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By R. T. Mishler

Silver-gold. mine, in northern Mexico, with arrow veins in rhyolite. One fourth area developed has been ore. Deposits average 20 in. wide and 73 oz. silver per ton; diluted in mining to 40 oz. per ton. Developed by drifts and raises at 100-ft. intervals. Samples cut every 5 ft. Ore and waste sampled separately to make combined stoping width 3 or 3 1/2 ft. Ore reserves figured to sloping width; high assays not modified. Tonnage and assay of ore extracted higher than estimates. Ore stoped principally by cut and fill method. Cars from each stope counted and sampled. Cars check tonnage to concen¬trator within 1 per cent.; silver assay 9 per cent. high. Tonnage and assay from scopes corrected to agree with feed to concentrator. Profit or loss for each slope estimated monthly. THE Lucky-Tiger mine is a silver-gold property, situated at El Tigre, in the northeastern part of Sonora, Mexico, at, an elevation of 6000 ft. in the Sierra Madre Mountains. It is 30 miles by wagon road from the Esqueda station on the Nacozari railroad. Since its discovery in 1903, the mine has produced forty million ounces of silver. The ore has averaged 40 oz. silver and 0.25 oz. gold per ton. Copper, lead and zinc have been of minor importance, having averaged 0.4 per cent., 1.1 per cent., and 1.5 per cent., respectively. The richness of the ore,, combined with its occurrence in narrow veins, required the use of the more expensive methods of mining.

Jan 2, 1925

By James Norman

SPODUMENE is a lithium-bearing pyroxene, and is an important source of lithium compounds. Because of its high alumina and lithia content, it might be a desirable constituent of glass batches. The use of spodu-mene in ceramics will undoubtedly increase, as it has been shown that a mixture of the proper proportions of this mineral with soda feldspar and potash feldspar has a much lower maturing temperature upon firing than has any one of the three components.1 The mineral spodumene seldom occurs as pure mineral, but ordinarily with feldspars, mica and quartz. All spodumene-bearing rocks tested contained these minerals as gangue. Small amounts of iron and manga-nese oxides also were present, usually as stains on the silicate grains. Mica associated with the spodumene carried a considerable amount of lithia. This was discovered in flotation tailings, which, although virtually free of spodumene grains when examined microscopically, showed 0.4 to 0.5 per cent Li2O on chemical analysis. The lithia content of micas picked from the North Carolina spodumene rock was variable. Some samples contained little lithia, others more than 3 per cent. In 1938, under the supervision of Oliver C. Ralston, ? the Bureau of Mines, in cooperation with the Tennessee Mineral Products Corporation, undertook to study the beneficiation of North Carolina spodumene by froth flotation. The Bureau had previously published investigations on the beneficiation of spodumene.2,3 The methods described in the second publication' did not give good results with badly weathered spodumene rock, so that more thorough investigation of the subject was warranted.

Jan 1, 1940

By N. A. Ziegler

CONSIDERABLE work has been and is being done on the changes of physical properties that take place in alloys at elevated temperatures, and much information on this subject is published. Much less is known, as pointed out by Rickett and Wood,1 about reactions between the alloys and atmospheric gases and still less is known about changes within the alloy itself under the influence of heat and given atmosphere. Moreover, most of the work published has been done on the alloys of "heat-resist-ing" type, in which chromium is an essential ingredient, the behavior of all other alloys being quite unknown, except perhaps of decarburization produced at the surface by oxidizing atmospheres. It has been shown' that iron, with total amount of foreign ingredients not exceeding 0.01 per cent, if heated in an oxidizing atmosphere at above 900° C., may be saturated with oxygen to 0.1 per cent. It was suspected that something of a similar nature may take place in iron-silicon alloys (transformer material), the mechanism of such processes being either a direct diffusion of oxygen into the alloy, or oxygen combining with silicon to form Si02 or more complicated (silicate) inclusions. Another possi-bility to be considered was that during annealing in oxidizing atmos-pheres, when scale is being formed, silicon may oxidize preferentially at the surface, thus impoverishing the alloy in silicon. In collaboration with Dr. T. D. Yensen,3 the writer set out to investigate this problem about two years ago in order to settle these questions.

