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By Michael B. Bever, Carl F. Floe

The solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to I300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. Review of Previous Work The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar5 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwasé3 reported large hydrogen solubility values for several compositions of copper-tin alloys, which appear to be in error.

Jan 1, 1944

By Carl F. Floe, Michael B. Bever

The solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to I300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. Review of Previous Work The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar5 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwasé3 reported large hydrogen solubility values for several compositions of copper-tin alloys, which appear to be in error.

Jan 1, 1944

By Robert E. Tally

CHAUNCEY L. BERRIEN, Butte, Mont. (written discussion).-Having had much actual experience with mine fires which have occurred or have been active in the mines of the Anaconda Copper Mining Co. during the past 4 years and having lately visited the fire zone of the United Verde mine with Mr. Tally, I wish to congratulate him for the success which he has had in controlling this fire and making the mine perfectly safe .for his miners. By this work he is not only keeping the property in operation but is reclaiming many lost orebodies. The ventilation system as described by him is practically the same as that used under my direction at the Mountain View mine fire in Butte in 1913 and at the Pennsylvania fire in 1916. This same system is at present being followed at the Leonard mine to extinguish a fire which has been active for 10 years although bulkheaded. The mining system in the Butte mine, at the origination of these fires was the same as that at the United Verde, namely, square setting .accompanied by the use of much timber bulkheading in the stopes owing to heavy ground. The pyritic content of the ore in Butte is not as high, but on the whole conditions have been the same, with the exception of actual location of the fire in the mine. I agree with Mr. Tally that flooding, the use of C02 or any gas, and the use of steam are all impracticable unless the fire zone can be absolutely sealed. His system of upcast escapement shafts in the fire zone, the use of bulkheads and fans to keep the gases away from the firemen, must be resorted to. By the method lie describes actual stoping may be carried on safely if started from the bottom of the fire and if the fire zone extends to the surface. In other words, the fire zone must be isolated from the rest of the mine by bulkheads and solid ground, with no ground above which can be damaged by spread of fire or caving. The serious fires in Butte have .occurred on or between levels in the mines where it was necessary to prevent their .extension upward, downward and laterally while the work of actually extinguishing them was in progress. This necessitated proper bulkheading should we lose control of the fire, the installation of ventilation similar to Mr. Tally's and the systematic drilling of holes with diamond drills for distributing water on the fire and around it.

Jan 12, 1916

By John G. Koert, Koert D. Burnham, John G. Broughton

Wollastonite in Essex County, New York, occurs as a typical contact mineral in a series of rocks metamorphosed by anorthosite. Sole current use is in various types of electric welding fluxes. Its uniform lathlike shape suggests its use as a specialized filler. Introduction Wollastonite (CaSiO3) was first noted in the vicinity of Willsboro, Essex County, New York, about 1810 by Dr. William Meade, and described from the same locality in 1821 by Lardner Vanuxem.' Recent exploration and development indicate that the deposit is of adequate size for continued exploitation on a larger scale than the present operations. The only other known occurrence of like magnitude in this country is in Kern County, California.* Wollastonite has been reported from Michigan, Pennsylvania, and Lewis County, New York, but these are little more than mineral localities. Geology The Essex County wollastonite has been found outcropping at numerous separate localities in a belt of contact metamorphosed sediments, 1/4 mile wide, which begins 2 miles southwest of the village of Willsboro and trends N. 70" W. for approximately 6 miles (Fig. I). In this belt, the pre-Cambrian Grenville has been injected and partially replaced by the more liquid portions of an anorthositic magma. Bud-dington and Whitcomb3 have described the rock in this contact metamorphosed belt as "Mixed gneisses: Grenville mafic, pyroxenic and garnetiferous gneisses and skarns* with local nearly uniform garnet or pyroxene layers and with gabbroic anorthosite sheets. A few limestone layers." These rocks are underlain, presumably at no great depth, by gabbroic anorthosite gneiss, the typical Whiteface border facies of the Adirondack anorthosite massif. The occurrence of wollastonite in large quantities was discovered during the quarrying of the garnet-rich layer that overlies the wollastonite at one opening. Further prospecting revealed its presence elsewhere in the belt, overlain in most places by the garnet. Accurate tracing of the wollastonite is difficult, owing to the glacial cover and to the fact that the weathered surface of the mineral has a dark, dirty brown color, and that the wollastonite itself has been dissolved more or less completely along the outcrops. It has, however, been noted at 10 localities within the skarn belt in the first 2 1/2 miles from its southeastern end. It has not been found in the northern half of the belt and therefore may be limited to the southern half. At the Fox Hill quarry, which is the main opening, 150 ft. have been exposed, showing an aggregate thickness of 30 to 35 it. Of

