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By M. Marciano, K. Kreider

Silicon carbide coated boron fiber (Borsic) reinforced aluminum composites were made which exhibit strength and modulus values predicted by the rule of mixtures. A successful technique for fabricating these composites consists of plasma spraying of monolayer filament reinforced tapes and subsequent diffusion bonding of these tapes into composites. The elastic properties of the composites were given by the rule of mixtures in reinforced directions. (The modulus parallel to the fibers was 32 x 106 psi for a composite with 50 pct by volume fibers. The other elastic properties for a composite with 50 pct fiber were transverse modulus = 14 to 16 X 10 psi, G = 9.5 x 106psi, and v,, = 0.23. Tensile strengths of over 190,000 psi were measured for the composites with 50 pct fiber and the average strength for these composites was 162,000 psi. These same composites had interlaminar shear strengths of 12 to 15,000 psi. Multidirectionally reinforced composites demonstrated the same reinforcement efficiency in strength and modulus as the uni-directimlly reinforced composites. Comrpessive strengths of composites with 50 pct by volume fiber were found to be greater than 250,000 psi. STRUCTURAL filamentary composite materials are being considered for use where high strength, high modulus, and lightweight materials are required. Metal matrix composites have been considered for use at temperatures ranging from cryogenic (aluminum stainless steel) to 6000°F (plasma sprayed tungsten plus tungsten fiber) and other requirements have been similarly diverse. Metal matrix composites offer high modulus and high strength in unreinforced directions, the ability to be joined by brazing or welding, and greater fracture toughness compared with the more easily fabricated resin matrix composites. This paper deals with the mechanical properties of aluminum boron composites, a system which is being considered for applications where lightweight, high modulus, and high strength are required at temperatures including those above the normal operating temperatures of resin composites. The boron fiber used in this investigation had an average room temperature strength of greater than 400,000 psi, a modulus of 58 x 106 psi, and a density of 0.09 lb per cu in. (2.6 g per cu cm).' The fiber used in the composites had a coating of silicon carbide to retard degrading reactions with the matrix at elevated temperatures. The coated fiber, which is sold commercially as Borsic: has been reported to have excellent resistance to degradation at temperatures up to 600°C in air and in aluminum2 and the same mechanical properties as the standard bare boron fiber. Fabrication of Composites. The composites were diffusion bonded from plasma sprayed monolayer tapes. These tapes were fabricated on a substrate of aluminum alloy foil which is incorporated in the composite matrix. The technique consists of winding a layer of fiber on the foil, and plasma spraying the balance of the matrix alloy over the windings which bonds all of the components together. Advantages of this process include the ability to achieve good fiber spacing, Fig. 1, the formation of a good bond between fiber and matrix (achieved during the plasma spraying), and the adaptability of the process for forming large and complex parts. This is particularly true when used with brazing foil backing which alloys low pressure bonding of the structural shape. PROPERTY EVALUATION TECHNIQUES Tensile test specimens, 5 to 7 in. long with a reduced gage section and ,030 to ,040 in. thick, were cut from composite sheets with a diamond saw. The gage section was .200 in. wide, while the gripped section was .240 in. wide and over 2 in. long in each grip. The standard gage length used was 1 in., however, transverse specimens (i.e., specimens with the fibers oriented 90 deg to the loading axis) were tested without a reduced section. Twelve specimens were also made with a 3-in. gage length but no significant effect of gage length was measured. The tensile test specimens were mounted in a fixture and aligned in friction grips using a 10X microscope. Unbonded foil doublers (0.010-in.-thick aluminum) were used to insure firm gripping with a minimum of damage to the fibers. The test specimens were transferred to the testing machine in a rigid fixture and mounted in the self aligning loading train. Testing was performed using a Tinius Olsen four screw testing machine with a torsion bar LVDT load