Jan 1, 1934

By R. J. Borg, C. E. Birchenall

The self-diffusion coefficients for a iron have been deternzined between 980° and 1167° K using Fe55 as the tracer. With decreasing temperature the diffusivity was found to decrease more rapidly than predicted by the Arrhenius equation in the region of the Curie temperature. The diffusion coefficients obtained well above the temperature of the magnetic transformation are more precise ard differ substantially from all the previously reported values. In the temperature region beginning at least 50" above T,, the diffusion coefficient is given by D = 118 (±2) exp 1 HE self-diffusion coefficients for a iron have been reported previously as the result of four independent investigations The general lack of agreement and the poor precision of most of the previous work prompted the redetermination by the present authors. The possible effect of the onset of ferromagnetism upon the diffusivity5 provided an additional impetus for this investigation. The earlier measurements of Birchenall and Mehl1 gave low values for the diffusion coefficient at temperatures below the Curie temperature, Tc. However, the precision of these measurements is not sufficient to establish an indisputable correlation between the low values and the magnetic transformation. The results of this investigation along with all the previous ones are shown in Fig. 1. EXPERIMENTAL Small rectangular samples, approximately 1 by 0.5 by 0.3 cm, of high-purity iron (Vacuum Metals Corp., "Ferrovac") are first heated in hydrogen at 900°C for24hr in order to remove possible trace amounts of dissolved carbon and oxygen. The small

Jan 1, 1961

Discussion of the paper of J. V. EMMONS, presented at the Pittsburgh meeting, October, 1914. and printed in Bulletin No. 93, September, 1914, pp. 2233 to 2248. ALBERT SAUVEUR, Cambridge, Mass.-Mr. Emmons is to be congratulated for having placed before us in so forcible and satisfactory a manner a question of much importance-that of the surface decarbonization of steel. Of course, both manufacturers and consumers have known for many years that during the heat treatment of high-carbon steel, surface deca.rbonization is always likely to occur to a greater or less degree, but the subject does not seem to have been investigated with the method and thoroughness it deserves. I am in substantial agreement with Mr. Emmons's conclusions, and I have but little to add to what he has so well said. His statement that carbon dioxide is just as effective an oxidizing agent as pure oxygen is likely to cause surprise and some will wonder whether his investigation has been carried far enough to warrant so unexpected a conclusion. The reaction C + 0 = CO, expressing the oxidation of carbon by pure oxygen, is decidedly exothermic, whereas the reaction C + C02 = 2C0, expressing the oxidation of carbon by carbon dioxide, is endothermic. Decarburization by pure oxygen, therefore, should take place much more readily than by carbon dioxide. One cannot help regretting that the author does not mention' the best way of preventing in a practical manner surface decarbonization while treating tool steel and other high-carbon steels.

Jan 4, 1915

By P. F. Richardson, J. L. Perisho, W. J. Roe

Handling and transport of coal during the winter months can be a severe problem. The inability to unload frozen coal from rail cars produces serious economic and logistic problems due to transportation delays, rail car shortages, and demurrage on the rail cars. One method of dealing with the problem of unloading frozen coal has been to spray freeze conditioning agents onto the coal before it is loaded into rail cars. Both water soluble and oil based formulations have been used as freeze conditioning agents. The water soluble treatments generally contain a polyhydroxy alcohol, such as ethylene glycol, or salts of alkaline earth metals, such as magnesium chloride and calcium chloride, as freeze point depressants. The oil based treatments consist principally of hydrocarbons, such as No. 2 oil or diesel fuel. The authors' tests have shown significant differences in the effectiveness of these freeze conditioning agents, depending on the particular coal substrate being treated. These differences correlate with the coal porosity and inherent moisture of the substrate. In general, the greater the porosity of the coal, the smaller the effect of the freeze conditioning agents. Coal porosity has a greater impact on water soluble freeze conditioning agents than oil based products. The authors investigated the pore structure of a variety of coals using mercury intrusion. Findings were related to the effectiveness of different freeze conditioning agents as measured by unconfined compression strength tests. In general, coals with a large number of very small pores (between 0.05 µm and 0.03 µm) do not respond as well to freeze conditioning chemicals.

Jan 1, 1986

By Lawrence Adler

MINE hoist ropes have hitherto been selected by successive approximation, a process both tedious and inexact. The proposed expression is a readily solved synthesis of existing data and the following standard equation:' [ W + Wr + (W + Wr) -a 9 (W + W)f + b] n=T [1] For convenience, a glossary of all terms appears on page 564. Since rope weight (W,) and bending load (B) are functions of unit rope weight (Wv), which in turn is a function of rope strength (T), W, and B can be expressed in terms of T. W, as a Function of T: A study of the curve in Fig. 1, unit rope weight vs strength, yields Eq. 2: W. = -f- [2] Therefore Wr = WvL = T. [3] iv B as a Function of T: From Fig. 2, unit rope weight vs diameter, Eq. 4 is obtained: W, = 1.6d2 [4] B is related2 to d and D, and d has been expressed in terms of W, by Eq. 4, so the curve B vs W, (Fig. 3) gives Eq. 5: 177,000 177,000 This may readily be checked from the expression3 for a 6x19 rope, i.e., d3 B = 288,000D Since d2 = 0.625 W, and N = substituting d into the above expression gives Ea. 6: 180,000 180,000 B T, which will be used. [6] Into Eq. 1 substitute Eq. 3 and Eq. 6, noting that f=0.02: W + T 1.02+=T. [7]