Jan 1, 1948

By Koert D. Burnham, John G. Broughton, John G. Koert

Wollastonite in Essex County, New York, occurs as a typical contact mineral in a series of rocks metamorphosed by anorthosite. Sole current use is in various types of electric welding fluxes. Its uniform lathlike shape suggests its use as a specialized filler. Introduction Wollastonite (CaSiO3) was first noted in the vicinity of Willsboro, Essex County, New York, about 1810 by Dr. William Meade, and described from the same locality in 1821 by Lardner Vanuxem.' Recent exploration and development indicate that the deposit is of adequate size for continued exploitation on a larger scale than the present operations. The only other known occurrence of like magnitude in this country is in Kern County, California.* Wollastonite has been reported from Michigan, Pennsylvania, and Lewis County, New York, but these are little more than mineral localities. Geology The Essex County wollastonite has been found outcropping at numerous separate localities in a belt of contact metamorphosed sediments, 1/4 mile wide, which begins 2 miles southwest of the village of Willsboro and trends N. 70" W. for approximately 6 miles (Fig. I). In this belt, the pre-Cambrian Grenville has been injected and partially replaced by the more liquid portions of an anorthositic magma. Bud-dington and Whitcomb3 have described the rock in this contact metamorphosed belt as "Mixed gneisses: Grenville mafic, pyroxenic and garnetiferous gneisses and skarns* with local nearly uniform garnet or pyroxene layers and with gabbroic anorthosite sheets. A few limestone layers." These rocks are underlain, presumably at no great depth, by gabbroic anorthosite gneiss, the typical Whiteface border facies of the Adirondack anorthosite massif. The occurrence of wollastonite in large quantities was discovered during the quarrying of the garnet-rich layer that overlies the wollastonite at one opening. Further prospecting revealed its presence elsewhere in the belt, overlain in most places by the garnet. Accurate tracing of the wollastonite is difficult, owing to the glacial cover and to the fact that the weathered surface of the mineral has a dark, dirty brown color, and that the wollastonite itself has been dissolved more or less completely along the outcrops. It has, however, been noted at 10 localities within the skarn belt in the first 2 1/2 miles from its southeastern end. It has not been found in the northern half of the belt and therefore may be limited to the southern half. At the Fox Hill quarry, which is the main opening, 150 ft. have been exposed, showing an aggregate thickness of 30 to 35 it. Of

Jan 1, 1948

By Harry M. Mikami

Refractories are heat-resistant, generally nonmetallic materials used as the linings of furnaces or high temperature vessels in the steel, iron, nonferrous metals, glass, cement, lime, ceramic, chemical, petroleum, paper, and power and heat generation industries. Refractories must have structural strength at high temperatures but also, in many applications, must simultaneously resist chemical-physical corrosion-erosion from stags, metals, granular solids, or gases. Among the major uses are the pyrometallurgical processes for producing iron, steel, copper, aluminum, nickel, lead, zinc, etc. Rotary cement kilns, glass tanks, refineries, utility boilers, chemical and ceramic (including refractories) plants, and a myriad of other smaller scale users employ refractories in the high temperature parts of their operations. Thermal, chemical, and structural conditions under which refractories are used differ widely so there is a great variety of refractories to fill the various needs. Two major classifications are the "basic" and "acid" types. Basic refractories include magnesia and chromite, singly and in combinations, dolomite, and forsterite (olivine). The acid category includes aluminosilicates, alumina, and silica. There are a number of other specialized types such as carbon, graphite, silicon carbide, zircon, and zirconia that have important applications but are used in much smaller amounts than the major categories. Physically, refractories can be divided into bricks and shaped products on the one hand and unshaped or monolithic products (also termed specialties) on the other. There are many further subclassifications and divisions, a discussion of which is beyond the scope of this chapter; see Refs. 2 and 9. Raw materials for the principal basic refractories are magnesia and chrome ore. Magnesia, generally termed magnesite or periclase, is obtained mainly from seawater or saline brines extraction, but substantial amounts are produced from mined magnesite (MgCO3). Dolomite (CaCO3•MgCO3), another important basic refractory, is obtained entirely from mined sources. Acid refractory raw materials are: fire clays, flint clays, kaolin, and other natural clay minerals; aluminosilicate minerals such as kyanite, andalusite, sillimanite, pyrophyllite, bauxitic clays; calcined refractory grade bauxite, alumina from the Bayer process for the alumina group; and quartzitic rocks for silica refractories. The total value of all refractories shipped in the United States in 1974 was $989 million, a record to that date. Of this amount, about 73% represents bricks and shaped products and 27% is in nonshaped or monolithic products which comprise mortars, cements, castables, plastics, and ramming and gunning mixes. Fig. 15.4E.1 shows the rising value of all U.S. refractory shipments in the period 1948-1974. Values of brick and shapes paralleled

Jan 1, 1976

By B. Silliman

The experiments detailed by Dr. Hunt,* having demonstrated the fact that the copper contained in the "clay ore" of Jones's Mine, was rendered completely soluble in the bath of ferrous chloride, used in the Hunt and Douglas process, after heating in contact with carbonaceous matter in a close vessel, I set myself to devise a form of muffle furnace adapted to the treatment of large quantities of these and similar ores by a continuous process. The result is shown in the diagrams on Plate X, reduced from the working drawings, after which this furnace was built early in 1876, at Phœnixville, by the Chemical Copper Company on their works at this place. The peculiar character of this ore determined the form, dimensions, and position, with reference to charging and discharging of these muffles. The ore arrived from the mine with from 20 to 25 per cent. of moisture, and when dried at 21o F., or more slowly at lower temperature, it falls to a light incoherent powder, with occasional lumps of undecomposed rock. In this condition it is readily mingled with coal-dust or any like reducing agent, and requires no other preparation for the muffle than the use of the shovel, to mix it well with the reducing agent. As it is a remarkably good non-conductor of heat, it was obvious that the mass, to be heated through in a reasonable time, must not be too thick, while the weight of the mass must be sustained in a way to avoid undue strain upon the walls of the muffle. These walls must be as thin as practicable, to favor the more rapid transmission of heat, and must, therefore, be so constructed as to admit of being stayed on the sides at frequent intervals to resist the lateral thrust of the very mobile mass of pulverulent ore, which, for obvious reasons, must be charged at the top and drawn from the bottom of each chamber. These considerations led to the form adopted, viz., two vertical muffles, standing upon very strong bridge tiles, seen in longitudinal section, on the line E, F, and in plan in Fig. 3, on the same plane. (Plate X.) The vertical section of the muffle is seen in Fig. 4, drawn in the plane G, H, of the longitudinal section, Fig. 6, which is the key to all sections. The walls of the muffles are built of the best firebrick, very care-

