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By R. Bainbridge

THE Consolidated Mining and Smelting CO. of Canada Ltd. has operated a lead smelter at Trail, B. C., for many years. In order to take advantage of metallurgical advances, as well as to improve materials handling methods, this company, commonly known as "Cominco," commenced planning a program of smelter revision and modernization some years ago. The first stage of this program involved the design and construction of a new blast furnace gas cleaning system. The selection of equipment, the design of facilities, and preliminary operating details of this system will be dealt with in this paper. The essential problem was to clean and collect 100 tons of dust daily from 153,000 cfm* (12,225 lb per min) of lead blast furnace gas which varied in temperature from 350º to 1100°F. Because it was desired to collect the dust dry, either a Cottrell or a baghouse cleaning plant was to be selected. Comin-co's many years of experience with both systems provided a background for choosing the most satisfactory installation. All information pertinent to the two methods of dust recovery was carefully investigated, and it was decided to replace the existing equipment with a baghouse. Very briefly, the reasons for this decision were as follows: 1—A baghouse installation would be practical because the SO2 content of the gas was low and corrosion would not be a problem if the baghouse operating temperatures were held sufficiently above the dew point. 2—Variations in the physical characteristics of fume and dust, which are inherent in this blast furnace operation, should not substantially affect the operating efficiency of a baghouse. 3—For the same capital cost, metal losses (stack and water losses) would be appreciably less in a baghouse. 4—A baghouse would be easier to operate, and would not require the use of highly skilled labor. 5—Operating and maintenance costs of a bag-house would be lower. 6—The only available space for reconstruction was relatively small, and not suited to a Cottrell installation. Once the baghouse system was decided upon, detailed design of the installation was begun. Baghouse Design Gas Cooling: Before the required capacity of the baghouse could be determined, the method of cooling the gas to the temperature necessary for bag-house operation had to be chosen. The problem confronting the design engineers was how best to cool 153,000 cfm of gas from a temperature ranging from 350°F to brief peaks of 1100°F, down to 210°F, the maximum safe baghouse inlet temperature. A survey of existing blast furnace gas temperatures in the outlet flue showed that the normal range was as given in Table I. The obvious choices of cooling method were: 1— cool completely by the addition of tempering air; 2—utilize a heat exchanger; 3—cool by radiation; and 4—cool with water spray in conjunction with the admission of tempering air. The advantages and disadvantages of the various cooling methods were: Air Addition: To cool completely by the admission of tempering air involved tremendous volumes, Fig. 1. For example, to cool 1 lb of blast furnace gas at 450°F requires 1.84 lb of air at 80°F or 1.60 lb at 60°F. As it is necessary to design for peak conditions, it can readily be seen that volumes of tempering air in the order of 1,500,000 cfm would have to be handled. Using the normal design figure of 2.5 cu ft per sq ft of bag area, a baghouse installation comprising some 600,000 sq ft of filter cloth would be necessary. Such design requirements would be prohibitive, not only from a standpoint of capital expenditure, but also because of space limitations. Heat Exchanger: The utilization of a heat exchanger was given serious consideration. A horizontal tube unit using air as the medium to cool the required volume of blast furnace gas from 400" to 250°F was investigated. Cooling above 400°F would be done by water spray, and below 250°F by admission of tempering air. The estimated capital cost of such a unit was found to be prohibitive. From an operating standpoint, there was considerable doubt as to whether the soot blowing equipment provided would effectively keep the dust from building up on the tube surface. The performance of heat exchangers operating on dusty gas in other company operations had not been too favorable. Radiation Cooling: Although somewhat cumbersome, gas cooling by radiation from 'trombone' tubes or other similar equipment (cyclones) is employed in many metallurgical operations. Such an installation was also considered. However, calculations showed that an installation much larger than the space available would be required to handle the gas volume involved. For example, to cool 153,000 cfm of blast furnace gas from, say, 600' to 250°F (i.e., remove in the order of 58,500,000 Btu per hr with heat transfer rates varying from 1.1 Btu per sq ft per hr per OF for the higher temperature ranges to 0.88 Btu per sq ft per hr per OF for the lower ranges) would need a cooling area of some 175,000 sq ft.

Jan 1, 1953

By J. A. Berger, G. W. Wiener

Several transition metal nitrides have been prepared and their saturation magnetization determined. On the basis of an atomic model of ferromagnetism involving a consideration of nearest neighbor interactions and the assumption that all atomic moments of the metal point in the same direction, it appears that the nitrogen interacts with d-shell of the transition metal in such a way as to reduce the magnetic moment. THERE is a large class of materials having metallic properties which are formed by a combination of hydrogen, boron, carbon, oxygen, or nitrogen with the transition metals. Several attempts have been made to establish the type of metal-nonmetal bonding in these interstitial alloys because it is believed that many of the physical properties of these materials are determined by the characteristics of this bond. Several of these alloys are ferromagnetic, and thus a powerful method is available for investigating the structures in a direct manner by measuring the saturation magnetization. The latter is a fundamental property of ferromagnetic metals and alloys which depends primarily on the electron distribution surrounding the atom. For the first row of transition metals, this refers specifically to the 3 d-shell. Since bonding involves the electronic configuration between atoms, there is reason to suppose that a relationship exists between ferromagnetism and bond type. In the case of the interstitial structures studied in this work, bonding will refer to the distribution of electrons between the transition metal and the nonmetal. Since these alloys have metallic properties, it is further proposed that any bonding interactions will involve the outer p-shell of the interstitial element and the incomplete d-shell of the transition metal. If this is the case, then the relationship between ferromagnetism and metal-non-metal bonding is established qualitatively. In order to investigate the subject quantitatively, certain transition metal nitrides were chosen because they have simple crystal structures, are ordered alloys, and are ferromagnetic. They also have sufficiently high saturation magnetization to be of technical interest. Currently there are two major theories of ferromagnetism, each of which has been applied to the interpretation of the saturation magnetization in terms of atomic structure. They are usually referred to as the band theory and the atomic theory. The former has found widespread application to the study of pure metals and certain solid-solution allays. However, it has not been applied to the interstitial structures or ordered alloys because it does not interpret the properties directly in terms of the crystal structure. The atomic theory on the other hand is especially suited to the study of interstitial structures because it permits an interpretation of ferromagnetic phenomena in terms of the crystal geometry. As has been pointed out previously, the nitrides have simple ordered crystal structures and, therefore, the choice of the atomic theory for the interpretation of the data is a natural one. One of the prime difficulties with the atomistic theory is that its mathematical justification is much more difficult, and for this reason its general acceptance will depend to a large extent on the value it has in explaining and predicting the results of experiment. Before the presentation of the theoretical basis for understanding the metal-nonmetal bond, it is useful to review the ideas existing prior to this work. Four different interpretations have been given to the metal-nonmetal bond. These are summarized as follows: 1—acceptance of electrons by the nonmetal from the incomplete d-shell of the transition metal, 2—transfer of electrons from the nonmetal to the incomplete shell of the transition metal, 3—no exchange of electrons between the two atoms, and 4— a resonating type of bond involving the p electrons of the interstitial atom giving rise to half bonds. Zener'-4 in a recent series of papers has proposed a new theory of ferromagnetism and has developed an explanation of the observed saturation magnetization of iron nitride (Fe,N) using the concept that nitrogen accepts electrons from the 3d-shell of iron. Jack," on the basis of atom size considerations in iron carbonitrides, has proposed that nitrogen transfers or donates electrons to the inner 3d-shell. He found that the effective size of the carbon atom was less than that of nitrogen and thus suggested that the interstitial atoms give up electrons. Kiessling" has studied the borides of several transition metal atoms and proposed that boron loses one p electron to the transition metal. He postulated that the additional electron added to the metal lattice compensates for the loss in metallic properties which results from the increased metal-metal atom separation. GuillaudT3" has proposed similar arguments from some recent magnetic studies he had made on manganese nitride. However, he did not base his conclusions on a quantitative argument. Pauling," in a recent paper, discussed electron transfer in in-termetallic compounds. He classified nitrogen as a hyperelectronic atom which can increase its valence by giving up electrons. He classified the transition metals as buffer atoms which are capable of either accepting or giving UP an electron. He pointed out that two factors are operating which promote electron transfer because they lead to increased stability. The first is an increase in the number of bonds, and the second is a decrease in the electric charges on the atoms. These ideas when applied to the interstitial nitrides would indicate a viewpoint favoring electron transfer by nitrogen to the transition metal. Hagg7s arguments in favor of no exchange are adequately summarized by Wells." Implicitly, Hagg