Jan 1, 1958

The following is an incomplete list of members and guests who called at Institute headquarters between Nov. 10 and Dec. 10, 1917. Harlan H. Bradt, Duluth, Minn. Lt. Geo. H. Morgan. Albert Burch, San Francisco, Cal. F. W. Osborn, Ajo, Ariz. J. A. Daniel, Institute of Mining & Metal- J. C. Ray, 2d Lt., 0. M. C., N. A. lurgy, London. A. E. Ring, Creede, Colo. Martin Fishback, Benson, Ariz. Geo. B. Rodgers, Dobbs Ferry, N. Y. E. L. Foucar, San Francisco, Cal. Forest Rutherford, Pueblo, Colo. I. A. L. Henderson, Institute of Mining & J. G. Scrugham, Reno, Nev. Metallurgy, London. A. F. Shurick, Forest Hills, L. I., N. Y. Jerome A. Hilbert, Santa Monica, Cal. Arthur C. Spencer, Washington, D. C. B. B. Hood, Chrome, N. J. Robert C. Sticht, Mt. Lyell, Tasmania. J. C. Hoyt, Jerome, Ariz. A. Perry Thompson, San Francisco, Cal. A. F. Kennedy, Duluth, Minn. J. B. Tyrrell, Toronto, Canada. Paul S. King, Wilmington, Del. Thor. Warner, Phoenix, Ariz. Alfred C. Levis, Golden, Colo. S. F. Wellman, Cleveland, 0. A. F. Lucas, Washington, D. C. Gardner F. Williams, San Francisco, Cal. B. E. McKechnie, Sharon, Pa. W. G. Woolf, Salt Lake City, Utah.' A. N. Mackay, Barranquilla, Colombia. C. W. Merrill, San Francisco, Cal. P. G. Beckett expects to be located in New York for some time, and may be addressed care of the Phelps, Dodge Corporation at 99 John Street. Corey C. Brayton and E. R. Richards have temporarily closed their San Francisco offices in order to give more time to their operations at Midvale, Utah.

Jan 1, 1918

By Robert Maddin

crystal prior to, polishing in order to eliminate coring. This treatment may be accomplished by wrapping the single crystal tightly in very thin, dead soft, brass foil and annealing in the presence of air for 20 hr at 800°C. Since the wrapping encircles the sptcimen three to four times, only a very slight amount of oxidation occurs on the specimen surface. On unwrapping one of these cylindrical single crystals. in. in diam by ro in. long (72.75 pct cu, 27.23 pct Zn, 0.01 pct P11, 0.01 pct re), mall light-gray depnrrits in the form of circular arcs werenoted on the part nf the foil which had been in contact with the single crystal, Fig r. (By superim- approximatetl). These deposits, which, from their color, suggest the appearance of sublimated zinc, were found to coincide roughly with a set of octahedral planes nearly perpendicular to the rod axis. The pattern shorn in the figure held no relation to the profle of the sample since the markin~s on the crystal More annealing werc attributed to traces of cube planes. It seems very likely that the deposits were formed by sutllimation of zinc diffusing from octahrdral planes since diffusian would Eogically take place along planes of maximum atomic spacing. However, it is difficult to understand why a continuous sublimation of zinc should occur from a single crystat in contact with a wrapping roil OF the same composition, and why diffusion would take place along specific octahedral planes and in a regular pattern.

Jan 1, 1949

By R. E. Smallman, J. C. Terry

J. C. Terry and R. E. Smallman (Llniuersity of Birmingham, England)—In a recent publication53 Wood and Westbrook have reported the results of an investigation of the tensile behavior of fl-phase AgMg alloys. These results agree in broad outline, but differ in the details, with those obtained in the above laboratory and, consequently, some discussion of their paper would seem appropriate. In our experiments, tests were carried out on extruded wires, 2 mm diam, in a hard-beam tensile machine, and while an oil bath was used for the tests up to 150°C, above this temperature the oil bath gave rise to serious contamination of the specimens and hence tests above 150°C were made in vacuo. This procedure is different to that adopted by Wood and Westbrook. The ß-phase alloys exhibit differences in mechanical behavior when they are tested in different temperature ranges. In agreement with Wood and Westbrook, three characteristic ranges are observed which may be classified as low, intermediate, and high temperatures, respectively. Our experiments show that in the low-temperature region, the shape of the stress-strain curves is similar to that reported. However, in addition, it is observed that the temperature at which the low-temperature region ends is markedly dependent on strain rate, and increase with increasing strain rate as shown in Fig. 18. The temperature at which a transition from the low to the intermediate temperature takes place is about 0.4 to 0.45 of the absolute melting point, Tm. This transition temperature coincides with that at

