuring the weight changes of the mixtures. The principles involved in the derivation of composition-activity relations from these measurements are illustrated by the composition triangle for the system Fe-FeZO3-Pt shown in Fig. 1. Take as an example a mixture of FeZO3 (hematite) and platinum such that the total composition is represented by point T. If this mixture is heated to 1300c in air (poz = 0.21 atm) and the oxygen pressure is then reduced gradually, the oxygen content of the oxide phase decreases and increasing amounts of iron enter the metal phase. As the oxide phase and the metal phase for all practical purposes are insoluble in each other, their compositions are represented by points moving toward Fe along the joins Fe-Fe,03 and Fe-Pt, respectively. The total composition of the mixture during this process also changes, but only with respect to oxygen content, because the vapor pressures of iron and platinum are negligible at 1300°C. Hence the change in total composition is described by a straight line (constant Fe/Pt ratio) radiating from the 0 apex of the composition triangle Fe-Pt-0, of which the triangle in Fig. 1 is a part. Only one such line ("oxygen reaction line", T-T",) is shown in Fig. 1. The total composition of the alloy-iron oxide mixture at any instant must, in addition, be located on the straight line (conjugation line) connecting the two points representing the compositions of the two coexisting phases. It therefore follows that the total composition of the mixture at any instant is represented by the point of intersection between the conjugation line and the oxygen reaction line. An example of the situation prevailing at a chosen oxygen pressure, po2, is shown in Fig. 1 by points a' (alloy composition), b' (oxide composition) and T' (total composition). Point b' is known from the work of Darken and Gurry,4 and point T' is experimentally determined by the observed weight change of the mixture (distance T-T). Hence, point a', the composition of the alloy, is determined from the above data as the intersection between the join Pt-Fe and the extension of the straight line bl-7'. The activity of iron in the alloy at equilibrium is identical to that of the iron oxide phase, if the same

Jan 1, 1962

By G. W. Healy, L. F. Sander

was investigated by reacting thin discs of calcium oxide with gas mixtures of CO2, CO, and Son. Its value was 19,300 * 300 cal independent of temperature in this range. No solid solubility of sulfur in calcium oxide was detected within the limits of the experimental method and it is estimated to be below 0.025 pct by weight. The importance of lime in desulfurization is well-established but complete information on the pure phase equilibrium: CaO + 1/2 s2 = CaS + +02 [11 is not yet available. The goal of this work was to evaluate solid solubility of CaS in CaO and to determine the free-energy change associated with Reaction [I] at temperatures of 1400" to 1650°C. The equilibrium constant for Reaction [1] can be written: It is convenient to rewrite Eq. [2] in the form: where A = {Ps /PqJ1'2 has been referred to' as the "sulfurizing power' of a gas mixture. In this work, thin discs of CaO were suspended in a vertical tube furnace and exposed to CO + CO2 + SOz gas mixtures having known values of A. The samples were then analyzed for sulfur. As expected, X-ray diffraction confirmed that CaS was the only sulfur-bearing phase formed at the relatively low oxygen pressures used. EXPERIMENTAL PROCEDURE Reagent-grade CaCO3 was pressed in a 3/8-in.-diam pill die and prefired in air to produce CaO discs weighing between 0.004 and 0.01 g. Several discs were used to provide a suitable weight for chemical analysis while maintaining a large surface area to react with gas mixtures. These were placed in a platinum mesh basket and suspended in the gas stream in the hot zone of a vertical tube furnace. Desired gas mixtures were prepared from cp grade CO and CO2 and anhydrous grade SO2. The method of soap bubble displacement was used to calibrate capillary flow meters. While this gave excellent results with CO and Con, some problems with bubble insta- bility and soap film "drag" arose with the use of SO2 at low flow rates. Hence, frequent sampling and analysis of gas mixtures was carried out to insure proper control of the ingoing SOZ. The furnace used for gas:solid equilibration was a vertical mullite tube externally wound with 60 pct Pt-40 pct Rh wire having a diameter of 0.028 in. An inner tube of $ in. ID served as the reaction chamber having Pyrex ground joints sealed to the mullite to provide gas-tight connections at top and bottom. A Pt-Pt 10 pct Rh thermocouple was inserted into a protection tube adjacent to the sample basket to measure sample temperature during a run. Constant-temperature control to 2C was observed at any desired set point within the range of this investigation. This was accomplished by a control thermocouple imbedded in the furnace windings which served to actuate an electronic controller wired for high-low operation. The sulfur analyses of the solid samples were carried out using a stoichiometric combustion technique based on the method of Fincham and Richardson. Some analyses were done using a modified evolution method3 but these were used primarily to check the results of the combustion method. The results were in good agreement but the combustion technique of-ferred an advantage in economy of time and material. CALCULATION OF GAS EQUILIBRIA Heating a given mixture of CO + CO + SO2 to high temperatures gives rise to a large number of product species. The details of calculating the partial pressures of these products of interaction and dissociation can be found in several references4,5 and need not be repeated here. The thermodynamic data selected for the major species in the gas mixtures are shown in Table I. Equilibrium constants from these reactions were combined with oxygen, carbon, and sulfur balances and a computer program written to facilitate the calculations. Some early difficulties in reproducing experimental results were finally traced to the effect of atmospheric pressure changes. No reference to consideration of this question had been found in the

