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By L. E. Young

The purpose of this paper is to start a discussion on: (I) methods of supporting the immediate roof, particularly of local areas of poor roof, during the mechanical loading of coal; (2) methods of increasing the rapidity of the movement of the mining faces so that, without the use of cribs, jacks, park walls, and filling, there will be no danger to men, equipment, and working places from the subsidence of the overlying strata. In the Pittsburgh district the application of mechanical loading devices in mines working in the Pittsburgh seam has been retarded by the difficulties of holding and handling the draw slate. Normally the thickness of this slate averages about 8 in. but the hardness varies, and a cut of coal cannot always be loaded without placing posts or crossbars to support the slate. Locally, the slate may be thicker and special methods of support may be required. If crossbars are placed to hold the slate when the coal averages 5 ft. in thickness, the standard methods of transporting the coal cannot be followed, and the use of conveyors may be desirable. Very little information is available on the effect of increasing the rate of movement of advancing or retreating break lines or longwall faces. A few British publications have presented some data but all such data relate to longwall faces that have moved not more than 6 ft. a day. The most rapid rate of movemerit of longwall faces in Germany is 6 ft. per day. In the ordinary hand-loading mine in western Pennsylvania break lines on full retreat will move about 2 ft. per day. If loading machines are used under similar conditions the rate of retreat may reach 4 ft. per day. In a mine where coal is loaded by hand on conveyors three shifts per day, the rate of retreat has ranged from 11 to 16 ft. per day, with an average of 13 ft. If mobile loading machines could be used to load on conveyors on break lines, the rate of retreat should be increased substantially During 1935 and 1936, the United States Bureau of Mines, under a cooperative agreement with the Pittsburgh Coal Co., carried on studies of roof movement at Montour To. 10 mine. The work war done urider the direction of Mr. H. P. Greenwald, Supervising En neer, Experi-

Jan 1, 1938

By L. E. Young

The purpose of this paper is to start a discussion on: (I) methods of supporting the immediate roof, particularly of local areas of poor roof, during the mechanical loading of coal; (2) methods of increasing the rapidity of the movement of the mining faces so that, without the use of cribs, jacks, park walls, and filling, there will be no danger to men, equipment, and working places from the subsidence of the overlying strata. In the Pittsburgh district the application of mechanical loading devices in mines working in the Pittsburgh seam has been retarded by the difficulties of holding and handling the draw slate. Normally the thickness of this slate averages about 8 in. but the hardness varies, and a cut of coal cannot always be loaded without placing posts or crossbars to support the slate. Locally, the slate may be thicker and special methods of support may be required. If crossbars are placed to hold the slate when the coal averages 5 ft. in thickness, the standard methods of transporting the coal cannot be followed, and the use of conveyors may be desirable. Very little information is available on the effect of increasing the rate of movement of advancing or retreating break lines or longwall faces. A few British publications have presented some data but all such data relate to longwall faces that have moved not more than 6 ft. a day. The most rapid rate of movemerit of longwall faces in Germany is 6 ft. per day. In the ordinary hand-loading mine in western Pennsylvania break lines on full retreat will move about 2 ft. per day. If loading machines are used under similar conditions the rate of retreat may reach 4 ft. per day. In a mine where coal is loaded by hand on conveyors three shifts per day, the rate of retreat has ranged from 11 to 16 ft. per day, with an average of 13 ft. If mobile loading machines could be used to load on conveyors on break lines, the rate of retreat should be increased substantially During 1935 and 1936, the United States Bureau of Mines, under a cooperative agreement with the Pittsburgh Coal Co., carried on studies of roof movement at Montour To. 10 mine. The work war done urider the direction of Mr. H. P. Greenwald, Supervising En neer, Experi-

Jan 1, 1938

By G. F. Jr. Butterworth

THE metallographic structures most frequently encountered in rifle barrels, and which are illustrated by the accompanying photomicrographs, fall naturally into two groups, distinguished by the method used to produce in the stock a physical condition having the requisite properties. The first group consists 'of "rolled" barrels; that is, barrels subjected to hot working by rolling in or near the critical range. In the second group, the stock, which is smaller in diameter than the first, is upset to form the butt end and is then heat-treated by giving it a quench and a draw. These barrels will be referred to as "heat-treated" barrels. The structure of the rolled barrels resembles closely that of the same steel after annealing. There is the same network of excess ferrite outlining the grain boundaries, but the grains themselves are composed of sorbite rather than pearlite. The grain size is closely related to the rolling temperature. The critical-point curves of this grade of steel, which is approximately 0.50 to 0.60 per cent. of carbon and 1.00 to 1.30 per cent. of manganese, show a single very pronounced point between 1300° and 1350° F. (704° and 732° C.). Barrels rolled within this temperature range give an exceedingly fine grain, shown in Fig. 1. In fact, the grains may be so fine that, at a low magnification, they may be confused with the heat-treated structure discussed below, Fig. 6. A magnification of 500 diameters, however, will always resolve a rolled barrel into the characteristic structure, shown in Fig. 2. As the temperature is increased, the grains are found to be larger. If, on the other hand, the rolling temperature is below the critical range, the structure previous to rolling will not be obliterated, the only effect of rolling being to elongate the coarse sorbite grains in the direction of rolling, Fig. 3. This distortion is greatest at the muzzle. Heat-treated barrels are quenched in oil from above the critical range, which should give a martensitic structure, Fig. 4, but the presence of some troostite in the martensite is frequently noted when the quench has not been sufficiently drastic, Fig. 5. The structure brought about by the subsequent draw is not so striking, though quite as typical. It is sorbitic or sorbito-pearlitic, and under- a low magnification appears