RICHARD A. CONKLING (communication to the Secretary*).-Mr. Hager says that his results on the correlation of well logs in the north Cushing field are the opposite to those of the author. Can he, then, explain why the structural dip of the formations increases with depth, as Dr. Ohern, in his criticism, sets forth that it does, and as all who have worked in these fields will admit, if the shales thicken on the crest of the anticline, as he says they do? We are willing to agree with Dr. Ohern that there is some evidence of a slight unconformity below the Bartlesville sand and think that we can prove, from a specimen in our office, that .this unconformity comes at the base of the Bartlesville sand in the south Cushing pool. On the Ingalls dome, in the southeast corner of Township 19 North, Range 4 East, however, we get results the same as those given by the author on Cushing. The Ballard well in the center of the Northeast Quarter of Section 33 is just 10 ft. higher, structurally, according to tile, surface contour, than the Ringold well -in the center of the Southwest Quarter of Section 34. The dip in the Bartlesville sand, between these wells, is 40 ft. and the dip on the top of the Mississippi lime is 75 ft. This also might be accounted for, partly by the unconformity, but the author used the interval between the top of the Oswego lime, which is about 420 ft. above the Bartlesville sand, and the oil horizon found in the lime in the Ballard well-just mentioned above-to find the depth at which the same oil should be found in a well in Section 5, Township 22 North, Range 3 East, 25 miles North. Using this interval below the Oswego in the former well, we predicted within 2 ft. where they would find the oil in the latter well. Of course, we know that it was accidental that we missed it only by 2 ft., but if there were much of an unconformity in this interval it would be more of an accident if we came within 100 ft. of the depth. Since it can be proven from most of the structures in this section that the clip continues to increase downward, below the Bartlesville at least, to the Mississippi lime, it does not seem necessary to the author to try to prove otherwise that the depth at which the shales will tend to thicken on top of a fold, has not been reached above the

Jan 6, 1917

By Irving Cadoff, Jack Medoff

THE linear thermal expansions of oriented single crystals of zinc were measured in the range from 20" to 416°C using a Leitz HTV optical lever differential dilatometer. The single crystals, supplied by Dr. J. J. Gilman, General Electric Research Laboratory, Schenectady, N.Y., were prepared from 99.999 pct-purity zinc, and were in the form of rods approximately 2 in. long by 0.15 in. in diameter having the following orientations: x = 1.5, 12, 20, 30, 37.5, 49, 60, 73, and 82 deg where x is the angle between the specimen axis and the (0001) plane of the crystal. From the family of expansion vs temperature curves, the instantaneous expansion coefficients were calculated at 100°C intervals, and Fig. 1 shows a plot of these derived coefficients for each orientation. Coefficients were obtained from the raw data using the chord-slope method. The curves in Fig. 1 indicate a positive temperature coefficient for low x, a negative temperature coefficient for high X, and an expansion coefficient invariant with temperature, amounting to about 43 x 106, for a crystal orientation of approximately 52 deg. From the available data, it is possible to arrive at the values for the axial thermal-expansion coef- ficients a, and a, by extrapolating the curve of the expansion coefficient vs orientation to zero and 90 deg orientations. More precise values for a, and a, are obtained if the instantaneous coefficients are plotted against the square of the cosine of the orientation angle, as shown in Fig. 2. The extrapolated terminal points of the best straight line through the data points of such a plot define the axial coefficients at that temperature. The theoretical justification for the linearity of this curve comes from inspection of a rearranged form of the general anisotropic equation for expansion: ax=a, + (a, -a,)cosZx [1I in which a, is the expansion coefficient in the "c" or [0001] direction and a, the expansion coefficient in the "a" or [ll50] direction. From Fig. 2, the axial coefficients at 100°C, for example, were found to be a, = 13.9 x 10'6 and a, = 62.4 x 10"6 per "C. In the same way, the coefficients were determined for 20", 200°, 300°, and 400°C. This data is summarized in Fig. 3. It is of interest to observe the common intersection of the curves in Fig. 3, which seems to bear out the earlier observation, from Fig. 1, of a