Jan 1, 1970

By Charles S. Barrett, Robert F. Mehl

A study of the structures arising from the decomposition of the ß solid solutions in the Cu-Zn and the Cu-A1 systems is of peculiar interest in the study of the mechanism of precipitation from solid solutions. It is possible in these alloys, by varying the composition within the ß field, to precipitate from the same basic lattice phases having different lattice structures. It has been rather generally assumed heretofore that the type of structure originating from the decomposition of a solid solution— the Widmanstätten structure—-is determined by the lattice structure of the parent solid solution alone. In the first paper of this series1 evidence was advanced which threw doubt upon this hypothesis; but definite proof of the correctness or incorrectness of the hypothesis should be forthcoming from a study of these alloys, for if the structures originating, for example, from the precipitation of the a phase from ß and of the ? phase from the ß in the Cu-Zn system should be shown to be crystallographically different, the hypothesis would necessarily be held as definitely disproved. Furthermore, the newer proposal enunciated in the first paper of this series—that the origin of the Widmanstätten structure lies in a cooperation between the lattice of the parent solid solution and that of the precipitate-—which at present seems the only a1ternative hypothesis, would in such an event be given added weight. The work here reported shows that the Widmanstätten structures originating in the precipitation of the a phase from the ß and in the precipit'at.ion of the y phase from the y in the Cu-Zn system are indeed crystallographically different; and incidentally presents some new descriptive information on the Widmanstätten structure from a more general point, of view.

Jan 1, 1931

By G. V. Woody, J. D. Price

Many producers of by-product coke have spent considerable time and given considerable thought to the use of a substitute for low-volatile coal as an admixture with high-volatile coking coal for charging high-temperature by-product coke ovens. Generally speaking, there are two principal reasons for this, one being occasioned by the lack, in certain localities, of low-volatile coal delivered at a cost sufficiently low to permit its use, and another being the desirability of finding a substitute product with a delivered cost lower than the cost of the low-volatile coal. It was for the first of these reasons that the Colorado Fuel and Iron Corporation was particularly interested in this subject. This paper deals with the experimental work and the results obtained by that company in producing and using low-temperature char. Overcoming Defects in Coke from Colorado Coals Colorado coking coals are all of the high-volatile type and were all laid down during the Cretaceous period, which makes them something like 80 million or so years younger, geologically, than eastern coals. They behave, when coked alone, something like the Pittsburgh-seam coals. They make a very brittle, highly cross-fractured, fingery coke of fair shatter value but quite low in resistance to abrasion. Mixed with a low-volatile coking coal such as Poca- hontas or certain Oklahoma coals, they make a coke that is equal to virtually any of the eastern cokes. The inferior quality of Colorado coke has long been recognized, and a considerable amount of time, effort and money has been spent upon investigations of means for improving its physical properties. While it has been found that some improvement in quality of coke can be secured by the adjustment and control of such variables as pulverization, moisture content, oven temperature and bulk density of charge, and through the addition of certain inert materials such as pulverized coke breeze, pitch, high-volatile noncoking or semicoking coal, the benefits so gained have been comparatively small. There are no low or medium-volatile coking coals available within a reasonable freight-cost distance. Therefore a substitute for low-vol-atile coal was developed through low-tem-perature carbonization—or, more correctly speaking, through the partial devolatiliza-tion—of high-volatile coals. The blending of this lower volatile char with the high-volatile coking coal distinctly improves the quality of coke made from Colorado coal. There is nothing especially new about this idea. In 1908 a Japanese patent was taken out by Kotaro Shimomura, whose claim was: The method of making a nonfingery coke out of bituminous coals, without using natural coals of low-volatile matter; according to which a certain coal is heated at a temperature between about 300°C. and about 600°C. so as to leave about 15 to 25 per cent volatile matter in the coal; this coal is mixed with the