Jan 1, 1963

By J. E. Schiller, S. E. Khalafalla

To improve technology for treating process water, US Bureau of Mines research has shown that magnesium oxide (MgO) has many advantages over lime or caustic soda for precipitating heavy metals. Sludge produced by MgO occupies only 0.2-0.3 times as much volume as the precipitate made wing a soluble base. While a settled, lime-formed precipitate is easily resuspended, the MgO-metal hydroxide sludge becomes cemented together on standing. Settling of the metal hydroxides from a dilute suspension is more complete than precipitates formed with other bases. Virtually any metal that can be precipitated by raising the pH can be treated using MgO. A three fold to fourfold stoichiometric excess of solid reagent is added. The mixture is reacted for five to 10 minutes. Polymer is added, and settling or filtration completes the process. Because of the greater cost of MgO compared with lime, large-scale practice of this technology will probably be limited to water containing 50 mg/L (3 gr per gal) or less of dissolved metals. For such dilute solutions, chemicals are not a large fraction of total treatment costs, so more desirable sludge properties might justify higher chemical expenses. While the MgO process is technically suitable for widespread application, the extent to which it is adopted will probably be determined by a trade-off between the greater cost of MgO compared with lime and the superior properties of the precipitates and their corresponding ultimate disposal costs.

Jan 1, 1985

By S. J. Rothman, A. L. Harkness, L. T. Lloyd

Self-diffusion in Y uranium has been measured using U235 as the tracer isotope. The diffusion coefficient fits an Arrhenius-type equation D = 2.33 x 10 -3 exp (- 28,5000/RT) cm2/sec The values of Do and Q are unusually low and are not consistent with the values expected from theories based on a simple vacancy mechanism of diffusion. CYLINDRICAL samples, 1 cm in diam and 1/2 to 1 cm long, were prepared from high-purity uranium containing 0.0343 pct u235, Table I. The samples were water quenched from 690°C (the a-ß transformation is at 668°C) to remove preferred orientation, and annealed at 450 "C to minimize residual stresses. One end of each cylinder was polished on a 1-µ diamond lap and electropolished in a phosphoric acid solution. After a final cleaning by cathodic sputtering, a 1- to 3-µ thick layer of the tracer isotope, uranium containing 93 pct u235, was sputtered onto the sample.' To prevent contamination during the diffusion anneal, the diffusion couples were placed in a tantalum cup and covered with another piece of uranium, and the whole assembly was sealed off in an evacuated quartz tube. Annealing temperatures were constant within +2.0°C. The samples were heated and cooled slowly between room temperature and the ß-? transformation (774°C) in order to minimize distortion of the sample surface that might arise from aniso-tropic thermal expansion and density changes during phase transformations. After machining off 1/16 in. from the radius to

Jan 1, 1961

THE total crude production from the Dutch East Indies, and the British Protectorates of Sarawak and Brunei for 1932 is given in the following table: BARRELS BARRELS (42 GAL.) (42 GAL.) North Sumatra 4,226,935 Ceram 326,207 South Sumatra 13,956,157 Sarawak 2,739,650 Java 3,845,568 Brunei 1,322,725 Dutch Borneo (main island) . 9,406,733 Dutch Borneo (Island of Tara- kan) 6,579,184 Total 42,403,159 Production, which had shown a rapid increase from 1921 to 1929, has since been reduced. Exploitation drilling in the majority of the larger fields was suspended and existing production kept within predetermined limits by beaning. Most of the smaller fields were shut down entirely. The depth of producing levels varies widely in the different fields. Shallow fields with drilling depths to 500 meters (1650 ft.) are still numer-ous as well as those with depths between 500 and 1000 m. (3300 ft.). A few of the newer fields reach greater drilling depths. up to 1600 m. (5250 ft.). The deepest exploration well drilled to date (Djambi field, South Sumatra) reached a depth of 2332 m. (7650 ft.) before abandon-ment in March, 1930. The specific gravities of the various crude oils produced range between 0.65 (86.2° A.P.I.) and 0.95 (17.5° A.P.I.). The lighter crudes have a high gasoline content and fuel oils are derived from the heavier crudes, which usually are rich in paraffin.