Jan 1, 1964

By James Norman, O. C. Ralston, John Dasher

MOST mineral products are used in the finely divided state, but some are sold in larger sizes. Coal, gravel, metallurgical fluorspar, phosphate rock, hematite, chromite, and other products are sold in sizes coarser than can be treated by many mineral-dressing methods. Gravity separation of coarser sizes by log washing and jigging is probably as ancient as any process now in use. The performance of jigs on a feed with sufficient difference in density of the minerals is excellent, but many families of minerals are too similar in density to be separated effectively by this method. The use of heavy suspensions of fine solids to separate coarse coal from bone and slate has been in use for some years. This separation by sink-and-float was limited until recently to light minerals. Development of galena and ferrosilicon as suspension media, by Minerals Beneficiation, Inc., at Mascot, Tenn., Pitcher, Okla., and Crosby, Minn., under patents granted during and since 1938, has permitted excellent results to be obtained on minerals of very similar densities up to 3.3. This process has been put in the hands of American Cyanamid Co. for exploitation, and further research now in progress may increase the density of suspension obtainable so that separations at a density of 4.0 may be practicable before this is published. The Huntington-Heberlein dense-medium process, developed in England, is also being commercialized in the United States by Sink and Float Corporation. Du Pont has developed a sink-and-float separation using halogenated hydrocarbons as parting liquids; at this writing, the method is used commercially only on coal but has been successful in the pilot plant on many other minerals using tetrabromethane at densities up to 2.95. While these processes were being developed to extend the range of separation by difference in density to the coarser sizes, the Bureau of Mines was engaged in developing a process that will extend the range of separation by difference in wettability up to 2-in. size. War work has pushed aside its further development indefinitely. The results are published here with the hope that some use may be suggested that will justify post-war development, and so that readers that may be able to make immediate use of the scheme may have the information. EARLIER WORK It has been known since the time of Herodotus (B.C. 484(?)-425) that water-repellent particles will adhere to sticky surfaces. That early historian reports the

Jan 1, 1942

By F. J. Mehringer, C. W. MacGregor

VARIOUS investigations have been carried out to determine the effects of cold-rolling on the common physical properties as represented by the yield strength, tensile strength, percentage of elongation and ordinary reduction of area. Very little information is available in the literature with reference to the effects of cold-rolling on the true stress-strain properties. Since the ordinary physical properties base both the stresses and the strains on the original dimensions of the test piece, which are greatly changed during the test, they are essentially empirical values and do not represent physically either true stresses or true strains. Consequently, they do not give an accurate picture of the effects of different conditions, both mechanical and metallurgical, on the strength and ductility of the material. It is not, however, the purpose of this paper to review the various advantages accruing from the use of true stress and true strain values, since these have been shown elsewhere,1-12 but to utilize them in representing the various effects considered. The true stress S and true strain (e = q') values mentioned above for the tension test are defined by1 [ ] where P, A, Ao are the axial load, the instantaneous area and the original area of cross section, respectively. From simultaneous readings of the axial load and the dimension or dimensions determining the instantaneous area of cross section, the true stress-strain curve is constructed by using the relations given in Eq. I. It is then the object of this paper to discuss the general effects of cold-rolling on the true stress and strain values for a low-carbon steel together with the effects of age-hardening and directionality on these properties. PRELIMINARY INVESTIGATIONS The material considered throughout the paper is a low-carbon steel of the following chemical analysis: C, 019 per cent; S, 0. 118; P, 0.092; Mn, 0.85; Si, 0.01. The stock was received in bars, 7 by 3/4 in., and was first annealed for one hour at 1650°F. followed by a furnace cool. Photomicrographs of this material showed considerable directionality even in the annealed condition. In view of the possible effects of the nonhomogeneity and directionality in this material, it was considered important to investigate their influence on the true stress-strain diagrams. In addition, the effect of strain-aging in this steel was also made the subject of a preliminary study. Elect of Aging on True Stress-strain Properties Since a certain time element would elapse between the cold-rolling operation and the final tension tests, it was determined to investigate the aging character-

Jan 1, 1945

By F. J. Meringer, C. W. MacGregor

Various investigations have been carried out to determine the effects of cold-rolling on the common physical properties as represented by the yield strength, tensile strength, percentage of elongation and ordinary reduction of area. Very little information is available in the literature with reference to the effects of cold-rolling on the true stress-strain properties. Since the ordinary physical properties base both the stresses and the strains on the original dimensions of the test piece, which are greatly changed during the test, they are essentially empirical values and do not represent physically either true stresses or true strains. Consequently, they do not give an accurate picture of the effects of different conditions, both mechanical and metallurgical, on the strength and ductility of the material. It is not, however, the purpose of this paper to review the various advantages accruing from the use of true stress and true strain values, since these have been shown elsewhere,1-l2 but to utilize them in representing the various effects considered. The true stress S and true strain (e = q') values mentioned above for the tension test are defined by1 S =1/A and where P, A, Ao are the axial load, the instantaneous area and the original area of cross section, respectively. From simultaneous readings of the axial load and the dimension or dimensions determining the instantaneous area of cross section, the true stress-strain curve is constructed by using the relations given in Eq. I. It is then the object of this paper to discuss the general effects of cold-rolling on the true stress and strain values for a low-carbon steel together with the effects of age-hardening and directionality on these properties. Preliminary Investigations The material considered throughout the paper is a low-carbon steel of the following chemical analysis: C, 0.19 per cent; S, 0.118; P, 0.092; Mn, 0.85; Si, 0.01. The stock was received in bars, 7 by 3/4 in., and was first annealed for one hour at 1650°F. followed by a furnace cool. Photomicrographs of this material showed considerable directionality even in the annealed condition. In view of the possible effects of the nonhomogeneity and directionality in this material, it was considered important to investigate their influence on the true stress-strain diagrams. In addition, the effect of strain-aging in this steel was also made the subject of a preliminary study. Effect of Aging on True Stress-strain Properties Since a certain time element would elapse between the cold-rolling operation and the final tension tests, it was determined to investigate the aging character-