Jan 1, 1956

By E. P. Hindes

The total amount of oil produced in the state of Oklahoma during the year 1928 was 242,286,400 bbl., as compared to 273,372,650 bbl. in 1927; 177,650,000 bbl. in 1926; and 167,900,000 bbl. in 1925. The year 1928 ranks second to 1927 in which more oil was produced in the state than in any previous year. The large in in 1927 and 1928 was due principally to the development of the Greater Seminole district. The decrease of approximately 31,000,000 bbl. in the 1928 production as compared with the production in 1927, was caused by a drop of nearly 8,500,000 bbl. in the Seminole district production and a more or less normal decline in the production of practically all the other older and more settled fields. During 1928 approximately 1800 producing wells were drilled in Oklahoma, which yielded during the year approximately 90,000,000 bbl. of oil. The average initial production of these wells was 850 bbl. per day, and the average daily production per well for the year was 137 bbl. The average daily production per well of the total number of wells producing in 1928 was 10.9 bbl., which is a 13.5 per cent. decrease from the 1927 average of 12.6 barrels. At the close of 1928 a total of 95,400 producing wells had been drilled in the state, and approximately 61,000 were still producing. The grand total amount of oil produced in the state from the time the first well was drilled up to and including 1928 was 2,553,000,000 bbl. The production in 1928 was 9.5 per cent. of the total oil produced in the state. Texas led all other states in 1928, with a production of 251,835,200 bbl. Oklahoma was second with 242,286,400 bbl., and California was third with 231,982,600 barrels. Fields outside Greater. Seminole District Practically all the old settled fields in Oklahoma experienced a normal and expected decline during the year 1928. The fields showing the most, pronounced decline as compared to 1927 were: Burbank, which dropped from 15,230,400 to 11,939, 150 bbl.; Tonkawa, from 7,692,000 to 4,952,900 bbl.; Garber, from 5,056,300 to 3,139,400 bbl., and Wewoka, from 6,188,-800 to 2,450,400 bbl. There were no new extensions, discoveries of

Jan 1, 1929

By W. H. Eardley

IT IS increasingly evident that the excellence of blast-furnace operation to a great extent depends upon the preparation of the products fed into the furnace. The preparation of these products is carried on largely in the roasting and sintering departments. Prior to the building of flotation plants in Utah and other western states for the treatment of lead-zinc ores, the gravity concentrates received at the Midvale smelter amounted to about 4000 tons per month, containing 24 per cent. lead and 10 or 11 per cent. zinc. This product was about 20 mesh-that is, 45 per cent. of it would be plus 20 mesh and the balance minus 20 mesh. About 1000 tons of pyrite per month, containing 5 per cent. lead and 10 per cent. zinc, was also received. These products were sent to the multiple-hearth roasters for calcining, after which they were sent to the Dwight-Lloyd machines for sintering with other ores. The sintering charge passed over the machines but once. The first flotation products received consisted of a wet, sticky, muddy mass, containing a large amount of moisture, up to 19 or 20 per cent., and it was almost impossible to feed .them with any degree of regularity, if at all, through our standard feeders; but the amount of flotation product received during the first year or so was relatively small and it virtually lost its identity by being mixed with a large amount of jig and table concentrates. As the quantity of flotation products increased, more efficient filtering was accomplished and the moisture greatly reduced. FLOTATION PRODUCTS RECEIVED At the present time the Midvale plant receives about 4300 tons per month of flotation product running 60 per cent. lead and 4.5 per cent. zinc, 85 per cent. of which is minus 200 mesh and contains about 8 per cent. moisture; and 4000 tons per month of pyrite of similar fineness, running about 2 per cent. lead and 3.5 per cent. zinc, containing about 10 per cent. moisture. The lower moisture greatly reduces the difficulties of handling, making it possible to run a 100 per cent. flotation feed on a multiple-hearth furnace without serious mechanical troubles. The calcine, however, would contain-nodules and balls of unroasted concentrates, sulfur elimination

Jan 1, 1928

Consolidated Gold Fields Limited published annually an excellent reference, GOLD 1978, GOLD 1979, giving the Supply and Demand for Gold, Recent Developments and Prospects, Soviet Gold Production, etc. This outstanding reference is authored by Christopher Glynn, Investment Department, London, Great Britain. The 1978 Report marked the tenth anniversary of Gold Field's review of world gold market developments; and from it and the 1979 report, the following information was derived. The recovery of gold is widespread in the Soviet Union. Originally, gold was mined principally in the Urals, but in the last few years several major deposits have been discovered in the southwestern areas of the Soviet Union. One of the most dramatic discoveries has been the Muruntau deposit in Western Uzbekestan. This deposit, discovered in 1958, is reported to be the largest and among the lowest cost producers in the Soviet Union. It is located in Armenia, approximately 750 km (465 miles) northeast of the Iran-Afghanistan border, lying in the center of the Kyzylkurn (Red Sands) desert at the foot of Muruntau Mountain. Free gold occurs in both fine and coarse size in quartz veins up to 20 m (66 ft) thick associated with a small percentage of sulfides, mainly arsenopyrite. The ore zone constitutes a large gold-enriched stock work of about 4 sq krn (1.5 sq miles). The development of Muruntau was a major undertaking with open -pit development and construction of the mill and refinery complex started early in 1967, and the first gold bar poured in mid-1969. At the end of the first construction stage in 1970, the mill building was an imposing structure about 38 m (125 ft) high and 330 (1,080 ft) in length housing, probably, 11 parallel milling circuits. The first construction stage also included six 50 m (165 ft) diameter thickeners and 30 Pachuca tanks. The original mill complex was tripled in size after large additional gold reserves were discovered at a depth of 600 m (1,970 ft); and the deposit is now being exploited by both open- pit and underground workings. Ore is ground in semi-autogenous mills with the free gold being recovered into a high-grade concentrate on shaking tables. Table tailings are purnped to duplex spiral classifiers in closed circuit with the grinding mills. Classifier overflow is then thickened before being transferred to the Pachuca building where cyanidation takes place. An ion exchange resin is then added in a countercurrent