Jan 7, 1919

By W. B. Triplett, H. I. Aaronson, G. M. Andes

A detailed morphological study has been made of the pro-eutectoid TiCr, and the eutectoid reactions in a Ti-17.42 pct Cr alloy isothermally transformed at temperatures from 775° through 5561°C. The morphologies of proeute,ctoid TiCr2 were found to be subject to description by the Dube morphological classification system. Grain boundary allotriomo.lphs are the dominant plpoeutectoid morphology throughout the temperature range investigated. lntragranular plates, and especially Widmanstatten sideplates, form only in small numbers. This morphological pattern differs markedly from that of the proeutectoid a reaction in hypoeutectoid Ti-Cr alloys (AIME Trans., 1957, vol. 209, p. 1227; 1958, vol. 212, p. 624), in which plates form prolifically throughout wide ranges of temperature. The eutectoid reaction is nonlamellar in character at 675°C. An increasingly prominent lamellar component develops at lower temperatures. The proeutectoid TiCr 2 and the eutectoid transformations have been studied metallographically in a hypereutectoid titanium-chromium alloy. This investigation was undertaken with the immediate objective of comparing these transformations with their counterparts in hypoeutectoid titanium-chromium alloys, studies of which have been recently completed.1,2 It was also intended, however, to contribute to the general literature on transformations of these types. Especially in the proeutectoid case, this literature is still sufficiently sparse to make difficult the testing of generalizations on the mechanisms of these transformations. TiCr, is the only intermetallic compound in the titanium-chromium system.3-5 The TiCr2 phase field extends to a maximum temperature of 1350°C) and encompasses the approximate composition range of 62 to 68 pct Cr at lower temperatures.3'4 At temperatures below 1000°C, TiCr2 has a MgCu,-type fcc structure, with 24 atoms comprising a unit cell.6,7 Only fragmentary observations on the morphology of proeutectoid TiCr2 have been previously reported. An observation which is of considerable importance with respect to the results obtained during the present investigation was made, however, on anisother-mally transformed alloys with high chromium (48 to 70 pct Cr) contents.3"8 Despite the occurrence of extensive impingement, it is apparent that a substantial proportion of the proeutectoid TiCr, which precipitated in these alloys grew in the form of Widmanstatten plates. Several observations have been made on the eutectoid reaction in hypereutectoid alloys during investigations of the titanium-chromium phase di-

Jan 1, 1961

By W. T. Lundy

THE forms in which sulphur is commonly found-native sulphur, sulphides of many metals and sulphates-are widely distributed throughout the world. The two first mentioned are the principal sources of sulphur. Substantial amounts of sulphur in some form are recovered from gases from industrial plants and from gases from smelters treating other minerals. In recent years, plants have been installed in the United States to recover sulphur in elemental form from sour gases."' The amount of sulphur so produced is small at the present time but undoubtedly will increase in the future. The recovery of sulphur from gases is not covered in this chapter, which is confined to: (1) native sulphur deposits of Texas and Louisiana; (2) those of Italy; (3) other scattered deposits of native sulphur; and (4) pyrites deposits found in many countries of the world.30 Sulphur, a nonmetallic element, occurs normally in well developed bipyramidal or tabular crystals of the orthorhombic system, as well as in stalactitic and earthy masses. The mineral has a distinctive yellow color, which may be dark and discolored by impurities; the streak is white; the luster is resinous; and the fracture is conchoidal to uneven. Sulphur is translucent to opaque; has a hardness of 1.5 to 2.5, a specific gravity of 2.05, and an atomic weight of 32.06.16 The molecular weight of the solid is expressed by the symbol SS and that of the liquid and vapor ranges from S2 to S8, depending on the temperature. Sulphur melts at a temperature between 2340 and 248°F, depending on its crystalline state, to a liquid of dark amber color, the boiling point of which is 832°F. The viscosity near the melting point is about that of water and increases to 50,000 times that of water at a temperature of 380°F, subsequently falling rapidly to a low figure at the boiling point. Crystallization changes slowly from rhombic to monoclinic above 205 °F and in cooling the transformation is reversed. The mineral is a very poor conductor of heat and electricity; it is insoluble in water and nearly all acids and is soluble in cold carbon bisulphide and carbon tetrachloride. It ignites in air at a temperature of 478°F, burning with a distinctive blue flame with evolution of sulphur dioxide.47

Jan 1, 1949

By Donald C. Barton

Success in the use of the Eötvös torsion balance method of mapping geologic structure depends largely on the accuracy in the interpretation of the observed results. Skill in that interpretation depends (1) on the knowledge of the types of the variation of gravity, the gradient of gravity horizontally, and of the differential curvature produced by bodies of different sizes, shapes, dimensions, and densities; (2) on the knowledge of the possible types of structural bodies which might produce the observed anomalies; (3) on the empirical knowledge gained by experience not only in the geological interpretation of torsion balance surveys, hut of interpretations of inadequate geological data; and (4) on a knowledge of the possible and probable types of geologic structures in the area of the survey. The knowledge of the anomaly which a known body will produce and conversely the knowledge of the body or bodies which will produce a known anomaly may be gained by empirical experience and by mathematical study. The knowledge gained by empirical experience is fragmentary and inexact. The geology of most structures actually is known very superficially. The surface geology may be known accurately. If the structure is petroliferous, the subsurface geology of the oil field will be known down to 3000, 4000, 5000 ft. or in a few oil fields down to 7500 ft., but the deeper geology will be unknown and the metamorphic, igneous, or massive limestone basement below the reach of the drill may contrast sharply in density with the overlying sediments. Away from the oil field, the subsurface geology is known only from scattered drill holes, which do not go to the basement. A fair but not necessarily accurate knowledge of the geology of the nonproductive area can be obtained by correlation of the wells but the degree of its accuracy in general is proportional to the density of the occurrence of the wells. The geology below the bottom of the wells however is unknown. An anomaly mapped by the torsion balance is the sum of the effects of the contrasts in mass of its whole geologic surroundings. If the dimensions of a body of abnormal density are large enough, depth or distance makes no difference in the effects on the gradient and differential curvature; and as a matter of fact, in many places, the basement and irregulari-