Jan 1, 1945

By William A. Mitchell

AN X-ray diffraction pattern for "calcined cold precipitated ferric oxide" is reproduced dia-grammatically along with data for other iron oxides by R. C. Mackenzie.1' This pattern, which shows spacings higher than those for any other form of iron oxide, was obtained from material prepared and photographed at several different times over a period of weeks, but later attempts to reproduce the results were unsuccessful, the pattern of hematite being obtained every time.2 In an attempt to solve this problem, the original photographs showing the strange diffraction pattern were examined and a marked similarity to the hematite pattern was noticed, suggesting that the pattern was in fact due to hematite but corresponded to a shorter wavelength of X-rays than the Cu Ka which was assumed to have .been used. The eight strongest lines were provisionally identified with the strongest hematite lines and, by means of the corresponding hematite spacings, the X-ray wavelength was calculated for each line. This gave an almost constant value, with the exception of the innermost line which was somewhat diffuse, and confirmed the presence of hematite. The value obtained, 0.703 ± 0.015Å, corresponds to the molybdenum Ka wavelength. The X-ray tube used was a four-filament demountable tube with a copper target. Other photographs, mostly of soil clays, taken during the same period gave normal patterns of Cu Ka radiation with one exception. This was a calcined soil clay with a high iron content and also showed Mo Ka lines of the hematite structure. The explanation is almost certainly that the copper target was contaminated with molybdenum, but it is not known how this occurred. Specimens of alumino-silicates gave their normal Cu Ka pattern, but as the K absorption edge of iron is a little longer than the Cu Ka wavelength, specimens with a high iron content greatly reduced the intensity of the Cu Ka diffraction lines relative to that of the lines due to the shorter Mo Ka wavelength. The formation of hematite on calcining cold precipitated hydrated ferric oxide3 is thus confirmed. References R. C. Mackenzie: Investigations on Cold-precipi-tated Hydrated Ferric Oxide and its Origin in Clays. Problems of Clay and Laterite Genesis, p. 69, Fig. 4, F. AIME Symposium, St. Louis, Mo. Feb. 19-22, 1951. Published 1952. 'R. C. Mackenzie: Ref. 1. Note added on proof. V. C. Hansen and L. T. Brownmiller: Equilibrium Studies on Alumina and Ferric Oxide and on Combinations of These with Magnesia and Calcium Oxide. American Journal of Science (1928) 5, No. 15, pp. 225-242.

Jan 1, 1954

By James Norman, O. C. Ralston, John Dasher

MOST mineral products are used in the finely divided state, but some are sold in larger sizes. Coal, gravel, metallurgical fluorspar, phosphate rock, hematite, chromite, and other products are sold in sizes coarser than can be treated by many mineral-dressing methods. Gravity separation of coarser sizes by log washing and jigging is probably as ancient as any process now in use. The performance of jigs on a feed with sufficient difference in density of the minerals is excellent, but many families of minerals are too similar in density to be separated effectively by this method. The use of heavy suspensions of fine solids to separate coarse coal from bone and slate has been in use for some years. This separation by sink-and-float was limited until recently to light minerals. Development of galena and ferrosilicon as suspension media, by Minerals Beneficiation, Inc., at Mascot, Tenn., Pitcher, Okla., and Crosby, Minn., under patents granted during and since 1938, has permitted excellent results to be obtained on minerals of very similar densities up to 3.3. This process has been put in the hands of American Cyanamid Co. for exploitation, and further research now in progress may increase the density of suspension obtainable so that separation, at a density of 4,0 may be practicable before this is published. The Huntington-Heberlein dense-medium process, developed in England, is also being commercialized in the United States by Sink and Float Corporation. Du Pont has developed a sink-and-float separation using halogenated hydrocarbons as parting liquids; at this writing, the method is used commercially only on coal but has been successful in the pilot plant on many other minerals using tetrabromethane at densities up to 2.95. While these processes were being developed to extend the range of separation by difference in density to the coarser sizes, the Bureau of Mines was engaged in developing a process that will extend the range of separation by difference in wettability up to 2-in, size. War work has pushed aside its further development indefinitely. The results are published here with the hope that some use may be suggested that will justify post-war development, and so that readers that may be able to make immediate use of the scheme may have the information. EARLIER WORK It has been known since the time of Herodotus (B.C. 484(?)-425) that water-repellent particles will adhere to sticky surfaces. That early historian reports the

Jan 1, 1942

By James Norman, O. C. Ralston, John Dasher

Most mineral products are used in the finely divided state, but some are sold in larger sizes. Coal, gravel, metallurgical fluorspar, phosphate rock, hematite, chro-mite, and other products are sold in sizes coarser than can be treated by many mineral-dressing methods. Gravity separation of coarser sizes by log washing and jigging is probably as ancient as any process now in use. The performance of jigs on a feed with sufficient difference in density of the minerals is excellent, but many families of minerals are too similar in density to be separated effectively by this method. The use of heavy suspensions of fine solids to separate coarse coal from bone and slate has been in use for some years. This separation by sink-and-float was limited until recently to light minerals. Development of galena and ferrosilicon as suspension media, by Minerals Beneficia-tion, Inc., at Mascot, Tenn., Pitcher, Okla., and Crosby, Minn., under patents granted during and since 1938, has permitted excellent results to be obtained on minerals of very similar densities up to 3.3. This process has been put In the hands of American Cyanamid Co. for exploitation, and further research now in progress may increase the density of suspension obtainable so that separations at a density of 4.0 may be practicable before this is published. The Huntington-Heberlein dense-medium process, developed in England, is also being commercialized in the United States by Sink and Float Corporation. Du Pont has developed a sink-and-float separation using halogenated hydrocarbons as parting liquids; at this writing, the method is used commercially only on coal but has been successful in the pilot plant on many other minerals using tetrabrom-ethane at densities up to 2.95. While these processes were being developed to extend the range of separation by difference in density to the coarser sizes, the Bureau of Mines was engaged in developing a process that will extend the range of separation by difference in wettability up to 2-in. size. War work has pushed aside its further development indefinitely. The results are published here with the hope that some use may be suggested that will justify post-war development, and so that readers that may be able to make immediate use of the scheme may have the information. Earlier Work It has been known since the time of Herodotus (B.C. 484(?)-425) that water-repellent particles will adhere to sticky surfaces. That early historian reports the recovery of gold from the mud of a lake