Jan 1, 1981

By Eugene S. Meieran

The effects of methods of crystal growing, wafer sawing, polishing, routine handling, diffusion, and epitaxial growth on the defects in GaAs are reviewed and studied using reflection and transmission X-ray topographic techniques. In general, it was found that boat-grown crystals exhibited fewer defects than Czochralski crystals, although all crystals showed large numbers of precipitates visible when examined in the electron microscope. Mechanical surface treatments such as sawing and mechanical polishing introduce damage to a depth of about 5 µ, most of which can be removed by suitable chemical or chem-mechanical polishing. In addition, defects can be introduced through routine handling of wafers, for example with metallic tweezers. These defects can be quite severe, and have been observed 20 µ below the wafer surface. Defects can also be introduced through diffusion and epitaxial growth. These defects, which include precipitates, growth pyramids, stacking faults, dislocations, and so forth, can be detrimental to device fabrication. It is shown that wafers or films which appear defect-free optically can contain defects visible in the X-ray topographs. WHILE the use of GaAs in the semiconductor industry has increased very rapidly in the last few years, due mainly to the recent development of many important GaAs devices,1,2 the major limit to the production of commercial quantities of many GaAs devices remains a severe lack of suitable materials technology. This lack is apparent in two critical areas. First, production quantities of high-quality GaAs crystals, reproducibly doped and precipitate-free, simply are not available commercially, although some reasonable quality material is available on a limited first-come, first-serve basis. Second, in comparison to silicon technology, little is known about the effects of processing variables on the defects either present in as-grown GaAs or introduced through processing and handling of wafers. These areas are now receiving some attention from semiconductor device manufacturers, who are studying defects in GaAs in order to better understand how either to prevent their occurrence or to cope with their existence. Most investigations of the defects in GaAs have been made by optical microscopy3-5 or transmission electron microscopy techniques.'-' Recently, however, the imaging techniques of X-ray topography, electron mi-croprobe analysis, and scanning electron microscopy are being applied to the study of GaAs.9-14 In the case of X-ray topography, a one-to-one image is obtained that must be photographically enlarged. In compensa- tion, the defects within entire wafers may be imaged by simple scanning (Lang technique15) if the wafer is reasonably perfect, or by using the scan oscillation technique developed by Schwuttke16 if the wafer is warped or distorted. The purpose of this paper is to both review and extend the general application of X-ray topographic techniques to GaAs. Emphasis will be placed on the effects of growth and process variables on the quality and perfection of both bulk and epitaxial GaAs. Reference to optical or electron microscopy results will be made when useful. Since the effects on defects of a wide variety of processing variables such as crystal growing, sawing, polishing, diffusion, and epitaxial growth will be somewhat superficially reviewed, a fairly extensive bibliography of the most important recent results in these areas is included. However, for completeness, important defects will be illustrated here, although such defects have been previously shown by others. While this paper is concerned with defects rather than with the physics of X-ray scattering, the mechanisms of contrast formation in the topographs will of necessity be briefly mentioned. EXPERIMENTAL GaAs crystals, both boat-grown18 and Czochralski-grown,'8 containing a variety of dopants of various concentrations, were purchased from outside vendors. Wafers were sliced from the crystals using a Hamco ID saw and were mechanically polished using 1 µ diamond paste. Chem-mechanical polishing was done in bromine-methanol as described by Sullivan and Kolb.18 Chemical polishing was done using a modified sulfuric-peroxide solution, 11 parts H2SO4, 1 part 30 pct H2O2, 1 part DI water.5 Zinc diffusion was carried out in a closed tube, using a 10 pct Zn-In source at 825°C for 1 hr. Oxide masking techniques were used to select the area to be diffused. Epitaxial wafers were either purchased or prepared here. All epitaxial runs prepared here were carried out using a Ga-GaAs-AsC13 source in a closed tube at a substrate temperature of 750°C. Wafers were chem-mechanically polished and gas-etched prior to deposition. The X-ray topographs were taken on a Krystallos Lang camera, operating in the transmission scanning geometry (Lang technique15) or in the reflection scanning geometry (modified Berg-Barrett technique20,21). MoKa, radiation was used for all transmission topographs using a Jarrell-Ash 100-µ spot focus. CuKal radiation was used for all reflection topographs using a General Electric CA-7 1-mm spot focus X- ray tube. Topographs were printed from an intermediate contrast inversion film, so the contrast shown in all figures here is the same as that of the original 50-µ-thick emulsion L4 Iiford nuclear plate used to record the topograph.

Jan 1, 1969

By F. B. Foley

With the possible exception of high-speed tool steel, the service demanded of rock-drill steel is probably more precarious than that of any other tool steel. Unaided by the helpful influence of alloys and dependent solely on the efficiency of the heat treatment applied for its ability to stand up under the abuse to which it is necessarily subjected, rock-drill steel is worthy of intensive study. For its heat treatment the smith has his fire, an oil fire perhaps, and a quenching bath; he judges the temperature by his eye. There are shops where excellent drills are produced by this method, but there are more where the product varies between very good and very bad. Pyrometers with specially designed equipment are used in but few cases. But the responsibility for rock-drill failures does not rest entirely on the smith. Little has been published concerning the efficiency of drill steel, though the Canadian Mining Journal1 published the breakage record of a large number of hollow drill steels. This record indicates that most of the breaks occur during the early life of the steel and that as a given batch of steel is used, its percentage of breakage decreases. This fact, the article points out, is at variance with the much-talked-of theory concerning failure from crystallization and fatigue. It seems to point to the fact that the greater part of drill-steel failure from breakage is traceable to faulty manufacture, resulting in defects in the bore of the hollow steel from inclusions of slag or oxides, etc. As this defective material meets with early failure, it is weeded out. In addition, some breakage may be caused by a lack of proper condition with respect to heat treatment of the steel as furnished by the manufacturer. In the article mentioned, the breakage of 1/14-in (3.17 cm.) hollow steel is given as 4.62 per cent. for the early period of use, with a decrease to 3.35 per cent. and 2.67 per cent. with time in use. For 1-in. (2.5 cm.) hexagonal hollow steel, the figures for breakage are 0.18 per cent. and 0.06 per cent.; attention is called to the great decrease in breakage by the use of smaller diameter drills. The figures are given as so many drills sharpened, but there is no way of determining the percentage of

Jan 1, 1922

By Francis Foley

WITH the possible exception of high-speed tool steel, the service demanded of rock-drill steel is probably more precarious than that of any other tool steel. Unaided by the helpful influence of alloys and dependent solely on the efficiency of the heat treatment applied for its ability to stand up under the abuse to which it is necessarily subjected, rock-drill steel is worthy of intensive study. For its heat treatment the smith has his fire, an oil fire perhaps, and a quenching bath; he judges' the temperature by his eye. There are shops where excellent drills are produced by this method, but there are more where the product varies between very good and very bad. Pyrometers with specially designed equipment are used in but few cases. But the responsibility for rock-drill failures does not rest entirely on the smith. Little has been published concerning the efficiency of drill steel, though the Canadian Mining Journal' published the breakage record of a large number of hollow drill steels. This record indicates that most of the breaks occur during the early life of the steel and that as a given batch of steel is used, its percentage of breakage decreases. This fact, the article points out, is at variance with the much-talked-f theory concerning failure from crystallization and fatigue. It seems to point to the fact that the greater part of drill-steel failure from breakage is traceable to faulty manufacture, resulting in defects in the bore of the hollow steel from inclusions of slag or oxides, etc. As this defective material meets with early failure, it is weeded out. In addition, some breakage may be caused by a lack of proper condition with respect to heat treatment of the steel as furnished by the manufacturer. In the article mentioned, the breakage of 1 ¼ -in. (3.17 cm.) hollow steel is given as 4.62 per cent. for the early period of use, with a decrease to 3.35 per cent. and 2.67 per cent. With time in use. For 1-in. (2.5 cm.) hexagonal hollow steel, the figures for breakage are 0.18 per cent. and 0.06 per cent.; attention is called to the "enormous decrease in breakage by the use of smaller diameter drills." The figures are given as so many "drills sharpened," but there is no way of determining the percentage of

Jan 6, 1921

By Edwin Chance

DURING the last decade many conditions have been encountered that have materially increased the cost of the production of coal. As in most cases it has not been practicable to increase the selling price of such coal sufficiently to insure the necessary margin of profit, the mine management has been forced to avail itself of what might be termed unusual means that costs might be held at as low a figure as possible. The so-called efficiency engineer has been called upon, costly power plants have been built and machinery has been installed to replace manual labor wherever possible. Another aid used recently to secure economies through the more intelligent production of coal, is the chemist. As the coal industry, barring the production of byproduct coke, does not at once give evidence of its need of the services of the chemist, the writer will endeavor to point out a few of the services that this branch of the staff has been able to render. The preparation of coal in the past has been carried on entirely upon an empirical basis, that is, the criterion adopted has been an ocular inspection. Unfortunately, the appearance of a coal and especially of an anthracite, has but little relation to its fuel value, and as long as coal is purchased for the heat that 'can be obtained from it by its combustion, the quantity of such heat that is purchased must be one of the principal desiderata in selecting or preparing a coal. Were coals purchased for use as bric-a-brac or for exhibition in museums it might be both wise and just to purchase them upon their appearance. After 4 or 5 years of investigation the fact has been established that coals of very inferior appearance, and I now have special reference to anthracite, might and often did possess heating and burning properties superior to those possessed by, bright coals which in the past had commanded considerable and uniform premiums in the market. This being the case the question arose as to whether the trade could be convinced of this fact. While at first some difficulty was experienced in establishing the quality of such dull coals, still it was found that the real obstacle to the sale of these