Jan 1, 1929

By T. N. McVay, E. E. Creitz

Rather large amounts of titanium minerals and some zircon and monazite are being recovered from dune sands about I. miles west of Jacksonville Beach, Fla. The Mining Branch of the Bureau of Mines, Southern Experiment station, has been interested in developing additional large deposits of similar sands in other areas of Florida. The results of a field study have been published1 concerning the sands occurring on Trail Ridge which runs north and south about 30 miles southwest of Jacksonville. This investigation was undertaken in order to identify the opaque titanium minerals occurring in Trail Ridge and because of the economic importance of Florida titanium minerals. Nature of the Problem The minerals present in the heavy fractions (sp gr > 2.94) of the sands are principally opaque minerals; staurolite, zircon, sillimanite, tourmaline, kyanite, rutile, a small amount of corundum, traces of the zinc spinel gahnite and garnet. Epidote, monazite, hornblende and ti-tanite are present in other dune sands but these minerals were not noted in the samples collected on Trail Ridge. All of the minerals except those which are opaque can be readily identified by the usual petrographic methods. However, Opaque minerals cannot be examined satisfactorily by transmitted light. Polished sections of the opaque-mineral grains were examined but these sections did not furnish useful information. Consequently, it was necessary to use means other than the usual petrographic methods to identify them. Previous Investigations of Heavy Minerals in Florida Sands Martens2 has described the heavy minerals in the Florida beach sands and has classified the opaque minerals as ilmenite with minor amounts of leucoxene. Miller3 studied a number of sands collected by Ross and Mertie in Florida. He states that the material from the Florida beach and dune sands that commonly has been called ilmenite has essentially the chemical composition of the material that has been called arizonite.4 The x ray diffraction patterns of several samples indicated that the supposed ilmenite is essentially amorphous, with only weak lines corresponding to ilmenite, and hence the material is unlike the type of arizonite from Arizona. Opaque Titanium Minerals Rutile is essentially titanium dioxide. However, as pointed out by Dana,5 important amounts of Fe+2 and Fe+3 as well as Cb and Ta are reported in some analyses.

Jan 1, 1949

By J.W. Halley

The effects of tin on steel have become increasingly important because of the necessity of using poorly detinned scrap, tin cans, and terne plate, in the open hearth. Since a tin can contains about 1.5 per cent tin, it would be possible to have up to 0.75 per cent tin in steel made with a 50 per cent scrap charge. In order to use tin-containing scrap, it is necessary to know the effect of tin on various grades of steel. The following investigation is by no means comprehensive but covers a number of steels in which tin content is important. Published Work A number of investigations of the effects of tin on rolling quality and physical properties have been published. It has been found that tin increases strength and hardness and reduces ductility and notched impact resistance. The decrease' in ductility and notched impact resistance becomes more marked as the carbon decreases. McKimml found no change in Olsen ductility, Kockwell hardness, yield strength, tensile strength or elongation in cold-reduced strip containing up to 0.124 per cent tin. A tin content of 0.1j per cent gave difficulties in rolling and increased the hardness but 0.21 per cent tin showed no change in properties from material containing very little tin. No explanation of this contradiction is offered. Andrew and Peile2 investigated steels containing 0.10 to 0.25 per cent carbon and up to 0.63 per cent tin. They found an increase in tensile strength of from 100 to 200 lb. per sq. in. for each 0.01 per cent tin on normalized samples. The elongation and reduction of area were decreased and the notched impact resistance was reduced markedly. Quenched and drawn samples did not show embrittling if water-quenched from the draw temperature of 1148°F. (620°C.). They could find no evidence of tin under the microscope. Whitely and Braithwaite3 investigated the effect of tin on rail steel containing 0.55 to 0.60 per cent carbon. They found that 0.08 per cent tin caused a marked decrease in elongation, notched impact resistance and the degree of bend. The tensile strength was increased in some tests and not in others. Bolsover and Barraclough4 investigated the effect of tin up to 0. 50 per cent on a 0.35 per cent carbon steel and on several alloy steels with from 0.30 to 0.40 per cent carbon. They found a comparatively uniform decrease in notched impact resistance with increasing tin on quenched and drawn samples. If the samples were quenched from the drawing temperature or reheated to the drawing temperature and quenched, the embrittling was much less severe. Steels containing molybdenum suffered much less embrittlement than other steels. Experimental WoRk Effect of Tin on Low-carbon Rimmed Steel Increasing quantities of tin were added to four ingots of a heat of the following ladle analysis: carbon, 0.08 per cent; manganese, 0.39; phosphorus, 0.009; sulphur, 0.025.

Jan 1, 1943

By J. W. Halley

The effects of tin on steel have become increasingly important because of the necessity of using poorly detinned scrap, tin cans, and terne plate, in the open hearth. Since a tin can contains about 1.5 per cent tin, it would be possible to have up to 0.75 per cent tin in steel made with a 50 per cent scrap charge. In order to use tin-containing scrap, it is necessary to know the effect of tin on various grades of steel. The following investigation is by no means comprehensive but covers a number of steels in which tin content is important. Published Work A number of investigations of the effects of tin on rolling quality and physical properties have been published. It has been found that tin increases strength and hardness and reduces ductility and notched impact resistance. The decrease' in ductility and notched impact resistance becomes more marked as the carbon decreases. McKimml found no change in Olsen ductility, Kockwell hardness, yield strength, tensile strength or elongation in cold-reduced strip containing up to 0.124 per cent tin. A tin content of 0.1j per cent gave difficulties in rolling and increased the hardness but 0.21 per cent tin showed no change in properties from material containing very little tin. No explanation of this contradiction is offered. Andrew and Peile2 investigated steels containing 0.10 to 0.25 per cent carbon and up to 0.63 per cent tin. They found an increase in tensile strength of from 100 to 200 lb. per sq. in. for each 0.01 per cent tin on normalized samples. The elongation and reduction of area were decreased and the notched impact resistance was reduced markedly. Quenched and drawn samples did not show embrittling if water-quenched from the draw temperature of 1148°F. (620°C.). They could find no evidence of tin under the microscope. Whitely and Braithwaite3 investigated the effect of tin on rail steel containing 0.55 to 0.60 per cent carbon. They found that 0.08 per cent tin caused a marked decrease in elongation, notched impact resistance and the degree of bend. The tensile strength was increased in some tests and not in others. Bolsover and Barraclough4 investigated the effect of tin up to 0. 50 per cent on a 0.35 per cent carbon steel and on several alloy steels with from 0.30 to 0.40 per cent carbon. They found a comparatively uniform decrease in notched impact resistance with increasing tin on quenched and drawn samples. If the samples were quenched from the drawing temperature or reheated to the drawing temperature and quenched, the embrittling was much less severe. Steels containing molybdenum suffered much less embrittlement than other steels. Experimental WoRk Effect of Tin on Low-carbon Rimmed Steel Increasing quantities of tin were added to four ingots of a heat of the following ladle analysis: carbon, 0.08 per cent; manganese, 0.39; phosphorus, 0.009; sulphur, 0.025.