Jan 1, 1943

By James Norman, O. C. Ralston, John Dasher

Most mineral products are used in the finely divided state, but some are sold in larger sizes. Coal, gravel, metallurgical fluorspar, phosphate rock, hematite, chro-mite, and other products are sold in sizes coarser than can be treated by many mineral-dressing methods. Gravity separation of coarser sizes by log washing and jigging is probably as ancient as any process now in use. The performance of jigs on a feed with sufficient difference in density of the minerals is excellent, but many families of minerals are too similar in density to be separated effectively by this method. The use of heavy suspensions of fine solids to separate coarse coal from bone and slate has been in use for some years. This separation by sink-and-float was limited until recently to light minerals. Development of galena and ferrosilicon as suspension media, by Minerals Beneficia-tion, Inc., at Mascot, Tenn., Pitcher, Okla., and Crosby, Minn., under patents granted during and since 1938, has permitted excellent results to be obtained on minerals of very similar densities up to 3.3. This process has been put In the hands of American Cyanamid Co. for exploitation, and further research now in progress may increase the density of suspension obtainable so that separations at a density of 4.0 may be practicable before this is published. The Huntington-Heberlein dense-medium process, developed in England, is also being commercialized in the United States by Sink and Float Corporation. Du Pont has developed a sink-and-float separation using halogenated hydrocarbons as parting liquids; at this writing, the method is used commercially only on coal but has been successful in the pilot plant on many other minerals using tetrabrom-ethane at densities up to 2.95. While these processes were being developed to extend the range of separation by difference in density to the coarser sizes, the Bureau of Mines was engaged in developing a process that will extend the range of separation by difference in wettability up to 2-in. size. War work has pushed aside its further development indefinitely. The results are published here with the hope that some use may be suggested that will justify post-war development, and so that readers that may be able to make immediate use of the scheme may have the information. Earlier Work It has been known since the time of Herodotus (B.C. 484(?)-425) that water-repellent particles will adhere to sticky surfaces. That early historian reports the recovery of gold from the mud of a lake

Jan 1, 1943

By M. R. Lorenz

Efficient visible light emission from p-n junctions in semiconductors is currently achieved in the four materials, Sic, GaP, ]Ga1-xAs and GaAs1-x,. Recent advances in materials preparation and p-n junction formation are briefly reviewed. The radiative recombination processes in the different materials depend largely on the band structure and the impurity states of each material. The spectral distribution of the emission ranges from the blue in Sic, to green in Gap, yellow in Sic and red in Gap, Ga1-x AlxAs and GaAs1-x Px. The origin of the various processes are discussed. The conversion of the electrical power into optical power and the measurement of the conversion efficiency are reviewed. The currently maximum quantum efficiencies at 300°K are: 3 pct in GaP(red), 1 pct in SiC(yellow), 0.1 pct in GaP(green), 0.2 pct in Ga1-x AlxAs at 66001, and 0.1 pct in GaAs1-x Px at 6800. The brightness and the interplay of the quantum efficiency and the luminous efficiency are given detailed consideration. VISIBLE light generated by the application of a direct current to a semiconductor crystal was first observed by Lossev1 in 1923. Light emission came from naturally occurring junctions in Sic crystals but little was known then with regard to the mechanism of charge transport and light emission. Some nearly 30 years later and with a vastly increased understanding of semiconductors the phenomenon of electroluminescence was studied in more detail, for example in p-n junctions of germanium.2 In these early studies, the efficiency of converting the electron current into a photon current was very low and therefore aroused little interest toward practical application. More recently it became apparent that in certain materials, for instance GaAs, and under certain conditions, the conversion efficiency was not low at all.3 The subsequent discovery of the p-n junction laser4-6 provided the impetus for increased studies of electroluminescence. Light emitted from GaAs occurs in the infrared region of the electromagnetic spectrum and is not visible to the eye. At nearly the same time the use of GaAs1-xPx led to laser action at low temperatures which was visible to the eye.7 Later a red light emitting diode, made from Gap, was reportedS which emitted incoherent radiation at 300°K with an external quantum efficiency of about 1.5 pct. The fact that such efficient devices were obtainable led to a more concentrated effort in the search for highly efficient room-temperature semiconductor light sources. It is some of this later work on p-n junction luminescence with which we will be concerned here. Since our aim is centered on visible light, with hv =1.8 ev ( ?=7000?), only the wider band gap semiconductors are of interest, i.e., Eg 1 1.8 ev. Although many compounds meet this criterion, only a limited number of those are also good semiconductors, i.e. contain low resistance n and p regions. Some of the more promising candidates are listed in Table I. We will only be concerned with light generation from a p-n junction. This limitation excludes essentially the group II-VI binary compounds, although we will briefly review the case of ZnTe and the solid solution ZnTe1-xSex. As we will show they may contain a p-n junction but only of a special kind. Most of the discussion will deal with the four materials, Sic, Gap, Gal-xAlxAs, and GaAs1-xPx. These appear to be at the present time the best visible light emitting semiconductors. In the following sections we will briefly consider: 1) the electrical properties of p-n junctions; 2) some recent advances in materials preparation; 3) the formation of p-n junctions; and then in somewhat greater detail we will consider: 4) the various radiative recombination processes; 5) the measurement and observation of the external quantum efficiency; 6) the luminous efficiency; 7) the brightness of light emitting diodes (LED'S). THE P-N JUNCTION The p-n junction in a semiconductor crystal is the interface between two differently doped regions. More specifically the p region is doped predominantly with acceptor impurities and the n region contains predominantly donor impurities. The energy band structure of a degenerate p-n junction at thermal equilibrium is shown in Fig. l(a). The excess electrons on the n side of the junction are confined to this region by the barrier potential Eg. Similarly the excess holes on the p-side of the junction are confined to the p-region by a similar potential barrier. If we now apply a dc voltage V such that the p region is made positive and the n region negative, the barrier potential EB is reduced by the applied voltage, V and the junction is said to be forward biased. With the barrier potential lowered, electrons and holes can drift toward the p region and n region, respectively, see Fig. l(b). The current voltage characteristics of p-n junctions in most wide band gap materials can be described by the relation: J = Joexp(eV/BkT) [1] where the functional form of Jo is determined by the recombination mechanism. Jo is generally a complicated parameter which depends on a number of different factors including temperature, junction width, bias voltage, and carrier lifetimes. The parameter B also depends on the recombination mechanism but