Jan 4, 1916

By A. Totani, S. Nakajima, H. Okazaki

The phase diagram for the SnTe-SnSe system has been studied in the temperature range from 300° to 900°C by differential thermal and quenching techniques. The X-ray measurements were made on quenched specimens. High-temperature diffraction was also made to study the phase transition in SnSe. The system is proved to be of a eutectic type in which no intermetallic compound exists. The eutectic point is at the composition SnTeo.55 Seo.45. the eutectic temperature being 755°C. Solid solubility limits are SnTeo.6Seo.r and SnT eo. 3s Seo.6s at the eutectic temperature, and change almost linearly to SnTeo.aaSeo.lz and SnTeo.18 Seo.az as temperature decreases to 300°C. It was shown that the SnSe phase has a phase transition of the second order at about 540°C and that the transition temperature decreases with increase of the SnTe content. THERMOELECTRIC properties of tin telluride (SnTe) and tin selenide (SnSe) have been studied extensively in recent years. The variation of physical properties with composition could be of interest if these compounds form an appreciable crystalline solution. The purpose of present investigation is to confirm the formation of crystalline solution or intermetallic compound, if any, and to establish the phase diagram for this system. The crystal structure of SnTe is NaCl type with a cubic unit cell1 (a = 6.313A). The crystal of SnSe having an orthorh2mbic unit cellz (a = 11.496, b = 4.1510, and c = 4.4437A) is isomorphous with tin sulfide (SnS) which has a distorted sodium chloride structure. It has been known that SnSe has a phase at at 540°C; the transition has been assumed to be of the second order. As far as we know, only two studies on the SnTe-SnSe pseudobinary system have been reported. The conclusion obtained in these papers is that, in the composition regions near SnTe and SnSe, the system forms a crystalline solution of the SnTe structure and the SnSe structure, respectively, and that, in the intermediate region, both phases coexist. However, neither the variation of the solid solubility vs the temperature nor the liquidus and solidus were investigated. Hence present writers have attempted to determine the phase diagram of the system by differential thermal analysis (D.T.A.) and X-ray diffraction. EXPERIMENTAL Sample Preparation. Starting materials, SnTe and SnSe, were prepared by the direct fusion of commercially available high-purity (99.999 pct) elements. Stoichiometric amounts of each couple Sn-Te or Sn-Se were weighed into a clear fused silica ampule. After evacuation to a pressure below 10-3 mm Hg, the am- pule was sealed, and annealed at 900°C for 5 hr. The melt was quenched in water. X-ray analysis confirmed the formation of a single phase of SnTe or SnSe. The other samples, SnTel-,Sex were synthesized from these SnTe and SnSe by mixing them in the required ratio, followed by annealing at 900°C and quenching. These samples were used directly for D.T.A. For X-ray measurements, samples were annealed at 700°, 600°, or 500°C for 100 hr or at 300°C for 150 hr, and then quenched in water. It was found that the lattice constants of the SnTe phase annealed for 150 hr at temperatures above 500°C did not differ from those annealed for 100 hr at the same temperatures. However the X-ray phase analysis showed that at 300°C the annealing for 150 hr was necessary to attain a true equilibrium state. D.T.A. The solid-liquid equilibrium temperature was determined from D.T.A. measurements. The sample was sealed in an evacuated silica tube and molybdenum powders sealed in an another tube were used as a reference material. The sample and the reference tube were placed in a nickel block and were heated from room temperature to 900°C at a rate of 3°C per min and then cooled down at the same rate to 600°C. Thermocouples for these measurements were Pt-Pt. Rh (10 pct) and the error of temperature measurements was within + l0C. D.T.A. curves were obtained on a two-pen recorder and an automatic controller (PID type) was used for the program of heating and cooling. When temperature reaches the solidus from the low-temperature side, there appears an endothermic peak. The solidus temperature was determined by extrapolation of the straight portion of the starting flank of this peak to the base line. In a similar way, the liquidus temperature was determined from an exothermic peak on D.T.A. cooling curve. In the case of supercooling, if any, its degree can be estimated from the magnitude of the abrupt temperature rise. X-Ray . X-ray powder patterns were taken by a diffractometer using CuK, radiation. Since the SnSe crystal is cleaved easily, the powders become flaky when SnSe-rich samples are ground in an agate

Jan 1, 1969

By M. J. Richards, A. Szirmae, G. R. Speich

The formation of austenite from ferrite, ferrite plus retastable carbide, spheroidite, and pearlite has been studied in a series of irons, Fe-C alloys, and plain-carbon steels using fast heating techniques. In the absence of carbide, austenite nucleates at ferrite/ferrite grain boundaries; nucleation is followed by the rapid growth characteristic of a massive transfornation. The trarnsformation occurs at 950°C at heating rates of 106º C per sec and cannot be suppressed. Metastable carbide dissolves before austenite forms and does not influence the transformation kinetics. For spheroidite structures, austenite nucleates preferentially at the jinction between carbides and ferrite grain boundaries. Growth from these centers proceeds until the carbide is completely enveloped; subsequent growth occurs by carbon diffusion through the austenite envelope. For pearlite structures, austenite nucleates preferentially at pearlite colony intersections. Carbide la)?zellae dissolve at the advancing austenite interface but complete solution of carbide does not occur; the residtial carbide is eventually dissolvled or spheroid-ized depending on the carbon cuntent. The magnitude and temperature dependence of the austenite growth rate into Fe-C pearlite when incomplete carbide dissolution is assumed are satisfactorily explained by an approximate colume diffusion model. The impurities present in plain-carbon steel reduce the growth rate of austenite in comparison to that jound in an Fe-C alloy. The formation of austenite has been studied in much less detail than the decomposition of austenite. This is primarily a result of the importance of harden-ability in determining the mechanical properties of steel. Recently, more interest in the kinetics of austenite formation has resulted from the discovery by Grange1 that rapid heating techniques strengthen steel by refining the austenite grain size. Although the strengthening effect is not large, it is accompanied by no loss in ductility. In addition, interest continues in rapid heat treatment of low-carbon steel sheet for tin plate applications.2,3 Among the few systematic studies of austenite formation are the early work of Roberts and Mehl4 on formation of austenite from pearlite and recent work of Molinder5 and of Judd and paxton6 on formation of austenite from spheroidite. Also, Boedtker and Duwez7 and Haworth and paar8 have recently studied the formation of austenite from ferrite in relatively pure iron, Kidin et al.9,10 have studied the formation of austenite in 8 pct Cr steels, and Paxton has recently discussed various aspects of austenite formation in steels." The present work was undertaken to determine the kinetics of austenite formation for a variety of starting structures including ferrite, ferrite plus metastable carbide, ferrite plus spheroidal cementite, and ferrite plus pearlitic cementite. Emphasis was placed on determining the active sites for austenite nucleation, determining the temperature and time range of austenite formation, and in the case of pearlite a careful study of the growth rate of austenite was made in the absence and presence of impurities. By using a variety of heating techniques including laser-pulse heating, it has been possible to study austenite formation in an isothermal fashion over a wide range of temperatures. EXPERIMENTAL PROCEDURE The alloys studied in the present work are a zone-refined iron with 4 pprn C, an Fe-C alloy with 130 pprn C, 2 Fe-C alloys with 0.77 and 0.96 wt pct C, and a plain carbon steel with 0.96 wt pct C. The zone-refined iron and Fe-C alloys contained 60 pprn and 200 pprn total substitutional impurities, respectively. The plain carbon steel contained 2400 pprn Si, 2000 pprn Mn, and 900 pprn Cr. Various heat treatments were given to these alloys to produce different starting structures of equiaxed ferrite, ferrite plus metastable carbide, fine pearlite, and spheroidite. These heat treatments are given in Table I. A wide range of heating rates were employed in this work because many of the reactions occur so quickly at temperatures in the austenite range that they are completed during the initial heating cycle unless very fast heating rates are used. Essentially the same heating techniques employed by Speich et a1.12 and Speich and Fisher13 were used in this work. For time intervals of 2 sec to 20 hr, simple hand immersion of 0.010-in. thick specimens in a Pb-Bi bath was employed. These specimens were quenched in a 10 pct NaC1, 2 pct NaOH aqueous bath. For time intervals of 100 m-sec to 2 sec, an automatic dunking and quenching device was employed with 0.002-in. thick specimens. Again, liquid Pb-Bi baths were used for a heating medium but now helium gas quenching was employed. For time intervals of 2 to 100 m-sec a laser heating device was employed with 0.002-in. thick specimens; a helium plus fine water-droplet spray was now used for quenching. Additional information on heating times shorter than 2 m-sec was obtained by study of the zones around the centrally heated laser spot. Here diffusion of heat from the centrally heated zone raises the temperature of the specimen locally to all temperatures between ambient and the peak temperature, but for times of the order of microseconds. All the heat-treated specimens were examined by