Jan 1, 1943

By T. L. Joseph

Blast furnaces are most efficient thermally when the CO2 in the top gas is highest. Oxygen introduced in the air blast is converted to CO in the combustion zones. The extent to which CO, generated in front of the tuyeres, is converted later to CO2 depends upon the ratio of ore to coke in the charge and the degree to which CO2, formed by reduction of iron oxides with CO, reverts to CO by the secondary reaction C + CO2 = 2CO. About 300 to 400 lb. of carbon' per ton of pig iron is normally involved in the solution-loss reaction or direct reduction of FeO with carbon, which produces the same over-all results; that is, lower CO2 in the top gas. Rich2 has recently reported a reduction in fuel consumption at slower rates of blowing on two furnaces in spite of higher heat losses per ton of iron. Lower fuel consumption at slow operating rates was due to more complete reduction of the ore that resulted in higher CO2 in the top gas and consequently more efficient use of carbon. Kinney3 has reported substantial savings in fuel as a result of crushing and sizing the ore charge. Improvements in practice brought about by sintering magnetite concentrates, flue dust and fine ores have been due to the establishment of conditions favoring more complete reduction of the ore in the upper part of the furnace. The extent to which oxides and fluctuations in composition in pig iron affect the quality of steel and finished product needs further study. There is evidence that more thorough preheating and reduction of the ore in the upper part of the furnace tend to give a better quality of iron. Bogatzkii4 found from laboratory work that the amount of oxygen entering electrolytic iron, melted under various slags, was directly proportional to the concentration of free FeO in the slag and inversely proportional to the basicity of the slag. Herty and Gaines5 concluded that the silicate content of open-hearth steel before deoxidation is related to the concentration of silica in the pig-iron charge, indicating that most of the persistent inclusions are silica from the iron. They also found that

Jan 1, 1936

By T. L. Joseph

Blast furnaces are most efficient thermally when the CO2 in the top gas is highest. Oxygen introduced in the air blast is converted to CO in the combustion zones. The extent to which CO, generated in front of the tuyeres, is converted later to CO2 depends upon the ratio of ore to coke in the charge and the degree to which CO2, formed by reduction of iron oxides with CO, reverts to CO by the secondary reaction C + CO2 = 2CO. About 300 to 400 lb. of carbon' per ton of pig iron is normally involved in the solution-loss reaction or direct reduction of FeO with carbon, which produces the same over-all results; that is, lower CO2 in the top gas. Rich2 has recently reported a reduction in fuel consumption at slower rates of blowing on two furnaces in spite of higher heat losses per ton of iron. Lower fuel consumption at slow operating rates was due to more complete reduction of the ore that resulted in higher CO2 in the top gas and consequently more efficient use of carbon. Kinney3 has reported substantial savings in fuel as a result of crushing and sizing the ore charge. Improvements in practice brought about by sintering magnetite concentrates, flue dust and fine ores have been due to the establishment of conditions favoring more complete reduction of the ore in the upper part of the furnace. The extent to which oxides and fluctuations in composition in pig iron affect the quality of steel and finished product needs further study. There is evidence that more thorough preheating and reduction of the ore in the upper part of the furnace tend to give a better quality of iron. Bogatzkii4 found from laboratory work that the amount of oxygen entering electrolytic iron, melted under various slags, was directly proportional to the concentration of free FeO in the slag and inversely proportional to the basicity of the slag. Herty and Gaines5 concluded that the silicate content of open-hearth steel before deoxidation is related to the concentration of silica in the pig-iron charge, indicating that most of the persistent inclusions are silica from the iron. They also found that

Jan 1, 1936

By MAGNE MORTENSON

IN laboratory work and industrial tests it is important to set forth the results of research, clearly. This is generally achieved by means of some form of diagram or graphical illustration. The most common form for such graphs of flotation research is a simple chart with two curves for percentage and recovery of the concentrate. This may be quite useful, especially for minerals which may be floated: by means of one reagent in variable and another in constant amounts. If both reagents are used in variable quantities the process may be illustrated by means of several diagrams, .keeping one reagent constant in each series of tests. A more useful form of diagram for a. system with two variable - components (reagents) may be established by drawing a chart with the weights of the two reagents as .abscissas and ordinates. Every test is marked down -in the diagram with an indication of the extraction and concentration gained. In this diagram there are drawn lines for equi-extraction and equi-concentration of the mineral that is floated out in the - concentrate. The contour of these lines gives a relatively clear impression of the conditions for flotation by means of .the chemicals used. The best conditions are of course found in diagrams where the 'areas for maximum extraction and high conntration are coincident