Jan 1, 1944

By J. D. Price, G. V. Woody

Many producers of by-product coke have spent considerable time and given considerable thought to the use of a substitute for low-volatile coal as an admixture with high-volatile coking coal for charging high-temperature by-product coke ovens. Generally speaking, there are two principal reasons for this, one being occasioned by the lack, in certain localities, of low-volatile coal delivered at a cost sufficiently low to permit its use, and another being the desirability of finding a substitute product with a delivered cost lower than the cost of the low-volatile coal. It was for the first of these reasons that the Colorado Fuel and Iron Corporation was particularly interested in this subject. This paper deals with the experimental work and the results obtained by that company in producing and using low-temperature char. Overcoming Defects in Coke from Colorado Coals Colorado coking coals are all of the high-volatile type and were all laid down during the Cretaceous period, which makes them something like 80 million or so years younger, geologically, than eastern coals. They behave, when coked alone, something like the Pittsburgh-seam coals. They make a very brittle, highly cross-fractured, fingery coke of fair shatter value but quite low in resistance to abrasion. Mixed with a low-volatile coking coal such as Poca- hontas or certain Oklahoma coals, they make a coke that is equal to virtually any of the eastern cokes. The inferior quality of Colorado coke has long been recognized, and a considerable amount of time, effort and money has been spent upon investigations of means for improving its physical properties. While it has been found that some improvement in quality of coke can be secured by the adjustment and control of such variables as pulverization, moisture content, oven temperature and bulk density of charge, and through the addition of certain inert materials such as pulverized coke breeze, pitch, high-volatile noncoking or semicoking coal, the benefits so gained have been comparatively small. There are no low or medium-volatile coking coals available within a reasonable freight-cost distance. Therefore a substitute for low-vol-atile coal was developed through low-tem-perature carbonization—or, more correctly speaking, through the partial devolatiliza-tion—of high-volatile coals. The blending of this lower volatile char with the high-volatile coking coal distinctly improves the quality of coke made from Colorado coal. There is nothing especially new about this idea. In 1908 a Japanese patent was taken out by Kotaro Shimomura, whose claim was: The method of making a nonfingery coke out of bituminous coals, without using natural coals of low-volatile matter; according to which a certain coal is heated at a temperature between about 300°C. and about 600°C. so as to leave about 15 to 25 per cent volatile matter in the coal; this coal is mixed with the

Jan 1, 1944

By J. D. Price, G. V. Woody

MANY producers of by-product coke have spent considerable time and given considerable thought to the use of a substitute for low-volatile coal as an admixture with high-volatile coking coal for charging high-temperature by-product coke ovens. Generally speaking, there are two principal reasons for this, one being occasioned by the lack, in certain localities, of low-volatile coal delivered at a cost sufficiently low to permit its use, and another being the desirability of finding a substitute product with a delivered cost lower than the cost of the low-volatile coal. It was for the first of these reasons that the Colorado Fuel and Iron Corporation was particularly interested in this subject. This paper deals with the experimental work and the results obtained by that company in producing and using low-temperature char. OVERCOMING DEFECTS IN COKE FROM COLORADO COALS Colorado coking coals are all of the high-volatile type and were all laid down during he Cretaceous period, which makes them something like 80 million or so years younger, geologically, than eastern coals. They behave, when coked alone, something like the Pittsburgh-seam coals. They make a very brittle, highly cross-fractured, fingery coke of fair shatter value but quite low in resistance to abrasion. Mixed with a low-volatile coking coal such as Pocahontas or certain Oklahoma coals, they make a coke that is equal to virtually any of the eastern cokes. The inferior quality of Colorado coke has long been recognized, and a considerable amount of time, effort and money has been spent upon investigations of means for improving its physical properties. While it has been found that some improvement in quality of coke can be secured by the adjustment and control of such variables as pulverization, moisture content, oven temperature and bulk density of charge, and through the addition of certain inert materials such as pulverized coke breeze, pitch, high-volatile noncoking or semicoking coal, the benefits so gained have been comparatively small. There are no low or medium-volatile coking coals available within a reasonable freight-cost distance. Therefore a substitute for low-volatile coal was developed through low-temperature carbonization-or, more correctly speaking, through the partial devolatilization-of high-volatile coals. The blending of this lower volatile char with the high-volatile coking coal distinctly improves the quality of coke made from Colorado coal. There is nothing especially new about this idea. In 1908 a Japanese patent was taken out by Kotaro Shimomura, whose claim was: The method of making a nonfingery coke out of bituminous coals, without using natural coals of low-volatile matter; according to which a certain coal is heated at a temperature between about 300°C. and about 600°C. so as to leave about 15 to 25 per cent volatile matter in the coal; this coal is mixed with the

Jan 1, 1944

By Earl S. Bardwell

The determination of suitable and safe annealing temperatures is one of the most important problems arising in the operation of a copper rolling mill. Certain of the larger mills have worked this problem out for themselves and in these mills the operation has become more or less standardized. In some of the mills pyrometers are used to measure the temperature of the annealing furnaces and careful watch is kept to see that overheating does not take place. In a considerable number of the mills, however, dependence is placed entirely on the judgment of the operator. The almost total lack of literature bearing on this subject seems sufficient warrant for the publication of this paper. ' The discussion of this subject naturally divides itself into two parts: (1) The effect of annealing temperature on physical properties; and (2) changes in the microstructure of refined copper due to cold rolling and annealing. I. The Effect of Annealing Temperature on Physical Properties For the purpose of investigating this phase of the subject six test bars were selected, varying in oxygen content between the limits of 0.036 and 0.070 per cent. The chemical composition of each of these test bars was as follows: Bar Number 1 2 3 4 5 6 Copper + silver...... 99.95 99.92 99.945 99.94 99.95 99.93 Oxygen.............. 0.041 0.070 0.046 0.050 0.036 0.058 As + Sb............. 0.0038 0.0038 0.0038 0.0038 0.0031 0.0031 The bars were heated in an electric muffle to about 1,650" F. and rolled into rods. The rods were annealed, pickled, and drawn to No. 12 B. & S. gauge wire. The wire which was to be used for the annealing test was cut into 38-in. lengths and each length made into a coil 6 in. in diameter. The separate coils were marked so that they might readily be identified