Jan 1, 1970

By H. G. Botset

A KNOWLEDGE of the water content of producing sands is becoming of increasing importance to the petroleum industry. It is now a generally accepted fact that practically all oil sands contain some free water. Recent experiments1 have shown that an appreciable fraction of the pore space of a sand may be filled with water while oil production from this sand is water-free. Crowther and Haines,2 in experiments on electro-endosmosis in soils, reported that there was no endosmotic flow of water when the moisture content of the soil was 14 per cent or less, indicating that the moisture content of the soil below 14 per cent was held by dif-ferent forces than the water content above this value. This result is confirmed qualitatively by Dunlap,1 who found that "as the volume of water in the voids exceeds approximately 15 per cent of the pore volume, the permeability of the core to kerosene is markedly reduced." The author3 has also found in other experiments that the gas flow through a water-saturated sand reaches essentially 100 per cent when the pores of the sand still contain from 10 to 15 per cent water. The velocities of the flowing fluid in the experiments cited were comparatively high, so that in practice one may expect, at lower fluid velocities, an even higher moisture content of the sands with water-free oil or gas production. Thus a knowledge of the water content of oil-field sands becomes of con-siderable importance in estimating petroleum and gas reserves, and effi-ciency of fluid recoveries from depleted reservoirs. Rapid and reasonably accurate methods of measuring the water content of sand cores have not been described so far in any literature that has come to our attention.4 The method described below is devel-oped from methods that have been used for some time to measure the water content of alcohols.5,6,7 It is an application of the fact that in the presence of certain organic liquids such as kerosene, carbon tetrachloride, xylol, etc., water and alcohol are only partly miscible. This relation-ship has been used for some time in the study of gasoline-alcohol mixtures where the presence of small quantities of water affect the solubility of

Jan 1, 1938

By S. Usui, I. Iwasaki

The effect of pH on the adsorption of dodecylamine at the mercury-aqueous solution interface was investigated by differential capacity and electrocapillary measurements. With dodecylammonium acetate, the differential capacity curves showed two desorption peaks in the cathodic branch with their relative intensities varying with the solution pH. With dodecyltrimethylammonium chloride, only one cathodic de-sorption peak was observed in the same pH range. Through thermodynamic analysis of the electrocapillary curves, the adsorption density of undissociated amine was evaluated separately from that of aminium ion. The adsorption densities of the un-dissociated amine and of the total amine increased with increasing pH. The ratio at the interface of undissociated amine to aminium ion was several orders of magnitude greater than the ratio in the solution and increased with increasing pH. The potential at the closest distance of approach of counter ions to the mercury surface was compared with values of zeta potential on quartz previously reported. The most important variable in the flotation separation of minerals is probably the pH of the pulp, and a number of theories have been proposed to explain its effect on the condition of the mineral surfaces, on the dissociation of collectors and of inorganic and organic species (accidentally present or intentionally added) in the pulp, and on the mineral-collector interaction. In the development of a theoretical background for oxide flotation systems, an experimental approach based on electrokinetic measurements has been of much value, although the effect of pH becomes confounded since it governs both the electrochemical conditions of the oxide surface and the dissociation of the collector. For investigation of the adsorption behavior of long-chain collectors on oxide minerals, however, electrokinetic potential measurements are the most widely used technique. Hydrogen and hydroxyl ions are found to be the potential determining species, thereby governing the interfacial electrical conditions. The electrostatic interaction between the charged mineral surfaces and ionized collectors is regarded as the driving force for the adsorption of the collectors. An association of alkylamine collectors adsorbed on quartz surfaces has been postulated from streaming potential measurements, and a term "hemi-micelles" has been proposed.' The possibilities of coad-sorption of undissociated amine along with aminium ion has been inferred from contact angle measurements? and from adsorption studies.~ Electrochemical titration as applied to silver sulfide provides a more quantitative approach to the analysis of the electrical double layer at an ionic solid-solution interfaceqG and the electrochemical evidence for the adsorption of amine at pH 4.7 indicates a specific affinity of dodecylammonium ion towards silver sulfide surfaces, whereas at pH 9.2 the adsorbed species might be free arnine." A combination of differential capacity and electrocapillary measurements on a dropping mercury electrode was reported to be a sensitive method of provid- ing reliable information on the adsorption behavior of dodecylammonium acetate (DAA) at a natural (near neutral) pH.? It was also shown that there were striking similarities in the properties of the double layer and in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide. The effect of pH on the differential capacity curves at a mercury-sodium fluoride solution interface has been investigated by Austin and Parsonss who reported that between pH 7 and pH 11 there was very little effect. In the present paper, the adsorption behavior of DAA was investigated as a function of pH through differential capacity and electrocapillary measurements and the information gathered was correlated with that available in literature on quartz and silver sulfide. Experimental The apparatus and the method used for determining the differential capacity and the electrocapillary curves were identical to those described previously.' The ionic strength of the supporting electrolyte was fixed at 0.1 M with potassium fluoride, and the pH of the solution with potassium hydroxide. Only the neutral to alkaline range was covered in order to avoid the dissolution of the glass vessel with hydrofluoric acid. Results In Fig. 1 the differential capacity has been plotted against the applied potential at a DAA concentration of 10-' M at three different pH values. The curves are characterized by one capacity peak in the anodic branch, by two capacity peaks in the cathodic branch, and by a marked depression in capacity between the peaks. The depression indicates an adsorption of the arnine in this potential range. One of the cathodic peaks appears at pH 7.3 near -1.4 v and decreases with increasing pH. The other appears at pH 8.9 near —1.2 v and increases with increasing pH. At pH 9.6 only the latter peak is observed. Beyond the cathodic peaks, all the curves tend to converge with the curve in the absence of DAA, implying that two different species are being desorbed in this potential region. The anodic peak near 0.0 v increases markedly with increasing pH. The well-defined anodic peaks at pH 8.9 and 9.6 were accompanied by an appreciable increase in the current flow (in excess of O.luA), and, therefore, is a "pseudo-capacity"'" due to a