Jan 1, 1931

By F. A. Forward, A. H. Ross, J. Halpern

IN treating carnotite ores by carbonate leaching it is often necessary to subject the ore to a prior roast. Among the advantages that may result from roasting are: 1) improvement in settling and filtering characteristics of the ore; 2) destruction of carbonaceous impurities that would otherwise contaminate the leach solution and consume carbonate reagent; and 3) substantial increase in extraction of vanadium, which is usually low when the un-roasted ore is leached. Recovery of vanadium may be an important factor in processing carnotite ores, and the fact that vanadium is usually recovered in good yield by acid leaching has often been an economic advantage over results obtained with carbonate leaching. It has been found that response of an ore to carbonate leaching, following roasting, depends primarily on its composition and on the conditions of the prior roast treatment, particularly with regard to the roasting temperature, the atmosphere maintained above the charge during roasting and cooling, and the presence of certain reagents. These factors, especially the last, virtually determine the extractions of uranium and vanadium attainable by carbonate leaching, as well as the reagent consumption on leaching, whereas adjustment of the leaching conditions has only a limited influence. These variables were examined systematically to elucidate roasting and carbonate leaching of carnotite ores and to establish a treatment yielding high recoveries of both uranium and vanadium. Tests were conducted on samples of four different Colorado Plateau ores, described in Table I. Roasting Procedure: The roasting tests were conducted in an electrically heated furnace in which the temperature was controlled to +15oC. The ore (usually a 500-g charge) was ground to —100 mesh, mixed with the desired reagent, and spread in a silica tray to a bed depth of about 1/2 in. During the roast the charge was rabbled at intervals of 15 min. To provide free access of air the furnace was usually ventilated; however, in a few experiments a controlled atmosphere such as carbon dioxide or hydrogen was maintained above the charge. Leaching Procedure: The pulp, generally comprising 500 g of ore and a 2000-cc solution containing 80 g per liter of Na2CO3 and 20 g per liter of NaHCO3, was agitated in an autoclave at 120°C, under 30 psi O2. Samples were withdrawn periodically, and the solution and ore residue were analyzed. Under the conditions employed, maximum attainable extractions were generally achieved in 4

Jan 1, 1958

By T. N. McVay, E. E. Creitz

INTRODUCTION Object RATHER large amounts of titanium minerals and some zircon and monazite are being recovered from dune sands about 10 miles west of Jacksonville Beach, Fla. The Mining Branch of the Bureau of Mines, Southern Experiment Station, has been interested in developing additional large deposits of similar sands in other areas of Florida. The results of a field study have been published1 concerning the sands occurring on Trail Ridge which runs north and south about 30 miles southwest of Jacksonville. This investigation was undertaken in order to identify the opaque titanium minerals occurring in Trail Ridge and because of the economic importance of Florida titanium minerals. Nature of the Problem The minerals present in the heavy fractions (sp gr > 2.94) of the sands are principally opaque minerals; staurolite, zircon, sillimanite, tourmaline, kyanite, rutile, a small amount of corundum, traces of the zinc spinel gahnite and garnet. Epidote, monazite, hornblende and titanite are present in other dune sands but these minerals were not noted in the samples collected on Trail Ridge. All of the minerals except those which are opaque can be readily identified by the usual petrographic methods. However, opaque minerals cannot be examined satisfactorily by transmitted light. Polished sections of the opaque-mineral grains were examined but these sections did not furnish useful information. Consequently, it was necessary to use means other than the usual petrographic methods to identify them. Previous Investigations of Heavy Minerals in Florida Sands Martens2 has described the heavy minerals in the Florida beach sands and has classified the opaque minerals as ilmenite with minor amounts of leucoxene. Miller3 studied a number of sands collected by Ross and Mertie in Florida. He states that the material from the Florida beach and dune sands that commonly has been called ilmenite has essentially the chemical composition of the material that has been called arizonite.4 The X ray diffraction patterns of several samples indicated that the supposed ilmenite is essentially amorphous, with only weak lines corresponding to ilmenite, and hence the material is unlike the type of arizonite from Arizona. Opaque Titanium Minerals Rutile is essentially titanium dioxide. However, as pointed out by Dana,5 important amounts of Fee and Fe3 as well as Cb and Ta are reported in some analyses.

Jan 1, 1947

By H. H. Klepfer, M. E. Snyder

UNTIL very recently, the commercial availability of the rare earths as metals has been very limited. Fabrication of mill products from these metals has not been studied in most cases. This note reports the results of the development of fabrication techniques for thulium. Thulium has a melting point of about 1550°C and a hexagonal close-packed crystal structure. It oxidizes in air to give a black oxide (TmzO,). The procedures for producing thin thulium foil were developed on one ingot weighing about 220 g and were subsequently applied in processing about a pound of metal to foil. Several alternates for the various fabrication steps were investigated and will be discussed. The metal fabricated was in the form of commercial chill-cast ingots 1 in. in diam and 2 in. long weighing approximately 220 g. Impurities in the ingots were reported by the vendor to be 4000 ppni tantalum, 2000 ppm calcium, 200 ppm nickel, 100 to 200 ppm iron, 100 ppm europium, and less than 100 ppm copper, lutetium, and ytterbium. In addition to these impurities, several salt-like inclusions as large as l/8 in. in diam were revealed along the center line of the one ingot sectioned. Preliminary tests indicated that small wafers cut from the as-cast ingot would not fabricate readily by rolling. Forging of copper-jacketed wafers was therefore attempted. At 1550"F forging was satisfactory but an apparent reaction of copper with thulium demanded investigation of lower temperatures. Therefore, the remainder of the test ingot was forged at 1450°F—with only minor cracking. All ingots forged were inserted into copper tubes of 1 in. 1D and 0.125-in. wall thickness. The jackets were sealed by flattening the ends of the tubes and welding under helium. Heating time at 1450°F was 30 min. Press forgings of 1/8 in. per pass were used, followed by 10 min reheats. When the ingots had been squared and reduced to 0.250 in. in thickness, the original copper jacket was stripped off and replaced by a new jacket in preparation for hot rolling. Hot rolling at 1450" F without edge cracking was readily accomplished after forging. Excellent results were obtained with 10 pct reductions of thickness followed by 5 to 10 min reheats. After reduction of thickness from 0.250 to 0.100 in. the copper jacket was removed. It was found, in fact, that hot rolling in air was possible. A tenacious black oxide similar to that seen on zirconium was formed during 3 min reheats at 1450°F. Reduction in air to 0.010 in. foil was possible taking 10 pct reductions per pass. The oxide coat formed during hot rolling in air could best be removed by sand blasting and pickling. Common pickling solutions containing polar solvents were found to attack the metal too rapidly and a concentrated nitric-hydrofluoric acid mixture attacked neither the oxide nor the metal. The most satisfactory pickling solution was 52 vol pct concentrated nitric acid-48 vol pct glacial acetic acid. After forging to 0.250 in., vacuum annealing and cold rolling was found to be another satisfactory alternate to hot rolling in copper jackets. After forging. a hardness of Rockwell B76 was found. Annealing in vacuum (2 X l0-5 mm of Hg) for 1 hr at 1200"F did not alter this value. Annealing at 1470"F for 1 hr brought the hardness down to R;]63. With cold rolling (5 pct per pass) the hardness returned to about R,1:76 after 20 pct reduction and edge cracking became noticeable. However, cold rolling to a total of 40 pct reduction in thickness (RI,,83) was possible before edge crack propagation became serious. Good surface finish was obtained, and the metal loss due to oxidation was minimized by cold rolling and vacuum annealing. Using this procedure the yield of 1.25 in. wide by 0.010 in. thick foil from a 1-in. diam ingot was about 40 pct.