Jan 1, 1933

By R. W. Balluffi, B. H. Alexander

RELATIVE diffusion rates of copper and zinc in a brass have been measured in a vapor-solid type of couple with which the amounts of copper and zinc diffusing past inert Kirkendall markers can be obtained by means of a few simple experimental measurements. If inert markers are placed on the surface of copper which is then exposed to zinc vapor from a brass chips, the particles become buried due to outward diffusion of the copper, as shown in Fig. 1. A schematic diagram of such a couple after diffusion is shown in Fig. 2. Consideration of the diffusion flow of copper and zinc shows that the entire hatched area, including the cross-hatched area, is proportional to the amount of zinc diffused inward past the markers and that the smaller cross-hatched area is proportional to the amount of copper diffused outward past the markers. These areas are completely determined by the expansion of the couple, the depth of the buried particles below the surface, and the chemical composition at the specimen surface. As Darken1 has shown, the ratio of diffusivities of copper and zinc is then given by the ratio of these two areas. Polycrystalline copper and two copper single-crystals made by the Bridgman method were prepared in the form of 1.5 cm diam disks approximately 0.5 cm thick with faces plane and parallel. Tungsten particles approximately 0.001 cm in diam were bonded to the surface of each disk by heating 5 hr at 1060°C in vacuo. Each specimen was next

Jan 1, 1953

By S. Nenno, T. Saburi, Y. Mizutani, M. Yomarnoto, K. Komatsu

In the equilibrium phase diagram of the Ni-Mo sys-tem1,2 available at present, intermetallic compounds (or ordered phases)ß(Ni4Mo) and ?(Ni3Mo) are known to exist to the nickel rich side. In our recent investigations on Ni-Mo alloys, however, it has been found that the quenched alloys from the high temperature region containing more molybdenum than the Ni4Mo do not decompose directly into 0 and when annealed isothermally below the peritectoid temperature, i.e., 865°C. This note is to report the existence of Pt2Mo type superlattice (possibly ordered Ni2Mo) as a metastable phase in the early stage of decomposition. Alloys containing 20.1, 22.7, and 24.4 at. pct Mo were prepared by vacuum-melting electrolytic nickel of 99.9 pct purity and molybdenum powder of 99.9 pct purity in an alumina crucible. From the resulting ingots, sheets 0.3 mm thick were obtained by forging, hot-, and cold-rolling. The sheet specimens were water-quenched from ! region and subsequently annealed for various periods of time at temperatures below the peritectoid temperature. On these specimens were made optical-microscopic and transmis-sion-electron-microscopic observations. Fig. 1- Optical micrograph of the 22.7 at. pct Mo specimen annealed for 100 hr at 700°C after quenching. (ß + ?) region, B, nucleated along a grain boundaries are invading the preexisting (ß + Ni2Mo) region, A. Details of A are observable only by electron microscopy. Etchant: 60 pct HNO3-40 pct CH3COOH.

Jan 1, 1970

By P. Somasundaran, I. J. Lin

There are several methods described in the literature for the determination of the order and the rate constant for the flotation of minerals. These often involve some type of computational or graphical procedures. A relatively simpler method developed on the basis of a technique used by Chang" in chemical kinetics is described in this paper. Chang's technique, like most others in chemical kinetics," is based on the law of mass action which states that the rate of a chemical reaction is proportional to the active masses of the reacting substances at any given time. Application of this law to the flotation of minerals would involve the adaptation of the terms "flotation" for "chemical reaction" and "floatable amount of the minerals" for "the active masses of the chemical reactants." There are indeed a large number of physical processes controlling the actual flotation rate. The most inefficient one of these could be considered equivalent to the slowest reaction in a series of chemical reactions. If variables such as aeration rate and agitation are kept at constant levels, the rate of flotation under free flotation conditions (i.e., conditions under which the suspension is dilute) will be given by the following equation: where C is the concentration of the floatable minerals in the pulp at any given time t, K is the rate constant, and n is the order of the reaction. If we represent the floated fraction of the floatable mineral at time t as m (0 m - 1) and C at t = 0 as Ca, integration of Eq. 1 yields