Jan 1, 1915

By M. von Heimendahl, G. Thomas

The microstructure of TD-Ni has been examined by transmission electron microscopy in the extruded, annealed. and deformed states. The tensile properties hove been correlated with the observed microstructures and the results ore com-pared with those obtained from pure nickel. The important conclusions are that the thorin particles in TD-Ni act as strong burriers to dislocntion motion during both deformation (slip) and annealing (climb). During deformation. the dislocations tangle around the particles and a cell structure is devleloped after 10 pct or more strain. The cell size appears to be determined by the spacing of the largest particles and is about five times smaller than that in pure nickel for the same strain. The higher work-hardening rate in TD-Ni compared to nickel is probably due to the more rapid rate of dislocation multiplication in the alloy as a result of dislocation-particle interactions. The Th0,particles inhibit recrystallization and twin growh so that some strengthening may arise from the high density of small annealing twins. THE strengthening of materials due to the presence of a dispersed second phase has been the subject of considerable experimental and theoretical investigation in recent years. One of the newest dispersion-strengthened alloys to be developed is TD-Ni,1 a system of approximately 2 vol pct thoria (ThO2) dispersed in a matrix of commercially pure nickel. This material is fabricated by powder-metallurgical techniques and offers high-temperature stability and useful mechanical properties virtually to the melting point of the base metal. While the mechanical properties of this system have been investigated,2,3 there have been no reports in the literature concerning the microstruc-ture of TD-Ni and its correlation to mechanical properties. This paper describes a transmission electron microscopy investigation of the micro-structure of TD-Ni together with its mechanical properties. The results are compared with the structure and properties of pure nickel.

Jan 1, 1964

By W. E. Gaby

INTRODUCTION SINCE the time of their discovery, the genesis of the ores at Mount Morgan, and the nature of the changes which have affected the surrounding rocks, have been the subject of investigation and speculation by geologists and mining engineers. Developments at this mine, for a long period the greatest gold producer of the world, show that with depth the orebody grades into copper, of which metal it now furnishes a large output, exceeding in value the gold. In earlier times, the purity of the gold and the first extremely heterogeneous character of the ore made it an interesting problem. Now, the probable depth of the copper enrichment, genesis, and true relations of the neighboring rocks furnish equally profitable material for investigation, and the present somewhat detailed description of these ores and rocks, from microscopic study, may prove of interest. The mine occupies a highly silicified portion of a belt of quartz-porphyry, which is believed to be the oldest rock of the region. This belt of quartz-porphyry and allied rocks runs north and south between two areas of a later intrusive granite, as shown on the geologic map,1 Fig. 1. Near the orebody the quartz-porphyry has been intruded by a dense basaltic mass called the "Old Basic." Cutting all three of these igneous masses are two sets of basaltic dikes, one running northwest-southeast, and the other, cross dikes, northeast-southwest. These dikes may be contemporaneous with, instead of later than, the ore. Their number has caused peculiar difficulties in extracting it, as the clay selvage of decomposed material affords no adhesion between dike and ore, causing great blocks to loosen and come down.