Jan 1, 1961

By J. W. Halley

THE effects of tin on steel have become increasingly important because of the necessity of using poorly detinned scrap, tin cans, and terne plate, in the open hearth. Since a tin can contains about 1.5 per cent tin, it would be possible to have up to 0.75 per cent tin in steel made with a 50 per cent scrap charge. In order to use tin-containing scrap, it is necessary to know the effect of tin on various grades of steel. The following investigation is by no means comprehensive but covers a number of steels in which tin content is important. PUBLISHED WORK A number of investigations of the effects of tin on rolling quality and physical properties have been published. It has been found that tin increases strength and hardness and reduces ductility and notched impact resistance. The decrease in ductility and notched impact resistance becomes more marked as the carbon decreases. McKimm1 found no change in Olsen ductility, Rockwell hardness, yield strength, tensile strength or elongation in cold-reduced strip containing up to 0.124 per cent tin. A tin content of 0.15 per cent gave difficulties in rolling and increased the hardness but 0.21 per cent tin showed no change in properties from material containing very little tin. No explanation of this contradiction is offered. Andrew and Peile2 investigated steels containing 0.01 to 0.25 per cent carbon and up to 0.63 per cent tin. They found an increase in tensile strength of from 100 to 200 lb. per sq. in. for each 0.01 per cent tin on normalized samples. The elongation and reduction of area were decreased and the notched impact resistance was reduced markedly. Quenched and drawn samples did not show embrittling if water-quenched from the draw temperature of 1148°F. (620°C.). They could find no evidence of tin under the microscope. Whitely and Braithwaite3 investigated the effect of tin on rail steel containing 0.55 to 0.06 per cent carbon. They found that 0.08 per cent tin caused a marked decrease in elongation, notched impact resistance and the degree of bend. The tensile strength was increased in some tests and not in others. Bolsover and Barraclough4 investigated the effect of tin up to 0.50 per cent on a 0.35 per cent carbon steel and on several alloy steels with from 0.30 to 0.40 per cent carbon. They found a comparatively uniform decrease in notched impact resistance with increasing tin on quenched and drawn samples. If the samples were quenched from the drawing temperature or reheated to the drawing temperature and quenched, the embrittling was much less severe. Steels containing molybdenum suffered much less embrittlement than other steels. EXPERIMENTAL WORK Effect of Tin on Low-carbon Rimmed Steel Increasing quantities of tin were added to four ingots of a heat of the following ladle analysis: carbon, 0.08 per cent; manganese, 0.39; phosphorus, 0.009; sulphur, 0.025.

Jan 1, 1942

By A. R. Calawa, T. C. Harman, M. Finn, P. Youtz

A study has been made of the growing, annealing, and diffusion parameters in PbSe, Pb1-ySnySe, and Pb1-xSnxTe. Single crystals of these materials have been grown using the Bridgman technique. For all of the above materials the as-grown crystals are p type with high carrier densities. To reduce the carrier concentration and increase the carrier mobility, the samples are annealed either isothermally or by a two-zone method. From isothermal anneals, the liquidus-solidus boundary on the metal-rich side of the stoichiometric composition has been obtained for some alloys of Pb1-xSnxTe and on both the metal- and seleniunz-rich sides for PbSe and alloys of Pbl-ySnySe. In Pbo.935 Sno.065 Se carrier concentrations as low as 5 x1016 Cm-3 and mobilities as high as 44,000 sq cm v-1 sec-1 at 77°K have been obtained. Inter diffusion parameters mere also studied. The ddiffusion experiments mere identical to the isothermal or two-zone annealing experiments except that the samples were removed prior to complete equilibration. The resulting p-n junction depths were determined by sectioning and thermal probing. Inter diffusion coefficients for various temperatures were calculated for both PbSe and Pb0.93Sn0.0,Se. RECENTLY, there has been considerable interest in the PbTe-SnTe and PbSe-SnSe alloys with the rock salt crystal structure. The unusual feature of these systems is the variation of energy gap EG with composition. Several investigations1-3 have shown that EG for the lead chalcogenides decreases as the tin content increases, goes through zero, and then increases again with further increase in tin content. The possibility of obtaining an arbitrary energy gap by selecting the composition is an especially attractive feature of these alloys for applications involving long-wavelength infrared detectors and lasers. In addition, some unusual magneto-optical, galvanomagnetic, and thermomag-netic effects should occur for alloys with low band gaps. If uncompensated low carrier density crystals can be obtained, then a small carrier effective mass, a large dielectric constant, and the resultant high carrier mobility should yield enormous effects at low temperature in a magnetic field. The relative variation of the energy gap with pressure should also be very large for these low gap materials. The primary purpose of this paper is to provide some information concerning the preparation of low carrier concentra- tion, high carrier mobility, and homogeneous single crystals with a predetermined alloy composition. I) DETERMINATION OF ALLOY COMPOSITIONS In all of the work described in this paper, the composition of lead and tin chalcogenides in the alloys was determined by electron microprobe analysis. Separate X-ray spectrometers are used to make simultaneous intensity measurements of the Pb La1 and Sn La1 lines emitted by the sample under excitation by a beam of 25 kev electrons focused to a spot about 2 µm in diam. These intensities are compared to the intensities of the same lines emitted by standards under the same conditions. The standards used are the terminal compounds of each pseudobinary system, i.e., PbTe and SnTe for Pbl-xSnxTe alloys, PbSe and SnSe for Pbl-ySnySe alloys. The composition of the sample is then obtained from theoretical calibration curves which relate the weight fractions of lead and tin in the alloy to the measured ratios of X-ray intensities for the sample and the standards. The lead and tin calibration curves for each alloy system were calculated by using corrections for backscattered electrons,4 ionization,5 and absorption,6 and assuming that the atom fraction of tellurium or selenium in the sample and standards is exactly +. Results obtained by using the microprobe are in good agreement with those obtained by wet chemical analysis. II) CRYSTAL GROWTH FROM THE VAPOR Early work on the vapor growth of PbSe was carried out by Prior.7 He used small chips of Bridgman-grown single crystals as the source material and frequently converted the whole charge of a few grams into one crystal. In the present work, vapor growth occurred using a metal-rich or chalcogenide-rich two-phased alloy powder as the source material. Small, nearly stoichiometric crystals are formed on the walls of the quartz tube. The procedure will now be described in detail. Initially, a 100-g charge containing (metal)o.51(chalco-genide)o 49 proportions or (metal)o.49(chalcogenide)o. 51 proportions of the as-received elements in chunk form are placed in a fused silica ampoule. After the ampoule is loaded, it is evacuated with a diffusion pump and sealed. The sealed ampoule is placed in the center of a vertical resistance furnace. The region containing the ampoule is heated to about 50°C above the liquidus temper-ature for the particular composition used. After about one-half hour at temperature, the elements are reacted and the molten material homogenized. The ampoule is quenched in water. The quenched ingot is crushed to a coarse powder for vapor growth experiments and to a fine powder for the isothermal annealing experiments which are discussed in a later section. Vapor growth experiments were carried out using the powdered, metal-rich or chalcogenide-rich alloys