Jan 1, 1971

By N. L. Svensson

The model developed by Tuylor for the calculation of Polycrystalline yield strength has been applied to the case of an aggregate hawing a preferred orientation. In general this procedure requires the specification of texture by means of weighting factors applied to specific orientations. The problem to which the model has been applied is that of the yield-strength aniso-tropy of cold-rolled aluminum whose rolling texture was described as a combination of (110)[112] and (311) [112] In this case yield-strength anisotropy is defined by the rutio of yield strength measured at an angle 8 to the rolling direction to that measured along the rolling direction. The method of calculation of yield-strength ratio as a function of ? is described and the results show good agreement with experimental values. The orthotropic yield criterion suggested by Hill has been applied to the results and the strain ratio R also calculated as a function of ?. This has been compared with calculations using the method suggested by Elias, Heyer, and Smith which does not exhibit suck good agreement with observation. one deficietlcy of the method presented is that the strain ratios used by are those applying to iso-Irobic materials. The method should therefore be reg-clrded only as a first abbroximation to the prediction of anisotropy. THE problem of calculating the stress-strain characteristics of polycrystalline aggregates from the properties of single crystals has attracted attention for a number of years. The most important contributions to this study have been those due to: Sachs,' Cox and sopwith,2 Taylor,3 Kochendorfer,4 Batdorf and Budiansky,5 Calnan and Clews,6 Bishop and Hill,7,8 Kocks,9 Budiansky, Hashin, and sanders, 10 Kroner,11 Cyzak, Bow, and payne, 12 Budiansky and Wu,13 and Lin.14 While the earlier work has been largely superseded, recent developments tend to support Taylor's solution" within the restriction imposed by his assumptions. The essential features of Taylor's approach were: 1) the material is rigid-plastic; 2) each grain experiences the same strain components as the aggregate as a whole (the problem was that of uniaxial deformation with principal strain components in the ratio 3) all regions of each grain deform uniformly; 4) work hardening occurs equally on all slip systems. While Bishop and Hill7 have generally validated this approach, there has been some criticism offered. Kocks? as pointed out that since multiple slip must occur the single-crystal data must be determined from orientations arranged such that polyslip takes place. Boas and Hargreaves,15 and others, have shown experimentally that the strain distribution within grains is not uniform, the strains in the vicinity of grain boundaries being less than those in the center of the grains. Both of these criticisms can be largely offset by the suitable choice of single-crystal critical shear stress. However, for the problem analyzed below, the critical shear stress is not directly used and, consequently, these criticisms lose their importance. The more recent contributions have attempted to obtain a more complete analysis by considering an elas-toplastic material and considering interactions between grains of differing orientations. Lin14 has considered the early stages of yielding for a polycrystalline aggregate having specific regions of defined slip plane orientations. On the other hand, Budiansky and Wu13 have allowed for these interactions for randomly disposed grain orientations and have calculated the polycrystalline stress-strain curves for crystals exhibiting either elastic-ideally plastic or kinematic hardening characteristics. This work has shown that yielding commences when the macroscopic stress is 2.2 times the critical shear stress for slip in a single crystal (7,). The yield stress-strain curve then rises becoming asymptotic to a value of 3.072 7,. This is close to the value obtained by Bishop and Hill (3.06) in their confirmation of Taylor's method. This, of course, is to be expected since, at large strain values, the elastic strains are negligible and the rigid-plastic model is satisfactory. The results of Budiansky and Wu indicate that the result obtained by Taylor is 7.7 pct high at a plastic strain which is two times the elastic strain at the initiation of yield. By defining the anisotropy in terms of relative values, the ratio of yield strength at orientation ?, to that measured in the rolling direction, the effect of the discrepancy in Taylor's solution is considered to be of lesser consequence. Therefore, it is anticipated that an analysis based on Taylor's solution, which can be quite straightforward, should provide a reasonable estimation of the anisotropy of materials having a preferred orientation texture. OUTLINE OF TAYLOR'S METHOD In fee metals there are four possible slip planes (the octahedral planes) and in each there are three possible slip directions (the edges of the octahedron), that is a total of twelve possible slip systems. von Mises16 has shown that at least five independent slip systems must become operative in each grain of the polycrystalline aggregate in order to preserve continuity of strain. With this geometrical requirement as basis and the assumptions previously listed, Taylor determined the operative slip systems for a number of orientations of the tensile stress axis specified in the unit stereographic triangle. For the ith slip system, the critical shear stress

Jan 1, 1967

By B. W. Christ, P. M. Giles

Mossbauer effect measurewents have been made on I-mil-thick foils of commercial 1 wt pct C steel and Fe-2 wt pct C alloy. The experimental method required about 3 to 5 vol pct of a phase in the nzultiphase steel sample for detection. Room-temperature Md'ssbauer patterns obtained on austenitized atid quenched samples exhibit fifteen, and possibly twenty-one, lines. A sharp parama&tetic singlet and a quadrupole doublet, poorly resolued from the singlet, are attributed to austenite. Remaining lines are due to tnartensite. Accurate evaluation of austenite line paranzeters is not feasible if significant amounts of other phases such as carbides or martensite occur simultaneously with austenite. This is demonstrated by comparison of hyperfine interactions determined for austenite in multiphase high-carbon samples with those reported for Fe-C austenite in a nearly 100 pct austenitic sanple. Lines from carbides are incompletely resolced from austenite lines, as demonstrated by comparison of austenite line positions with carbide line positions calculated frow published values of hyperfine interactions. One martensite line overlaps an austenite line in the pattern for commercial 1 wt pct C steel. Results of this study suggest that the usefulness of e M6ssbauer pectroscopy for quantitatizle analysis of austenite in bulk samples of quenched and tempered high-carbon steels is restricted by poor resolution. Use of Mossbauer spectroscopy for phase identification and for evaluation of atomic and electronic structures appears quite feasible, however, The Mijssbauer effect has been widely discssed,'-and e Mossbauer effect measurements have been reported on materials of metallurgical interest.7"20 In particular, it has been proposed that e Mossbauer patterns of commercial steels and laboratory-made Fe-C alloys, in the quenched condition, are composed of lines originating in two phases, Fe-C austenite and Fe-C martenite.-' Evidence accumulated in this study demonstrates that three absorption lines found in the central region of the e Mossbauer pattern obtained on quenched steels are attributable to retained austenite. This interpretation is supported by parallel decreases in the intensity of these three lines caused by subambient cooling of commercial 1 wt pct C steel samples after water quenching to room temperature. A second result of this study is to clarify effects of line resolution and sensitivity in the Mossbauer patterns of multiphase steels on the accu- rate determination of austenite line parameters. Experimental line widths (full width at half height) are generally 1.5 to 3 times larger than the natural line width of 0.19 mm per sec. At least two lines, and sometimes more, from a single phase such as cementite (Fe3C), other carbides, martensite, and austenite fall in the energy band, i0.85 mm per sec. hhis band width is employed simply for convenient reference. It represents approximately the energy interval between the + 112 to 112 transitions in ferrite and is expressed as the velocity needed to Doppler shift a 14.4kev 7 ray to the aforementioned ferrite energy levels. This energy band is referred to as "the central region of the Mossbauer atttern:: in this paper. Hence, due to the large number of lines from different phases in a multiphase steel falling in a relatively narrow energy band, absorption lines from the different phases may overlap. Analysis of available data, presented below, indicates that this occurs to a significant extent for phases which commonly occur in quenched and quenched and tempered high-carbon steels. One consequence of limited resolution in the Mdssbauer patterns from multiphase steels is difficulty in accurate determination of such line parameters as position, width, and intensity. In fact, it appears that quantitative analysis for retained austenite in quenched and tempered high-carbon steels is not practical with the present experimental method. Line resolution is influenced to some extent by sensitivity. We point out below that atom or volume fractions of less than about 3 to 5 pct are not detected by the present experimental method. Thus, the presence of a multiplicity of phases does not always lead to impaired resolution. Finally, we report in this paper room-temperature MGssbauer parameters determined for austenite in a freshly quenched, commercial 1 wt pct C steel and in a freshly quenched laboratory heat of an Fe-2 wt pct C alloy. These parameters are compared with others reported in the literature. Three types of hyperfine interactions are detectable in a Mossbauer effect measurement: isomer shift, quadrupole interaction, and magnetic dipole interaction. These interactions are evidenced by one, two, and six line patterns, respectively.'-4 More than one type of interaction has been reported in certain metallurgical phases thus far studied by this method. Isomer shift is the experimentally measured displacement of line position from some arbitrarily defined reference position. In the case of a multiline pattern, isomer shift is given by the displacement of the centroid (center of gravity) of that pattern from the reference position. All isomer shifts measured at finite temperatures contain a second-order Doppler effect characteristic of that temperature. The isomer shift is related to the total s electron density at the nucleus, becoming more negative with increasing s electron density. The first-order quadrupole effect arises from the interaction between the nuclear quadrupole moment and any axially symmetric electric field gradient in