Jan 1, 1969

By E. S. Machlin, W. R. Yankee

IN a previous study1 of the effect of heating com-mercial titanium in air on its subsequent friction coefficient against other metals, as well as itself, it was found that the friction coefficient markedly decreased from a value of about 0.7 to about 0.3. A tentative explanation was given that surfaces normally produced at room temperature are not contaminated sufficiently to prevent seizing or welding of the titanium to the softer mating metals. The latter tend to cleanse themselves during rubbing over the harder titanium. It was thought that the lack of a contaminant protective film on the titanium was due to the high solubility of titanium for oxygen and nitrogen and hence an inability to form a contaminant oxide or nitride. This explanation requires the ratio of the surface absorption rate to the diffusion rate to become much lower at room temperature than it is at high temperatures. In order to check the phenomenon further, commercial titanium specimens were nitrided or oxidized at 800°C for 20 hr in flows of prepurified N2 and 01, respectively, at about 1/2 in. H2O above atmospheric pressure. Friction runs were made in argon using a freshly cut copper hemisphere (cut in argon) on surfaces cut successively into the diffusion layers in the titanium (cut in argon) using the techniques described in a previous publication.' DPH values (100 gram load) were made as a function of depth into the diffusion layer using a Tukon tester. Also, micrographs were taken at separate cross sections to indicate the diffusion layers. The results obtained are presented in Figs. 1 and 2, which show the "static" friction coefficient vs hardness for the nitrided and oxidized specimens, respectively. A separate measurement of the friction coefficient of clean copper vs iodide titanium also was made. From results reported in the literature' giving the oxygen and nitrogen contents as functions of the hardness, cross plots were made showing the friction coefficients as functions of the amount of interstitial solute. These plots are given in Figs. 3 and 4. From micrographs of the diffusion layers and the phase diagrams, it was deduced that the data in Figs. l through 4 correspond to the single phase a region. The points observed on the compound regions have been excluded from the figures. It is apparent that nitrogen or oxygen in solution in the a titanium markedly affects the friction coefficient against a softer mating metal. Discussion of Results These results are extremely interesting from both a practical and theoretical viewpoint. The theoretical implications will be discussed first. According to Bowden, the friction coefficient should be given to a good approximation by the relation where a is the fraction of contact area that has welded, a is the shear strength of weaker component, and H is the hardness of softer component. Using this relation alone, it is difficult to understand the results because none of the terms should be affected by a variation in the oxygen or nitrogen content of the harder and stronger metal, titanium. Even if the ratio of S/H for titanium is used in Eq. 1, the ratio has been shown to be independent of oxy-gen or nitrogen content.' If a more rigorous equa-tion is used combining Eq. 1 and a result given pre-viously" for the case where welding is absent, then the relation obtained is µ = a S/H + (1-a) a W aß/H where a is constant and Waß is the work of adhesion between the two metals comprising the friction couple. This relation states that if a is less than 1/2 or so, variation in the work of adhesion Waß between copper and the titanium should affect the friction coefficient markedly. It is reasonable to expect that the work of adhesion will depend on the oxygen or nitrogen content of the titanium. Available data4 show that clean metals and oxides have much lower works of adhesion than the same metals against the

Jan 1, 1955

By K. Winterton

The effect of a near-saturation unidirectional magnetic field was to decrease slightly the endurance life in Armco iron in the annealed condition. This is expected since the energy-absorbing mechanism associated with domain wall movemenfs is inhibited bv the strong field. THE factors determining failure under dynamic loading are not yet clearly recognized. One of the properties of a metal which might be thought to influence fatigue life is its damping capacity. Foppl1 conducted an alternating torsion test at a frequency of 700 cpm continuously for a period of 3 years, without the test piece breaking or showing any sign of deterioration after 1100 Million cycles of stress; the rate of dissipation of energy was sufficient to maintain the test piece at about 100°C above the ambient temperature. cazaud2 concludes from this, and others follow him, that ('the capacity for dissipation in the form of heat by internal damping is unlimited" and that therefore "damping is not directly related with fracture by fatigue." Future work may necessitate qualification of this rather uncompromising view. It is shown later that in all

Jan 1, 1960