Jan 1, 1974

By C. B. Alcock, R. G. Hudson

Sulfur pressure measurements above FeS in equilibrium with iron have been carried out by the Knudsen orifice method. A comparison is made of the weight loss of the cell per unit time obtained in the above experiments, that calculated from Richardson and Alcock's measurements of the S2 pressure above FeS in equilibrium with iron, and the dissociation constant for diatomic sulfur from spectroscopic and thermal data. EXTENSIVE equilibrium measurements have been made to determine the sulfur potentials of a great many systems of metallurgical interest.' In order to confirm their reliability, to supply data which may be of use in further thermodynamic calculations, and to establish the reliability of the Knudsen orifice in obtaining accurate thermodynamic values at high temperatures, the present investigation on the pressure of the gaseous species above FeS in equilibrium with iron has been carried out. The Knudsen orifice method has been used for these pressure measurements. Experimental The apparatus and general technique for this investigation are the same as that reported for the determination of the vapor pressure of silver.' To reduce the residual gas pressure in the evacuated chamber, a titanium getter, maintained at run temperature, was introducbed. Several types of Knudsen cells were used—platinum, zircon, and fused silica. The orifice in the zircon cell was fashioned with a small diamond wheel. The same precautions were used in this investigation as were employed in the work on Mo2S2.3 The FeS-Fe mixture was prepared by heating a sample of pure FeS,, supplied by K. K. Kelley of the Bureau of Mines, with excess iron powder, cp grade, obtained from the Fisher Scientific Co. These two substances were heated in a closed Armco iron crucible at 960°C, held in a vacuum of less than 10" mm Hg for 24 hr. The mass was then removed from the cell and ground in an agate mortar. In this form it was charged to the various Knudsen cells. Heating the Knudsen cell for an additional two days was sufficient to obtain constant rates of weight loss of the cell. The data obtained in this investigation are recorded in Table I. To establish whether or not a sulfide of iron is volatile at these temperatures, 0.7646 g of the FeS-Fe mixture, described above and containing 69.2 pet Fe, was placed in the zircon Knudsen cell. Run Nos. 103 to 109 were performed on it. After the completion of these runs, the total amount of iron left in the cell was obtained by chemical analysis. It contained 0.537 g Fe, compared to 0.529 g in the original charge. Thus, there was an apparent gain in iron of 1.5 pet. This is attributed to unknown experimental error, and the conclusion is that no sulfide of iron is volatile. The vapor pressure of pure iron4 is about one thousandth that of the sulfur pressure' at these temperatures. The vapor pressure of iron inside the Knudsen cell will be almost exactly that of pure iron, since in the iron-rich phase the percentage of sulfur is of the order of 0.025 pet.At this low percentage of sulfur Henry's law is probably obeyed by the sulfur. Thus, the iron will obey Raoult's law. In any event, the vapor pressure of iron will be lower than that of pure iron and, since the vapor pressure of pure iron is negligible compared to the pressure of sulfur, the weight loss of the cell due to the vaporization of iron should be negligible. Since neither iron nor FeS is volatile to an appreciable extent, the total weight loss of the cell must be due to the vaporization of sulfur. Discussion and Calculations On the assumption that S, is the only gaseous species present in appreciable quantity, its pressure