Jan 1, 1969

By Donald Warren, J. F. Libsch

HIS investigation originated as a result of a pre-vious experimental study' of the magnetic properties of Fe-Co alloys fabricated by the powder metallurgy technique. Densities of powder compacts prepared for the magnetics investigation varied from 7.45 to 7.70 g per cu cm or from 93 to 95 pct of the experimental value of 8.08 g per cu cm for a fused alloy of the same composition.' While this range of density is considered sufficiently high for most applications, the highest possible density is to be desired for maximum magnetic properties. By applying a technique similar to the one described above to a pure electrolytic iron powder, Rostoker³ was able to achieve a density of 7.895 g per cu cm, which is the highest density ever reported for sintered iron. While Rostoker's work involved the sintering of an elemental powder rather than a mixture, it was believed that higher densities should also have been obtained for alloys using the above technique because of the recoining operation and the high sintering temperature. Consequently, it was decided to investigate the various factors affecting the density of this alloy with the idea that such a study might lead to higher densities and, as a result, powder alloys having magnetic properties identical with those of the fused alloys. It was believed that the principal reason that near-theoretical densities for the powdered alloy were not obtained was the interference of gases with the normal sintering mechanism. When present during the sintering operation, gases can exert several harmful effects: they can remain on the particle surface and interfere with surface diffusion and plastic flow; they can be released and, under certain conditions, expand the void spaces through gas pressure; or they can remain trapped in the pores and exert a hydrostatic pressure that retards elimination of the pores. Jones,4 Rhines,5 Goetzel," and others have given the effect of gases in the sintering of powder compacts an extensive treatment. Among the more important sources of gases in the sintering process are dissolved gases, adsorbed gases, air entrapped during pressing, and gaseous products of chemical reactions. During sintering adsorbed gases are partly released at a relatively low temperature, while those gases entrapped during pressing cannot escape until their pressure is increased sufficiently through increasing temperature to expand the interpartjcle openings. The remaining adsorbed gases, gaseous reduction products, and dissolved gases produce a similar effect at the higher temperatures. If, in the sintering process, gas evolution occurs after the interpore channels have been sealed, an exaggerated expansion of the void spaces results. This is particularly true if the temperature is high enough for extensive plastic flow. In his fabrication of powder bars from tantalum, Balke7 had to consider the effect of adsorbed hydrogen and provide for its escape during sintering by limiting the compacting pressure to a maximum of 50 tons per sq in. The effect of gases entrapped during pressing was first noted by Trzebiatowski8 when he found that gold and silver powders decrease in density with increasing sintering temperature if pressed at 200 tsi, while they exhibit the usual increase when pressed at 40 tsi. Recent investigators9-11 have also noted that entrapped gases have an effect on the expansion of copper compacts during sintering. Proper provision for the escape of gaseous products of reduction must be made in order to avoid deleterious effects. Myers" states that in the sintering of electrolytic tantalum powder, the temperature was gradually raised to 2600°F with a pause at 2000°F to permit reduction of the oxides. Experimental Details For the present study, 50 pct Co-50 pct Fe compacts in the form of circular disks 1½ in. in diam and 0.15 in. thick were fabricated by the pressing and sintering of a mixture of the elemental powders. It was decided to follow the sintering process by means of liquid permeability measurements, because it was thought that such measurements might serve as a measure of relative pore sizes, as well as a possible indication of the point at which most of the interpore channels become sealed. However, since the permeability as measured by the flow of a liquid, such as ethylene glycol, does not give an absolute indication of the point where the pores have become isolated, a method for determining the percentage of pores connected to the surface was set up. As an additional cross check on the permeability measurements, metallographic methods were used to study the relative pore size. Finally, the property of ultimate interest, the density, was measured. Raw Materials: The powders used consisted of an annealed, 99.9 pct pure, —150 mesh grade of electrolytic iron powder, and a 98 pct pure, —200 mesh grade of reduced and comminuted cobalt powder. The cobalt powder was not further processed either by hydrogen reduction or annealing. The screen analyses for the iron and cobalt powders are given in Table I, while the chemical analyses for each type of powder are listed in Table 11. Table 111 gives the hydrogen loss measurements for the powders according to the M.P.A. Standard Method and for a higher temperature as well. Preparation of Compacts: Equal amounts of the elemental powders were mixed by rotation for 1 hr and then pressed into compacts approximately 0.15