Jan 1, 1969

By G. A. Chadwick, D. Jaffrey

The morpho1ogies and orientation relationships of the phases in the Sn-Zn and A1-A13Ni eutectic systems were examined by electron microscopy and X-ray diffraction techniques. In each alloy the "transition" from the lamellar to the fibrous morphology was found to be one of scale, not of type. The minor phase in both systems exhibited certain well developed facets which were not affected by changes in the ingot solidification rate. The crystallographic relationships displayed by the pairs of phases in both systems were also insensitive to the growth rate. In the Sn-Zn alloy, the unique relationship of: growth direction - II [1201 Sn - II [01101 Zn and ribbon interface plane 11 (101) Sn 11 (7012) Zn was determined. The Al-Al3Ni alloy phases did not possess any particular orientation relationship, though the Al3Ni phase invariably grew in the [010] direction and exhibited the same set of facet planes. These results are discussed in relation to current eutectic growth theories and explanations of the "lamellar to fibrous transition". THE lamellar to fibrous transition that occurs in many eutectic alloys has been the subject of considerable speculation and experimental study. In some alloys it can be induced solely by an increase in the solidification rate,'-3 whereas in others the transition supposedly occurs only if the lamellae are forced to grow out of the overall ingot growth direction.4-6 he cause of this latter type of transition has been attributed to deviations of the lamellae from their low energy habit planes;4'5'7 fibers are produced because the sustaining force for lamellar growth (a low energy boundary) is destroyed. Implicit in these explanations is the assumption that fibers are circular in cross-section and completely lacking in low energy inter-phase interfaces. The "natural" growth rate dependent transition has been studied less thoroughly although Tiller8 has attempted a theoretical explanation of it. Tiller's arguments are not completely satisfactory9 but his suggestion that the relative undercoolings of the solid/liquid interface for lamellar and fibrous morphologies are growth rate dependent cannot be totally discounted; it is possible, for instance, that the relative interfacial undercoolings could alter and produce the observed morphology change if the orientation relationships between the phases and the associated interphase bound- ary energies were sensitive to growth rate. Salkind et al." have reported finding a change in the orientation relationships in the A1-A13Ni system accompanying the lamellar to fibrous transition, but contradictory evidence has also been reported for this3'" and another system,12 so the position remains unclear. In an attempt to clarify matters a study was made of the "lamellar to fibrous" transition in the Sn-Zn and A1-A13Ni eutectic systems; the morphologies of these two selected systems are quite similar when viewed by optical microscopy. In the present research the morphologies and morphology changes were investigated by electron microscopy. The orientation relationships existing between the eutectic phases were also determined for both morphologies in both eutectic systems. EXPERIMENTAL PROCEDURE The materials and method of alloy preparation and ingot solidification for the Sn-Zn system have been reported previously.2 In this investigation nine horizontally grown ingots of the highest purity (99.9997 pct) were used. The temperature gradient in the melt was not intentionally varied and was approximately 10°C per cm. Seven growth rates between 1.3 cm per hr and 20 cm per hr were imposed. The A1-A13Ni alloys were prepared from "Spec. Pure" nickel and 99.995 pct aluminum by melting the components in an open alumina crucible and casting the melt into the cold graphite mold. Six ingots of the Al-Al3Ni alloy were unidirectionally solidified at growth rates from 1 cm per hr to 12 cm per hr under high purity argon. A typical ingot was 20 cm long, 1 cm wide, and 0.75 cm to 1.5 cm thick. Samples taken from the bars at positions 12 cm from the nucleation end were examined by conventional orthogonal-section metallo-graphic techniques. When required, samples were mounted for X-ray diffraction analysis using the Laue back-reflection technique with a finely focussed X-ray source. The surfaces of the A1-A13Ni specimens were prepared by mechanically polishing them down to the 1 µ diamond pad stage followed by an electropolish in 80/20 methanol/perchloric acid solution at 0°C and 20 to 30 v. The Sn-Zn specimens were repeatedly polished on an alumina pad and etched in hot dilute (2 pct) nitric acid until the diffraction spots were found to be sharp. Thin films of the alloys were prepared for observation in an electron microscope by spark machining thin discs (0.03 to 0.04 in. thick) from longitudinal and lateral sections of the bars and elec-trolytically thinning them via a jet polishing technique. For the A1-A13Ni eutectic alloy, an 80/20 mixture of ethanol/perchloric acid at 40 v and 20°C was found to be satisfactory. A solution of 70/20/10 methanol/perchloric acid/butylcellosolve at 25 v and 20°C was used on the Sn-Zn alloy. For the former alloy the jet nozzles (cathodes) and the disc clamps were of aluminum;

Jan 1, 1970

By R. W. Heckel, R. E. Trabocco

The recovery process in 400 Monel filings was followed, principally, by using the Warren-Averbach technique of X-ray peak profile analysis. The deformation fault probability, a, was 0.006 in samples of unannealed filings. a , the twin fault Probability , was approximately 0.002 in samples of unannealed filings. Both a and 0 were found to "anneal out" at 600°F. The effective particle size and mzs strain increased and decreased in the (111) direction, respectively, with increasing annealing temperature. The actual particle size was found to be almost equivalent to the effective particle size. Tile small values of deformation and twin fault probabilities accounted for the similarity in values of the effective and actual particle sizes. Stored strain energy and dislocation density calculations based on rms strain decreased with increasing annealing temperature. The dislocation density decreased from 10" per sq cm in the unannealed filings to 10' per sq cm in the partially re-crystallized filings. The square root of the dislocation density based on strain to that based on particle size indicated a random dislocation distribution in the unannealed filings. The dislocation arrangement changed to one with dislocations in cell walls with increasing annealing temperature. THE recovery processes which occur in metals are generally thought to be a redistribution and/or annihilation of defects.' Investigators' have shown that recovery processes can be characterized by X-ray line-broadening analyses. Michell and Haig4 measured the stored energy of nickel powder by calori-metry and found the value to be greater by a factor of 2.5 than that from X-ray data obtained by the Warren-Averbach technique.= Minor increases in particle size occurred up to 752°F (recovery), while above 752°F the particle size increased greatly due to recrystalliza-tion. X-ray microstrain values decreased between room temperature and 392"F, remained constant from 392" to 752"F, and decreased from 752°F to a negligible value at 1112°F. Faulkner developed an equation for calculating stored strain energy based on X-ray line-broadening data which gave a closer correlation of measured and calculated stored strain energy based on the data of Michell and Haig. The stored strain energy released during recovery is predominately dependent on the decrease in dislocation density which was p-enerated from cold work.7 Stored energy has been measured8 in alkali halides during recovery and recrystallization and 80 pct of the stored energy was found to be released during recovery. Dislocation distributions have been studiedg in a number of fcc metals by thin-film electron microscopy. Howie and Swann" found the stacking fault energy of copper and nickel to be 40 and 150 ergs per sq cm, respectively. ~rown" has pointed out that these stacking fault energy values should be corrected to 92 and 345 ergs per sq cm, respectively. The dislocation distribution of a metal is directly dependent on the stacking fault energy of the system. Metals of high stacking fault energy such as aluminum cross-slip readily and do not form planar arrays of dislocations. Metals of lower stacking fault energy such as stainless steels" do not cross-slip readily. Cold-worked nickel has been found to form a cellular dislocation structure after annealing.13 The relatively high stacking fault energy of nickel and copperlo to a lesser extent favor cellular structures of dislocations rather than planar arrays after deformation. The present study of recovery was carried out on a Ni-Cu alloy (Monel 400) to compare with prior studies for pure nickel and pure copper. X-ray line-broadening techniques were used to measure the effect of recovery temperature on rms strain and particle size and the results were compared with previous studies on copper'4-'7 and nickel., Calculations were also made on stacking fault probabilities, dislocation density, dislocation distribution, and stored strain energy as affected by temperature. EXPERIMENTAL PROCEDURE The nominal analysis of the Monel 400 used in this investigation was: 66.0 pct Ni, 31.5 pct Cu, 0.12 pct C, 0.90 pct Mn, 1.35 pct Fe, 0.005 pct S, 0.15 pct Si. The annealed material was cold-reduced in two batches, one 50 pct and the other 80 pct. It was originally planned to conduct line-broadening studies of these bulk samples; however, rolling textures that developed produced low-intensity peaks which were not suitable for line-broadening analysis. Filings were prepared at room temperature from both the 50 and 80 pct cold-reduced specimens, series A and series B, respectively, and were not screened prior to heat treatment or X-ray studies. Heating to the annealing temperature, 200" to 120O°F, was accomplished in a matter of minutes in a hydrogen atmosphere. Following heat treatment, some of the filings were mounted and polished for microhardness measurements with a Bergsman microhardness tester, using a 10-g load. A G.E. XRD-5 diffractometer using nickel-filtered Cum radiation was used to obtain all diffraction patterns. Only (111)- (222) line-broadenin data were used in the present study since the {400f peaks were too weak to use. The Fourier analysis of the (111) and (222) peak