Jan 9, 1916

By William E. Ford, Edward Salisbury Dana

5. Crystallography. - The subject of Crystallography includes the description of the characters of crystals in general; of the various forms of crystals and their division into classes and systems; of the methods of studying crystals, including the determination of the mathematical relations of their faces, and the measurement of the angles between them; finally, a description of compound or twin crystals, of irregularities in crystals, of crystal- line aggregates, and of pseudomorphous crystals. 6. Definition of a Crystal.- A crystal * is the regular polyhedral form, bounded by smooth surfaces, which is assumed by a chemical compound, under the action of its intermolecular forces, when passing, under suitable conditions, from the state of a liquid or gas to that of a solid. As expressed in the foregoing definition, a crystal is characterized, first, by its definite internal molecular structure, and, second, by its external form. A crystal is the normal form of a mineral species, as of all solid chemical com- pounds; but the conditions suitable for the formation of a crystal of ideal perfection in symmetry of form and smoothness of surface are never fully realized. Further, many species usually occur not in distinct crystals, but in massive form, and in some exceptional cases the definite molecular structure is absent. 7. Molecular Structure in General.- By definite molecular structure is meant the special arrangement which the physical units, called molecules, assume under the action of the forces exerted between them during the formation of the solid. Some remarks are given in a later article (p. 22 et seq.) in regard to the kinds of molecular arrangement theoretically possible, and their relation to the symmetry of the different systems and classes of crystals.

Jan 1, 1922

[NORTH AMERICA UNITED STATES ALABAMA AUBURN Sturm & O'Brien, Consult. Engrs. °Sturm, Rolland G. BESSEMER Granger, W. C. BIRMINGHAM Air Reduction Sales Crockett, John M. Amer. Cast Iron Pipe Co. Carter, Sam F., Jr. Donoho, C. K. Anderson Elec. Corp. Davis, Moss V. J. B. Clow & Sons Neptune, Maurice D. Connors Steel Div. °Sandelin, Robert W. Hayes Aircraft Corp. Ricketts, W. E., Jr. Willhelm, A. Clyde, Jr. McWaine Cast Iron King, O. H. Worthington, B. W. Shook & Fletcher Sup. Co. Gearhart, Thomas A. Southern Res. Inst. Dismukes, Edward B., Wheelahan, Edmund J. Thomas Foys Miller, Ralph M. Union Carbide Metals, Co. Brandler, Edgar A. U. S. Pipe & Fdry. Co. Clay, Donald H. Unaffiliated Berg, H. A. Caldwell, H. A. Gilmer, H. U. Harris, Thomas H. Templeton, J. B.]

Jan 1, 1961

By F. N. Rhines, A. H. Grobe

At elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible1 and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscaleiormation) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detai1.5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the 1-6 and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 40 alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. Experimental Procedure Silver.—The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By A. H. Grobe, F. N. Rhines

At elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible1 and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscaleiormation) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detai1.5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the 1-6 and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 40 alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. Experimental Procedure Silver.—The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By Pual M. Tyler

BLIZKRIEG tactics in the present war have consumed metals on such a profligate scale that some of the best-laid procurement plans for civilian and military needs of even a year ago seem in retrospect incredibly meager. Conservation of raw materials has reached an all-time climax in Germany, where metals are worth more than human life and throwing away an empty toothpaste tube may be legally punished by death. Even the United States and the British Empire, proud masters of nine tenths of the world?s known mineral reserves and processing plants, are being driven to metals and feverishly expanding production facilities that not long ago were deemed overbuilt. After the war is over and inevitable postwar readjustments are completed, it is reasonable to expect that purchasing power ? or at least the ability to procure the comforts and luxuries of life ? will be distributed among vastly larger population than ever before, accelerating the rising trend in demand for industrial raw materials in ever greater quantity and variety.

Jan 1, 1942

By H. W. Gillett

CLYDE WILLIAMS has reminded me that in the fall of 1929, gave, in MINING AND METALLURGY, an account of the hopes and aspirations of Battelle Memorial Institute, which was then just swinging into initial operation; and that therein I remarked that B.M.I. should stand, as well, for Better Metallurgical Industries, since helping to better them was the Institute's aim. So he has suggested that some of the betterments of the past fifteen years might well be listed. A yearly summary of progress comes pretty close to the ultimate in futility, for everything proved of value in that year had its inception in earlier years, and everything really new has still to be proved. Plenty of things hailed as wonderful achievements for that year, by some enthusiasts invited to contribute to the summary, turn out in later years to be inglorious flops. But over a decade and a half, betterments that are really such become self-evident, and recounting some of them can be done without guesswork or wishful thinking. An inventory of what was known and utilized in 1929 compared to what is now known and used is not too hard to make. Perhaps the most clear-cut picture of what is known and used at a certain date is drawn by the handbooks, textbooks, and equipment catalogs of that date, with scientific periodical literature forecasting what knowledge may later be used when it is verified and assimilated. The tools available for production or for research limit the application of old and the finding of new knowledge.