Jan 1, 1952

By C. C. Clark, J. S. Iwanski

The purpose of this investigation was to study mi-crostructural changes that take place in a commercial nickel-chromium-iron alloy, such as Incoloy "901," over long periods of time at temperatures up to 13 50°F and to correlate such changes with creep-rupture properties. of the alloy. In the course of the investigation, some microstructural changes were observed which correspond to microstructural alterations found in previous studies of Inconel "X." Microstructural phases have been identified in both alloys with the aid of electron and X-ray diffraction and an electron probe microanalyzer. The materials used in this investigation were from commercial heats of the following chemical composition: Pct Cr Pct Ni Pct Mo Pct Fe Pct Cb Incoloy "901" 12.51 43.67 5.72 Bal. -Inconel "X" 14.61 73.44 - 6.61 1.02 Pct A1 Pct Ti Pct Mn Pct Si Pct C Incoloy "901" 0.10 2.46 0.46 0.24 0.05 Inconel "X" 0.70 2.43 0.51 0.36 0.04 Long-term creep-rupture tests were conducted on Incoloy "901" at temperatures of 1000°, 1200°1 and 1350°F. A summary of these results is shown in Table I along with the results of a long-term creep-rupture test conducted on Inconel "X" at 1500°F. The heat treatments given the specimens are also shown in Table I. When the creep-rupture results on Incoloy "901" are compared with shorter-tertn data, there is no evidence of any undue deterioration of the creep-rupture strength with time, nor is the elongation decreased more than would be expected from the influence of time alone. INCOLOY "901" PHASE IDENTIFICATION Microscopic examination of the Incoloy "901" specimens reveals a dark etching grain boundary constituent in the specimen which was under test for about 11,500 hr at 1000°F. This grain boundary constituent was seen to increase in size as the test temperature was increased to 1200" and 1350°F, Figs. 1, 2, and 3. Simultaneously, an acicular structure of definite crystallographic orientation appears within the grains of the 1350°F specimen, Fig. 3. Under examination with the electron microscope, a fine precipitate is observed in the 1200 °F specimen. Fig. 4. It becomes considerably larger in the 2850-hr 1350°F specimen, Fig. 5. In a few areas the precipitated particles have been replaced by, or transformed to, small needles or platelets. After 7380 hr at 1350°F, Figs. 3 and 6, the needles are much larger and have replaced nearly all of the fine precipitate. X-ray diffraction studies detected the presence of hexagonal Laves phase and hexagonal n phase (Ni,Ti) in the 1350°F specimens, Table 11. Only the Laves phase was detected by X-ray diffraction in the 1200°F specimen and none was detected in the 1000°F specimen. In this latter specimen, however, the small quantity of precipitate in the grain boundaries (presumed to be Laves phase) precludes its detection by X-ray diffraction. Composition of the hexagonal Laves phase is not yet known, although its diffraction

Jan 1, 1960

By R. C. Amero

FULLERS earth is a general name applied to claylike minerals that have high natural ad-sorptive powers. They are usually distinguished from ordinary clays by a higher content of combined moisture and a lower apparent density. The definition is based on the ancient use of the material for fulling, or cleansing woolen cloth of oil and grease; a more modern definition should mention the ability to decolorize oil and should differentiate between fullers earth, which is naturally active, and certain bentonites which only develop decolorizing power after being leached with strong mineral acids. The distinction between fullers earth and activable bentonite is not a sharp one, since all types of intermediate clays can be found that are more or less naturally active, yet more or less responsive to acid treatment. The differences seem to depend somewhat on the amount of leaching that has been effected by natural ground waters. Physical Properties The principal mineral constituent of activable bentonite is montmorillonite, a hydrous aluminum silicate to which the following formula is generally assigned: Al,Si,O,, (OH), • 12H,O Fullers earth, as well as bentonite, is usually composed of some variety of montmorillonite, but in the United States the largest tonnage of fullers earth is mined from deposits of attapulgite. Attapul- gite is a clay mineral composed of monoclinic crystals of colloidal size, having a fibrous shape similar to that of asbestos. A sectional model of the attapulgite "molecule" is shown in Fig. 1. A single unit is about 18.0 A wide and 12.9 A high. The length of the molecule is variable, but this same molecular pattern is repeated to form needlework crystals, rather than flakes, as is characteristic of the montmorillonite crystals. Attapulgite has been assigned the following formula,' although actually, the magnesia has been largely replaced by alumina: (0%) . (OH), • Mg, . Si, • Olp . 4H20. The fibrous nature of the mineral is clearly shown in the electron micrograph, Fig. 2. Although the deposits contain 5 to 30 pct quartz and carbonate minerals, impurities in the commercial products are held at a low level, principally by selective mining on the basis of oil decolorizing efficiency. The particle size distribution of this fullers earth has been estimated from settling rates, using sodium citrate as a dispersing agent.' Since Stokes' law only applies to spherical particles, the equivalent particle diameter calculated below is probably more nearly an index of diameter rather than length of the needlelike crystals: Eqnivalent Arbitrary Particle Distribution, Size Diameter Pci Classil3catian 0.05 mm 0.80 0.80 pct sand 0.05-0.02 mm 10.96 0.02-0.01 mm 9.65 42.10 pct silt 0.01-0.005 mm 11.40 0.005-0.002 mm 10.09 2-0.5 micron 10.61 0.5-0.2 micron 29.09 56.58 pct clay 0.2-0.05 micron 14.86 0.05 micron 1.96 The differential thermal analysis shown in Fig. 3 is unique and supports the theory that this is a distinct mineral species.' ~ Other general properties of the mineral as shown in Table I.

Jan 1, 1952