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By L. F. Mondolfo, F. A. Crossley

The mechanism of grain refinement by the addition of small amounts of titanium, molybdenum, zirconium, tungsten, and chromium to aluminum was investigated. The results indicate that the grain refinement is caused by the peritectic reaction which, by transforming the intermetallic compound into crystals of aluminum solid solution, seeds the melt with nuclei above the freezing point of aluminum. THE feasibility of reducing the grain size of aluminum alloy castings by the addition of small amounts of titanium, zirconium, molybdenum, tungsten, columbium, boron, and chromium has been known for a long time, and the use of some of these elements as grain refiners is common practice in the aluminum foundry industry. The purpose of the present investigation was to determine the mechanism by which these additions produce the grain refinement. Asato et al., on the basis of extensive work on copper, antimony, and silver alloys, presented a theory of grain refinement based on the occurrence of the peritectic reaction. Briefly, this theory states that during cooling of the melt crystals of the primary phase form, which react peritectically with the liquid upon further cooling. The peritectic reaction transforms at least partially the primary crystals into crystals of the secondary phase, which then act as nuclei for solidification of the remaining melt. As the peritectic reaction takes place the primary crys- tals break in pieces, and each piece acts as a nucleus. Fine dendritic crystals which can easily break are the most effective for grain refinement. Sicha and Boehm," in investigating the refining effect of titanium on an AI-Cu alloy, concluded that TiA1, crystals serve as nuclei to initiate crystallization, but did not offer further information on the mechanism of refinement. Bonsack in the discussion of their paper suggested that refinement was due to clouds of some solid in the melt, probably TiO² which hindered grain growth. Eborall,' after studying the effect of titanium, zirconium, vanadium, tungsten, columbium, chromium, and boron on some alloys, concluded that the peritectic reaction was not an essential feature of grain refinement. Her conclusion was based mainly upon the observation that under her experimental conditions (sand casting) the Al-Cr alloys, which undergo a peritectic reaction, did not show appreciable refinement. Cibula" investigated the mechanism of grain refinement and reported that two types of grain refinement exist: 1—Grain refinement produced by restriction of grain growth by the concentration gradient mechanism proposed by Northcott.' 2— Grain refinement produced by the presence of particles in the melt, upon which the melt crystallizes easily. He further concluded that very marked grain refinement results from a combination of the two mechanisms. Since Tic was found present in aluminum alloys refined by the addition of titanium, it was identified as the nucleating agent. In the case

Jan 1, 1952

By H. C. Spaulding

The rapid increase, during the last few years, in the number and magnitude of applications of electric power-transmission to commer cial uses in this country, has been due principally to three causes: first, the ability and enterprise of those who have been identified with the progress of electrical industries, since electric illumination became an economic fact instead of a laboratory-experiment: sec ondly, the readiness of the American people to adopt new and ad vanced methods as soon as their superiority has been fairly demon strated; and thirdly, tile economy and flexibility of the apparatus employed, when properly designed and constructed, and installed under suitable conditions. Basing our judgment on the world's advance in scientific devel opments during the past century, we may reasonably conclude that in no other country would the pioneeis of electrical invention, whose names have now become household words, have received the prompt and plentiful financial support which has enabled them to inaugurate undertakings of exceptional magnitude, even in this era of tremendous monetary organizations. And, on the other hand, we have seen, in the numerous financial and engineering failures inseparable from such rapid development, the natural results of a too implicit faith in electrical omnipotence. It is not to be wondered at that conservative engineers have been slow to adopt this new and mighty agent in the solution of exten sive problems, and under circumstances where a single failure means not only a greater or less financial sacrifice, but the loss, in a greater or less degree, of professional reputation. Be mechanical engineer, while recognizing the fact that thousands of horse-power are to-day transmitted by electrical means, from sunning the lathe in a dentist's office to the operation of a fifty-ton travelling crane; from passing a cooling draught of air through a