Jan 1, 1945

By J. N. Maycock, P. W. M. Jacobs

Previous measurements of the thermoelectric power of ionic crystals are reviewed briefly. It is concluded that, while extensive measurerements are available on systems in which the electrode M has a cation in cornon with the sall MX, there is as yet little modern work on systems in which the metal electrode M' does not haue a calion in common with the salt. We haue now measured the thermoelectric power of- single cryslals of KC1 and of KC1 + SrCl2 between plati.nu?n electrodes over a much wider range of temperature than before. individual ionic heats of transport, which, while probably not very accurate, are of a reasonable order of magnitude, are obtained from this data on the basis of an assumption that charge carriers do not cross the electrode/salt interface. RELATIVELY little work has been done on thermal diffusion in ionic crystals. Reinhold and coworkers1-I measured the thermoelectric power and Soret effect in silver and cuprous salts and their mixed crystals. One electrode was kept at constant temperature and electromotive force was measured as a function of the temperature gradient. This is not a satisfactory technique if the results are to be compared with theory; rather should the electromotive force be measured for small temperature differences as a function of the mean temperature of the two electrodes. They used electrodes having the same cation as the salt. Patrick and Lawsons measured the thermoelectric power of AgBr and of AgBr containing 0.25 mole pct CdBr2 using silver electrodes and temperature gradients of 10°C in the temperature range 100° to 400°C. The results were analyzed using the Teltow9 values of the ratio of the mobility of the two types of charge carrier (cation vacancies and interstitials) found from conductance measurements and the wagnerlo estimate of the heterogeneous contribution to the thermopower, Ohet They obtained values of qi = 0.017 ev and q$ = -0.385 ev for the heats of transport of interstitial Ag ions and cation vacancies, respectively. Their data has been reanalyzed by Haga using the corrections to the Wagner formula for ehet given by Howard andLidiard; Haga found ev. Christy et a1.14 have measured the thermopower of AgBr containing 0.01 to 1.0 mole pct CdBr,. They analyzed their results in terms of the theory of Howard and Lidiard and found that excellent agreement with the theory was obtained if q5 + : + hF was set equal to 0.70 ev at 175°C and equal to 0.58 ev at 250°C. Since Teltow's value for hF, the enthalpy of formation of a Frenkel defect pair, is 1.27 ev, this means that qt + q: increases in magnitude from -0.57 ev at 175°C to -0.69 ev at 250°C. This result is in poor agreement with Patrick and Lawson's value of -0.37 ev for pure AgBr (for which the corrections to the Wagner estimate for ehet are very small). christy1' has also reported thermopower measurements for pure silver halides and for the systems he finds that qr + qt for AgBr increases in magnitude from about -0.55 ev at 150°C to about -1.1 ev at 400°C. The temperature dependence of the sum of the heats of transport in AgCl is very similar in magnitude. The sum qi + q cannot be decomposed into the individual interstitial and vacancy heats of transport without a knowledge of the entropy contribution from the change in the lattice vibrational frequencies around the interstitial and vacancy. Despite this it seems an inescapable conclusion from Christy's analysis that and -6 = Q Ag are quite strongly temperature-de pendent and that -q: is much greater in magnitude than the corresponding activation energy for vacancy migration, +0.37 ev. It remains a mystery as to why the data for pure AgBr are fitted so well by the assumption of temperature-independent heats of transport if association of impurity ions and vacancies is neglected.l The values for q$ and q: so obtained are also much more in line with those expected from a simple kinetic interpretation of the heats of transport due to wirtz.17 Christy and Hsueh have also measured the thermopower of CuCl between copper electrodes; 0 for pure CuCl is comparable with that for the silver halides but, owing to the limited solubility of divalent cation impurities it was not found possible to deduce values for the heats of transport. In contrast to these extensive measurements on cells of the type M MX 1 M, there have been relatively few attempts to measure the thermoelectric power of cells of the form M' 1 MX I M'. (We specifically exclude from discussion cells of this type in which the metal electrodes M' are in contact with gas containing a controlled partial pressure of either M or X,, since in these cells the electrochemical reactions are analogous to those of the first type.) The thermoelectric power of Pb12, PbC12, TlC1, TlBr, TlI, NaNO3, and KNO 3 between platinum electrodes was measured by Thie1e.l3 In discussing these measurements Holtan20 asserts that the thermopotential initially fluctuated wildly and even changed sign before approaching a steady value. A high degree of irreproducibility is also evident in the work of Nikitinskaya and Murin21 who first studied the thermopower of NaCl and KC1 between platinum electrodes. Much better reproduci-bility was achieved in our earlier measurements on KC1;22 these were, however, confined to a relatively narrow temperature range and one of the objects of the work reported in this paper was to extend the temperature range of the measurements of the thermoelectric power 8 of KC1. The only other published