Jan 1, 1969

By David B. Scott

The Mogollon mining district, New Mexico, has received little public attention, although for 15 years it has been the leading silver producer of the state; it is situated in a region remote from the principal lines of travel, and its activities have usually been limited to the operations of two or three companies. The value of the total production of the district in the 44 years of its history has been estimated at $15,000,000. For the years 1904 to 1917, inclusive, the output was: gold, $4,370,000; silver, 10,042,000 oz.; copper, 874,862 lb.; total value, approximately $10,500,000. In 1913 the district contributed 80 per cent. of the total silver production of New Mexico, but in 1917 only 41 per cent., due to serious interruption in the operations of the leading producer. Since 1914 the silver output has diminished one-half, and the present high value of silver is nearly offset by the increase in cost of production. The output of gold has rarely exceeded 35 per cent. of the total for New Mexico. The ratio of silver to gold, by weight, has averaged 46:1 based on the whole output of the district. Location and Topography The town of Mogollon is 75 mi. (121 km.) by a poorly located highway ,. from the nearest railroad terminals, at Silver City and Tyrone. All supplies are transported by motor trucks and teams. The area, sometimes called the Cooney Mining District, lies on the western flank of the Mogollon Mountains, which occupy the western part of Socorro County. The elevations drop steeply on the west to the valley of the San Francisco River, adjacent to the Arizona boundary. The topography is very rugged, the whole area being sharply dissected; deep canyons with steep gradients and rugged walls are characteristic of the whole western slope of the Mogollon Range. The main canyons i run east and west, and usually maintain a flow of water during the entire year. As would be expected in a region of such deep dissection, the mines are generally dry. The mountain ridges between the canyons have altitudes varying from 7000 to 10,000 ft. (2130 to 3050 m.) and drop sharply, on their western face, to the floor of the San Francisco Valley at an elevation of 5000 ft. (1525 m.). Erosion has been rapid, and the

Jan 1, 1920

By J. W. Leonard, J. C. Anderson, C. T. Holland

PREPARATION CONTROL IN UNDERGROUND MINING Selective Mining According to district Depending upon the particular geographic location or seam characteristics modem raw coal preparation practices can be used to obtain improved product quality and uniformity. Nevertheless, certain coal markets may require only marginal quality while others may require very high quality and these objectives may be sought by commencing the preparation of coal underground at the "working face." Underground preparation involves choosing those portions of the bed which can be cleaned to satisfy predetermined market requirements involving (1 ) maintenance of uniformity in chemical quality, (2) elimination of removable impurities, (3) control of sizes and size ratios and (4) control of moisture. The methods employed to attain these objectives vary widely with the (1) seam under development, (2) mining equipment available and (3) changing trends in the consuming markets. When a mining property is opened and development progresses from one section to another the (1) petrography of the coal in the bed does not re- main uniform, (2) character of roof and floor are subject to change and (3) character and prevalence of mineral impurities are subject to considerable variation. The quality of coal shipped to market from any mine depends upon intelligent foresight, planning, execution and supervision. Mining becomes a highly technical art. The quality of coal as determined by chemical and petrographic analysis is without question one of the most important considerations in the development and life of any coal-mining property. Variations in such proper- ties as volatile matter, ash, sulfur, Btu content and petrography are of considerable interest and to a limited extent so are such properties as phosphorous content, free swelling index, plasticity, hardness, pressure formation during coking and ash composition. The maximum and minimum specifications of these characteristics as established by competitive market conditions place definite limits on the marketability of a coal. The prospecting and evaluation of any area containing one or more salable coal beds by means of channel samples taken from outcrop openings and/or from diamond-drill cores can yield valuable data on coal characteristics. By correlating the data developed from distinct petrographic sections of channel and/or drill core samples, the quality of the bed according to stratification will be evident. There are few coal beds that do not show wide variations of such characteristics as ash and sulfur

Jan 1, 1968

By R. G. Ward, John Henderson. R. G. Hudson, G. Derge

Densities of melts of the iron oxide-silica system in contact with solid iron have been measured by the maximum hubble pressure method in the composition range O to 37 wt pct SiOz and the temperature range 1255 to 1410C. The constitution of the melts is discussed and it is postulated that the structure changes from a dislribution of iron ions in an oxygen ion network at pure "FeO" to a distribution. of iron ions in a network of silicate tetrahedra at the orthosilicate composition. JOHN HENDERSON, Junior Member AIME, was formerly with the Metals Research Loborotory, Carnegie Institute of Technology, Pittsburgh, Pa., on leave from Broken Hill Proprietary Co., Ltd., Research Division, Shortland, Australia. R. G. HUDSON, formerly with Metals Research Laboratory, is now with the John Jay Hopkins Loborotory for Pure and Applied Science, General Atomic Division, General Dynamics Corp., LaJolla, Calif. R. G. WARD, was formerly with the Department of Metal lurgical Engineering, Carnegie lnstitute of Technology, while on leave from the Department of Metallurgy, University of Sheffield, England. G. DERGE, Member AIME, is Jones and Laughlin Professor of Metallurgical Engineering, Carnegie lnstitute of Technology. Manuscript submitted January 19, 1961. ISD The system iron oxide-silica is an important one metallurgically because it forms the basis of several complex slag systems in use for industrial smelting and refining processes. In recent years considerable work has been done on liquids of this system but there are still many points of difference among workers using different experimental techniques and theoretical approaches. Phase equilibria/"3 activity,4-6 electrical conductivity,' current efficiency,' transference number,8 viscosity,9 surface tension,'' and density" measurements have all contributed to an understanding of the problem. Measurement of density is one procedure which is directly indicative of liquid structure since any deviation from ideality must be a result of structural interactions. Liquids of the iron oxide-silica system are of special interest because this is one of the few metal oxide-silica systems on which measurements can be carried out conveniently over the entire composition range from pure oxide to silica saturation. This includes the range of high basicity which has received relatively little attention in other systems. Although one investigation of density in this system has previously been undertaken," the results seem of sufficient importance to warrant the independent redeter-mination reported here.

Jan 1, 1962