Jan 1, 1957

By C. S. Giggins, F. S. Pettit

The oxidation properties of Ni-Cr alloys with fine grains, coarse grains, and deformed surface layers have been studied at temperatures of 900" and 1100°C in 0.1 atm of oxygen. The oxidation rates of alloys containing between 10 and 30 wt pct Cr have been found to be dependent upon the grain size of the alloy. Finegrained alloys had smaller oxidation rates than coarsegvained alloys because of the selective oxidation of chromium at alloy grain boundaries. In this compositional range alloys with deformed surface layers behaved similar to fine-grained alloys due to recrys-tallization of the deformed surface layer. In the preceding paper1 it was found that during the oxidation of Ni-Cr alloys, the volume fraction of precipitated Cr2O3 could be greater at alloy grain boundaries than at other areas of the alloy surface. In the case of alloys with chromium concentrations equal to or greater than 30 pct,* the volume fraction of Cr2O3 *AIL compositions are given as weight percent unless specified otherwise. precipitated at grain boundaries and within grains on the alloy surface both exceeded the critical amount required for lateral growth of the Cr2O3 particles and the surfaces of these alloys were completely covered with a continuous, external layer of Cr203 during oxidation. However, in the case of alloys with chromium concentrations between approximately 5 to 30 pct, the volume fraction of precipitated Cr2O3 exceeded the critical value required for external scale formation only at grain boundaries.but not within the interior of the grains. Consequently, the surfaces of these alloys had external scales of Cr3O3 over the grain boundaries but internal Cr2O3 subscales with external scales of NiO away from the grain boundaries. Under these latter conditions, it was found that chromium could diffuse laterally in the alloy from those areas covered with an external layer of Cr2O3, i.e., grain boundaries, to areas where the Cr2O3 was present as a subscale. This diffusion of chromium resulted in an increase in the volume fraction of Cr2O3 precipitated in the sub-scale zone and continuous layers of Cr2O3 could be formed at the subscale front in these regions. For the alloys used in the previous studies,' continuous layers of Cr2O3 were formed on Ni-20Cr alloys in the subscale regions after approximately 30 hr of oxidation at 900°C. For shorter periods of oxidation, the Cr2O3 layer was semicontinuous with the continuous portion at the subscale front emanating from points where the Cr2O3 had been formed as an external scale over alloy grain boundaries. Some lateral growth of a Cr2O3 layer in the subscale region was observed on Ni-15Cr and even Ni-10Cr alloys but this layer was never continuous after 30 hr of oxidation. These results indicate that the selective oxidation of chromium in Ni-Cr alloys with chromium contents between 5 to 30 pct may be dependent upon the grain size of the alloy. Fine-grained specimens in this compositional range should have a larger fraction of the surface covered with external Cr2O3 than coarsegrained specimens and the subscale areas required to be sealed via lateral diffusion of chromium should be smaller. It is therefore to be expected that a continuous layer of Cr2O3 can be formed on alloys in this compositional range after short periods of oxidation providing the alloy grain-size is sufficiently small. bo studieS2,3 have established that the oxidation behavior of alloys can be significantly influenced by pretreatments which produce mechanically deformed surfaces. It has been found that deformed surfaces usually promote the selective oxidation of elements in alloys and it is believed that these effects are due to rapid diffusion of elements in the deformed layer. In view of the previous results,' which showed that alloy grain boundaries may play an important role in the selective oxidation of chromium in Ni-Cr alloys, deformed surfaces may promote the selective oxidation of elements in alloys as a result of the numerous grain boundaries formed on the alloy surfaces via recrys-tallization during heating to the oxidation temperature. The purpose of the present studies was to determine the effect of alloy grain size and surface deformation on the selective oxidation of chromium in Ni-Cr alloys at temperatures of 900" and 1100°C in 0.1 atm of oxygen. EXPERIMENTAL The average grain diameter of the alloys used in the previous studies1 was not less than 0.04 mm and alloys with compositions between 5 and 30 pct chromium had average grain diameters between 0.04 and 0.14 mm. Since the oxidation kinetics were already available for these relatively coarse-grained alloys, it was desirable to use these same alloys in the present studies. The surfaces of the alloys listed in Table I of the previous paper were deformed by using a Model F S.S. White Industrial Airbrasive Unit, which delivered a controlled mixture of 25 µ Al2O3 particles in a stream of dry air at high velocity against the surface of a specimen. The amount of surface deformation produced by this treatment was not determined but a re-crystallized layer about 15 µ thick was formed upon annealing deformed specimens. The grain size at the surface of the specimens was reduced to an average grain diameter of 0.01 mm by annealing the deformed specimens, i.e., grit-blasted,

Jan 1, 1970

By D. H. Polonis, Gary A. Dreyer

This investigation involved a study of the reactions occurring during aging of supersaturated a phase in a CIL-Si alloy. The aging processes at temperatures below 552°C were studied by means of metallography, microhardness, and electrical resistivity measurements. During the initial stage of aging in the temperature range 275o to 525oC an anisotropic phase, which is visible in the form of striations in the micro-structure formed prior to the appearance of the -phase. This transition phase has been designated k' due to its structural similarity to the k phase. The rate of K' formation during aging increased with aging temperature. At 450o and 525°C the reaction appeared to reach completion before significant amounts of precipitation were observed. The overall precipitation reaction in this system involved four stages: formation of formation of at a grain boundaries, growth of particles in 7-egions, and coagulation of into large particles. The relative role of each of these processes is dependent on the temperature of aging. The formation of phase from supersaturated a during aging increases the electrical resistivity and slightly increases the hardness of a 4.9 pct silicon alloy. The formation of during aging decreases the electrical resistivity and increases the hardness until coalescence of particles begins during the final stages of aging. The coalescence of results in a decrease of both electvical resistivity and hardness. THE available literature does not record a detailed analysis of the aging processes in Cu-Si alloys. Such an analysis has been difficult due to both the limited data available and misleading microstructural observations which have been reported. Previous work suggests that a rather complicated series of processes may be involved in the aging of supersaturated a. The present investigation is concerned with an analysis of the sequence of these aging processes in a 4.9 pct Si alloy. The currently accepted version of the Cu-Si equilibrium diagram, Fig. 1, was published by C. S. Smith in 1940.' This diagram shows a eutectoid at 5.2 pct Si with the high temperature phase, having its composition range entirely to the right of this value. By quenching alloys in the composition range 4.6 to 5.2 pct Si from the region, Smith was able to retain the phase. However, this phase exhibited a striated microstructure which was anisotropic to polarized light. These striations were suggested by Smith to be duplex twins. Using an oscillating crystal X-ray method Barrett2 studied alloys containing 4.0 to 5.4 pct Si quenched from the and regions. The striations observed in quenched specimens were attributed by Barrett to quenching stresses. He found that striations could also be formed by deformation after quenching and identified them as stacking faults in alloys containing 4.0 to 5.0 pct Si. Barrett related the striations in alloys containing 5.0 to 5.4 pct Si both to stacking faults and to a metastable phase which he called The striated structure reported by smith' was also obtained by Hoffmann, et al. 3 By deeply etching their specimens the anisotropic phase on the surface was removed, leaving a structure which was microscopically similar to pure copper. By means of X-ray analysis before and after deformation at room temperature it was concluded that the anisotropic phase was metastable This conclusion has been questioned by Barrett who attributes the discrepancy to superposition of k and lines on the powder patterns of Hoffmann, et alm3 The decomposition of supersaturated according to smith' and Anderson,4 is very sluggish. However, Nony and Dreyer,5 and Hoffmann, et al.' found that deformation increases the rate of decomposition. X-ray studies by Hoffmann, et al on