Jan 1, 1970

By Jacques Steininger, Robert E. England

Single crystals of ZnTe and ZnTe1-,Sex with x up to 0.13 have been grown from the elements by temperature gradient solution zoning using excess tellurium as a solvent. Best results have been obtained with charges with the compositions 45/55 at. pct Zn, Te, for ZnTe and increasing amounts of selenium for ZnTe1-xSex. The temperature in the molten zone was maintained at about 1070°C with a gradient of about 10°C per cm. Chemical analyses of quenched ZnTe ingots show tellurium concentrations in the molten zone as high as 70 pct with concentration differences across the zone of 1 to 2 at. pct Dark dots which are observed by transmitted light microscopy in as-grown crystals can be removed by annealing in zinc vapor at 900 C. INTEREST in wide band gap semiconductors has led to a new study of ZnTe and ZnTel-xSex crystal growth. ZnTe is the only II-VI compound with a wide band gap (2.3 ev) that can be made p type with low resistivity. Attempts to make it n type with low enough resistivity to be useful for p-n junctions have so far been unsuccessful.1 ZnSe has a band gap of 2.65 ev but can be made n type only. However, ZnTel-xSex solid solutions with x as low as 0.36 have been made both highly n and p type2 with a minimum band gap around 2.12 ev3 at room temperature and appear to hold the best promise for efficient injection electroluminescence in the visible. ZnTe has the lowest melting point of the zinc chal-cogenides (1295°C) and consequently attempts have been made to grow crystals from both the liquid and the vapor phase.4 Complicated apparatus is required for growth from stoichiometric melts because of the high vapor pressures of the elements at the melting point of ZnTe and because of the problem of quartz devitrification. Small crystals have thus been grown in high-pressure equipment by Fischer5 and by Narita et a1.6 with pressures of the order of 50 atm of argon to prevent excessive evaporation from the melt. Large crystals of ZnTe can be obtained by growth from the vapor phase4 but they often present numerous dislocations and inclusions. An improvement in the quality of vapor- grown ZnTe crystals was reported by Albers and Aten7 by equilibration of mixtures of small crystals with compositions lying on either side of the solid single-phase field at fixed temperature. The same technique was later applied by Aten8 to the growth of ZnTe1-xSex crystals with less than 1 pct inhomo-geneity. Because of the higher liquidus temperatures of the solid solutions and the high vapor pressure of selenium, previous attempts to grow ZnTel-xSex from the melt have been limited and unsuccessful.9 The phase diagram of the Zn- Te system is reproduced in Fig. 1, based on data from Kobayashi10 and Kulwicki.11 Carides and Fishher12 have reported lower liquidus temperatures on the tellurium-rich side, but their data would require confirmation. The liquidus temperature on the tellurium-rich side decreases rapidly with increasing tellurium concentration and the Te2 vapor pressure over the liquidus also decreases accordingly.'3 The decrease in liquidus temperature and vapor pressure therefore makes it possible to use conventional apparatus if there is a sufficient excess of tellurium in the melt. Single crystals of ZnTe have thus been grown by Kucza,14 in a modified Bridgman technique, from solutions containing up to 60 at. pct of Te by lowering unsupported quartz ampoules through a temperature gradient at about 1200°C. Under these conditions, the phase diagram indicates that the entire charge is initially molten. Crystal growth can therefore proceed by normal freezing and rejection of excess tellurium into the melt. The modified Bridgman technique has several major limitations. Because of the rejection of excess tellurium into the melt during freezing, the melt composition and the temperature at the growth interface vary continuously. They tend to follow the liquidus until the eutectic which is very close to pure tellurium (447°C, >99 pct Te). Since the solidus composition also varies with temperature,15 crystals grown by this method are inhomogeneous. They present small variations from stoichiometry which may affect their structure and physical properties. The simultaneous increase in tellurium content and decrease in melt temperature also combine to reduce the rate of diffusion of tellurium away from the growth interface, thereby causing constitutional supercooling and possibly dendritic growth. To minimize these effects, the initial melt composition is in practice kept relatively close to stoichiometry (less than 60 pct Te). This however limits the possibilities of operating at low temperatures and pressures. This paper describes a modified method of crystal growth by temperature gradient solution zoning (TGSZ) which is an adaptation of the temperature gradient zone-melting technique developed by pfann16 and of the traveling solvent method of Mlavsky and weinstein.I7 The TGSZ method now applied to the growth of ZnTe and ZnTel-xSex crystals is characterized by its very simple experimental arrangement and sample preparation technique. Unlike the modified Bridgman technique, there is no increase in the tellurium concentration in the melt and therefore it is possible to operate at lower temperatures and pressures. This method is also suitable for maintaining a constant temperature at the growth interface.