Jan 1, 1967

By J. L. Rodda, R. L. Wilcox, E. C. Truesdale

In recent years various problems in connection with research work on the preparation and properties of zinc-base alloys have required reliable information concerning the constitution of the zinc-rich portion of the iron-zinc equilibrium diagram. On numerous occasions rather positive indications were obtained that, for example, the solubility of iron in zinc was incorrectly represented on the current equilibrium diagrams. A careful study of all the available literature relating to the iron-zinc system led to the conclusion that much of the early work was unsatisfactory as measured by present standards of experimental accuracy, and as a result it was decided to redetermine the location of the liquidus curve and of adjacent portions of the diagram. Part I of this paper comprises a description of the experimental methods and a summary of the results by means of which the zinc-rich end of- the iron-zinc diagram has been revised in the following ways: 1. Measurements of the solubility of iron in liquid zinc by several different sampling methods, leading to a relocation of the liquidus curve. 2. Microscopic, conductivity, and X-ray studies of the solid solubility of iron in zinc, which, together with thermal analyses, have resulted in new values for the solid solubility and the eutectic temperature and composition. 3. Heating and cooling curves, obtained by a refined differential method, leading to new locations for the two peritectic horizontals. In Part I1 of the paper the attempt is made to review all of the published work having a bearing on the constitution of the iron-zinc system, and to correlate the present results, and some recently published data involving the use of X-ray technique, with the earlier work, much of which was done from 25 to 30 years ago.

Jan 1, 1936

By Joseph C. McCaskill

The writer assumes that this volume is not intended to serve as a source of statistics on international trade and that the reader is not interested in wading through a lot of statistical tables copied from the various reporting agencies. Generalizations therefore are made whenever possible and not always is the source of the information meticulously cited. The United Nations regularly publishes trade data on mineral commodities. E. J. Gealy, and C. L Kimbell, of the U S Bureau of Mines (USBM), work with these data and estimate that they cover approximately 78% of total mineral commodities traded. In addition the General Agreement on Tariffs and Trade (GATT) publishes analyses of certain trade data The most complete report of production and trade in minerals 1s probably the international volume of the U.S. Bureau of Mines Yearbook The latest available edition is for 1968, and some of the data in this edition cover only as late as 1967. Unless otherwise stated, the source of data used in the chapter is this Yearbook Other staff members of the Bureau were most helpful and cooperative They are not to be held responsible for conclusions or points of view to be found in the chapter. THE NATURE AND SCOPE OF INTERNATIONAL TRADE The two and a half decades since World War II have witnessed an unprecedented growth international commerce The end of the war found the world economy seriously crippled. Many countries had suffered severe war damage; international trade was disrupted and nations had to resort to exchange controls and bilateral trading arrangements. The postwar recovery, however, was remarkably rapid Within two decades, world Income more than doubled, and world trade which was less than $60 billion in 1948 exceeded $200 billion in 1968, 8 and reached $278 billion in 1970.18 The growing world trade contributed to world prosperity which in turn fostered growth of trade. This dramatic growth of international commerce was made possible by the progressive liberalization of trade and capital movements by the major trading nations of the world which began immediately after the War and has not yet completely lost its steam. The modern-day stimulus of the expanded trade movement was the enactment by the Congress of the United States in 1934, of the

Jan 1, 1976

By Kenneth S. Ritchie

The natural emulsion samples used in this study were shipped directly from twelve California oil fields, through the courtesy of the superintendents of the main producing companies in those fields. Representative parts of each sample were chosen for the slides. Preparation of the slides was generally made in less than two minutes, including time of exposure; in a few cases, about five minutes was required. The short time was intended to minirmize the changes in conditions. Whenever comparison was of value, standard conditions were established. Spreading by gravity was adopted instead of smearing. Cover glasses were not allowed to rest on the films. General Characteristics of Emulsions The main purpose of the general views (Figs. 1-16) is to illustrate the general characteristics of the dispersed droplets together with any other constituent or impurity that may be found in each emulsion. The magnification is given so that dimensions could be measured from the plates. The slides used for these views had spherical recesses; they gave the best light. Where crystals were intended to be shown in the picture a filter (green was the best') was usually used. Emulsions that showed a tendency to move by concentrated light were pictured without a condenser.