Jan 1, 1962

By George R. St. Pierre, John Chipman

METALLURGISTS have been studying the chem-ical behavior of sulfur in steelmaking for many years in order to have a better control of the sulfur content of finished steel. During the refining period in the open hearth, molten steel is separated from a gas phase by molten slag. Chemical reactions occur principally at the slag-metal interface and at the slag-gas interface. A need for physical-chemical investigations of reactions between sulfur-bearing gases and steelmaking slags was recognized some time ago.'.' From the early work, it can be qualitatively concluded that increased sulfur content and low partial pressure of oxygen in the gas phase favor the passage of sulfur from gas to slag. Using radioactive sulfur S Koch and Fink' have demonstrated the rapid rate of exchange of sulfur between gas and slag in an open hearth furnace. Gurry and Darken and Darken and Shields (as reported by Derge and Marshall') have equilibrated lime-iron oxide slags with SO—O2 gas mixtures. The major conclusion from the reported results is that sulfur content increases with increasing lime content in lime-iron oxide slags equilibrated with a gas of high oxygen pressure (10-2). The data were interpreted as indicating the presence of SO, and S,O, ions. Richardson and Fincham' have conducted the most extensive experimental study of sulfur equilibria between gas and slag. Their results confirmed many of the conclusions drawn from calculations of Richardson" and Withers. Richardson and Fincham's data fitted very well into the sulfur scheme represented by the reactions 1/2 s2 (g) + (0) melt - 1/202(g)+ (S) melt [II 1/2 S, (g) + 3/2 O (g) + (0) melt - (SO,) melt. [2] At oxygen pressures greater than 10 to 10 they found that reaction Eq. 2 was predominant while reaction Eq. 1 was controlling at oxygen pressures less than 10." to 10.". The slag compositions and gas mixtures used in their investigations were different from those used in the present study. Wherever possible, comparison has been made between their results and these, and agreement is excellent. It is evident that the distribution of sulfur between slag and gas depends upon the oxygen pressure of the gas. In FeO slags, a change in oxygen pressure produces a change in ferric oxide content, and a knowledge of this equilibrium is a prerequisite to studies of sulfur distribution. The data are found in the work of Darken and Gurry" on the FeO system and the more recent experiments of Gurry and Darken" and of Larson and Chipman" on FeO slags containing lime and silica. The effect of oxygen pressure on the ratio Fe /(Fe" + Fe ), the so-called j-ratio, reported by these investigators will be used in interpreting the results which follow. Experimental Method The purpose of the experimental program was to determine the equilibrium sulfur content in slags exposed to gases of known oxygen and sulfur pres- sures. The slag compositions selected for study were from the lime-silica-iron oxide system. Additions of magnesia were made to some of the slags. Apparatus—The apparatus used by Larson and Chipman was modified slightly to accommodate the addition of SO2 to the gas mixtures. As in their work, slag samples of 0.5 to 2.0 g were held at temperature (lcc) in platinum crucibles under a steady stream of gas, 100 to 200 ml per min, for several hours and then rapidly lowered to the bottom of the furnace where they were quenched in mercury. Preparation and Analysis of Gas Mixtures—Mixtures of SO,-CO were prepared from Virginia Smelting Co. Extra Dry liquid SO, and Pure Co. CO,. After removing traces of water vapor with an-hydrone, the CO, was passed over graphite at 1200°C, at which temperature the conversion to

Jan 1, 1957