Jan 1, 1969

By C. S. Smith

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers according to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Dr. Gerhard Derge; Editorial Assistant, M. A. Redmyrski; Staff Coordinator, James J. Burke. THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Post-President; John Chipman, Vice President; T. D. Jones, Treasurer; R. W. Shearman, Secretory. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. W. Thornton, Chairman- Dennis Carney John Chipman J. C. Fulton J. H. Hollomon H. H. Kellogg, A. E. Lee, R. Moddin, J. D. sullivan, and D.' Swan. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: T. B. King, Chairman; S. J. Dickenson, R. P. Hermsdorf, R. Schuhmann, Jr., and P. T. Stroup. lnstitute of Metals DM lion: Robert Maddin, Chairman. F. Lincoln Vogel, Jr.. Vice chairman. W. A. Backofen R. W. Boliuffi J. H. Bechtold' M. B. Bever R: S. Busk C 6. Goetzel poul Gordon C. D. Grobom, Jr., Robert F. Hehe-mann R. I. Joffee F. i. Joumot Jr. lrvin R. Kromer, A. J. Leno. Horold Morgolfn, C. J. McHargue, Russell A. Meussner, J. B. Newkirk, H. W. Paxton, G. E. Pellissier, I. S. Servi, Alon U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman. T. B. King, F. C. Laogenberg, W. O. Philbrook, and T. 0. Winkler. Publishod bimonthl by the American Institute of Mining Metollurgicol and Petroleum Engineers Inc., 29 West 39th Street, New York 16, N. Y. Telephone: PEonylvanie 6-9220. Subscription $20 par yew for non-AIME members in United States and North, South and Control Americo $25 foreign; $5 for AIME members. Single copies, $4.00, single copios foreign $5,00. The AIME is 1958 by the Amarican mode or opinion axpressed in it* publications ... Copyright by the Amarican lnstitute of Mining, MataIlurgicol, and Petrolum Engineers, Inc,. . . Reg. istered cable address AIME New Yark ... Indexed in Engineering Inderx, Industrial Arts ...Index and Chemicol Number5. Absrtracis . . . Second class postage paid at New York,Indor. N. Y., Industrialond Ann Arbor, Mich.

Jan 1, 1959

By Charles S. Barrett, Robert F. Mehl, Shueling Woo

WHEN one solid phase is generated from another, fixed and rational orientation relationships are observed to subsist between the parent and the new crystal. The principle has been proposed' that the relationships obtaining between the same two phases are identical whatever the type of phase change involved, or whichever of the phases may act as parent. Many types of phase changes have been studied: allotropic transformations in pure metals, precipitation from solid solutions, eutectoid decompositions, peritectic reactions, the formation of oxide layers, and others.2 Phase layers generated by diffusion of one metal into another constitute an additional type of reaction. This report provides new data on the orientation relationships occurring between , phase layers formed by diffusion, in the Cu-Zn system, § and furnishes further evidence in support of the principle. MATERIALS AND METHODS The Cu-Zn system is especially suitable for these studies since the high vapor pressure of Zn provides an opportunity readily to create one phase poorer in Zn upon a parent phase richer in Zn by removing Zn by vaporization, or to reverse this process by adding Zn from Zn vapor; e.g., the beta phase can be found as a layer upon gamma by dezincing, or gamma can be found on beta by addition of Zn from Zn vapor. Since orientation relationships are to be sought, requiring crystals large enough for orientation determinations, it is convenient to prepare single crystals or large grains of the parent phase. The samples were prepared from oxygen-free high-conductivity copper and Horse Head zinc by melting under a borax flux in a graphite crucible. Large crystals of beta brass were grown by the strain-anneal method, in plates sectioned from the cast ingots, by the following procedure. Rockwell-hardness indents were made at I cm. intervals-and with various loads, then the plates were annealed for .4 days at 700°C. in Nichrome boxes packed with beta-brass chips and graphite. Surface layers were removed by grinding and etching to a depth of about 1.0 mm., and individual grains were cut out. Crystals of alpha and gamma brass were prepared by freezing, by lowering a graphite crucible at speeds less than one inch per hour through a furnace held at a constant temperature above the melting point. Single crystals were cut out with a jeweler's saw, ground, polished and etched. Care was taken to remove cold worked layers from the finished crystals

Jan 1, 1944