Jan 1, 1931

By K. M. Kolobova, E. Z. Kurmayev, A. Z. Menshikov, S. A. Nemnonov, V. A. Trapeznikov

The present work represents a review of our intestigations into the X-ray spectra of solids, which have been carried out by us along two lines of upproach: 1) St@ of the electronic structure of high -rnelting compounds of transition metals; 2) stzddy of the interatomic binding forces by the fine structure of absorption spectra under varying temperature and concentration conditions. With this in mind, int>estigations hare been made into the emission and absorption spectra of the K-series of atoms of transition elements in alloys and compounds. In the problem concerned with the electronic structure of high-melting compounds of transition metals, considerable importance is attached to the question of ascertaining the role played by 3d4sp electrons of metal and 2p electrons of metalloid in the formation of chemical bonds and of giving, on the strength of this data, an explanation of the properties which seem to be contradictory at first sight: good conductivity inherent in metals and high brittleness and high-melting characteristics typical of covalent compounds. Over the last few decades this question has attracted the attention of many investigators whose studies were devoted to this type of compound. Many works, both of theoretical1-3 and experimental4- l5 nature , have contributed much to the elucidation of the physical character of the phenomenon referred to. Alongside the investigations in the field of electric resistance, Hall effect, paramagnetic susceptibility, electronic heat capacity, and the temperature of transformation into a superconducting state, we should particularly emphasize the studies on X-ray spectra, which have played a significant role in the development of the zonal theory for high-melting compounds. This fact has become highly evident after the theoretical calculation of the energy spectrum has been made and the density of states curve in Tic, TiN, and Ti0 has been plotted by Ern and Switendick3 who used the method of augmented plane waves. Correlation of the results of the theoretical calculation of the band structure in the compounds listed above with the data obtained by X-ray spectroscopy studies showed that X-ray spectra can be a source of valuable information on the electronic structure of high-melting compounds within a wide range of ener- gies. It is well known that X-ray emission spectra basically give a direct picture of the occupied excited states above the Fermi level of a solid (valence band, conduction band) and that the absorption spectra (region of initial absorption) give a similar picture of states corresponding to the unoccupied levels near the Fermi surface. Full information on the density distribution of electronic states by energies can be obtained by combining the emission and absorption spectra. Such an opportunity arises from investigation

Jan 1, 1970

By P. A. C. Wilson

Instantaneous outbursts of carbon dioxide in coal mines have occurred in Germany only in one part of the Waldenburg-Neurode mining district.' This mining region comprises the northeastern fold of the "Innersudetian" coal basin. The basin (Fig. 1) is in the form of a geologic trough approximately 60 km. (37 miles) long and 30 to 35 km. (19 to 22 miles) broad and is enclosed on three sides by ancient truncated mountain ranges—the Riesengebirge, the Bober-Katzbachgebirge and the Eulenge-birge. Only the southeastern part of the trough is not enclosed by mountains of older rock formation. The floor of the basin before the building up of the coal measures was formed on the western, northwestern and northeastern borders by the material from Archean rocks (gneiss and mica schists); in the northern part over this was deposited the Silurian formation. The carboniferous period is represented both by the Lower ("kulm") and Upper Carboniferous, with an unconformity between the stages; that is, the kulm was tilted up and partly eroded before the Upper Carboniferous was deposited. The kulm is a salt-water formation (with marine fauna) but Upper Carboniferous rocks are nonsaline water deposits, with fresh-water flora only. The Lower Silesian coal measures were thus formed in a lime basin fed by the running water coming down from the mountains. As already indicated, the bottom series of the Upper Carboniferous formation, termed "Waldenburg strata" were laid down unconformably on the Lower Carboniferous. Over the Waldenburg strata there are the "Weisstein strata," an intermediate barren stage without coal beds, 400 to 500 m. (1300 to 1600 ft.) thick. Another unconformity followed, which is overlain by the '(Saarbrucken" series, which contain the upper coal measures, and the ('Ottweil" strata. In the last named, it is only on the southwestern fold that beds of coal are developed.

Jan 1, 1931