Jan 1, 1891

By W. L. Fink, L. A. Willey

This paper is the nineteenth of a series from the Aluminum Research Laboratories, presenting the results of the investigations of equilibrium relations in aluminum-base alloys made from electrolytically refined aluminum. In previous papers equilibrium relations have been determined and correlated for 12 binary systems. Equilibrium relations have also been determined for portions of the aluminum corners of three ternary systems (aluminum-iron-silicon, aluminum-magnesium-silicon and aluminum-copper-magnesium). The object of the present paper and those to follow is to increase our knowledge of the aluminum corner of the more important ternary systems. In 1926 Dix and Keith † suggested a new method for designating the phases encountered in alloy systems. The system has been used to a very limited extentl,2,3 The system has since been slightly modified and will be used in this and future papers. In the system as modified, a phase is designated by placing in parentheses the chemical symbols of the elements essential to the formation of that phase. The symbols in the parentheses are separated by dashes in order to clearly distinguish them from a chemical formula. Elements that are not necessary to the formation of the phase in question, but which may be present in solid solution, are not indicated in the designation. If two or more phases would have the same designation according to these rules, they are distinguished by prefixing Greek letters, and are definitely identified by X-ray diffraction patterns. Previous Investigations The solid solubility of magnesium in aluminum has been well established by the work of Dix and Keller4, Schmid and Siebe15, and Saldau and Sergeev6. There is no agreement as to the composition of the magnesium constituents at the aluminum end of the binary aluminum-magnesium system. Hanson and Gayler7 report Mg2Al3; Boyer8 found that the alloy

Jan 1, 1937

By Royal B. Jackman, Carle R. Hayward

Two comprehensive papers have appeared regarding the forms of copper that occur in smelter slags, one by Frank E. Lathe1 and the other by C. G. Maier and G. D. Van Arsdale.2 These authors comment on other published results and draw conclusions from their own investigations. The development of X-ray examination of minerals and improvement in high-power microscopic methods make it possible today to get additional evidence by means that were not available to earlier investigators. The present work was confined to reverberatory slags obtained from five different plants. Some definite conclusions were reached regarding the forms of copper present in these slags. In most cases these agree with some of the findings of Maier and Van Arsdale but new methods of attack were used in the investigation. Conclusions of Previous Investigators Various important conclusions reached by previous investigators are summarized in the following paragraphs, arranged chronologically. William A. Heywood:3 Slag losses increase with grade of matte but with the same grade of matte losses decrease as the acidity of the slag increases. Lewis T. Wright:' Slag losses are only partly due to prills of matte. It is suggested that part of the copper is dissolved in the slag. J. Parke Channing9 A considerable part of the copper enters the slag as silicate or oxide and not as sulfide. C. A. Grabill:6 Slag losses are both physical and chemical. Physical losses, due to poor settling, gas flotation and slight differences in specific gravity, are small under normal conditions. Chemical losses may- be due to formation of oxides or to solution of metals and sulfides. The last is considered the most important. John W. James:' The copper in converter slag is largely the oxide and as such enters the reverberatory slag when converter slag is added to the charge.

Jan 1, 1934

By W. J. Babyak

The habit planes for hydride precipitation in large grains of alpha zirconium and Zircaloy-4 were determined in specimens containing 161 and 136 ppm hydrogen, respectively. In zirconium, the hydride platelets precipitated on various pyramidal planes inclined to the basal plane at angles ranging from 10 to 50 deg and 75 to 90 deg. Hydrides were most frequent at inclinations of about 20 deg and 90 deg. In Zircaloy-4, hydride plates were inclined to the basal plane at angles vanging from 5 to 25 deg with the predominant inclinatioiz equal to 12 deg; no platelets were found near the prism plane position. In both zircoinium and Zir-caloy-4, hydrides were principally, but not exclusively, parallel to (1011) type planes. When the Zircaloy-4 gmins were subjected to tension stresses of 12,100 psi and 19,400 psi during hydride precipitation, the hydride habit was unchanged except that precipitation favored those habit planes which were inore nearly perpendicular to the stress direction. The stress-orientatioiz effect increased with the magnitude of the stress. THE hydride habit plane in a zirconium has been determined by several investigators. Langeron and Lehr1 in 1956 found platelets parallel to (1010) slip planes. In 1962, Westlake and Fisher2 confirmed these findings and showed that hydride precipitation on twin planes, as reported by Kunz and Bibb,3 was probably due to incomplete removal of worked metal from specimen surfaces. Secondary habit planes, ( 1011) and (1015), were also found by Westlake and Fisher under particular charging conditions where a hydride layer may have existed at the hydrogenation temperature. Most recently, walters4 and westlake5 again observed the (1010) habit exclusively in zirconium. Louthan and hgermans have reported that hydrides precipitate on various ( 101l ) and (112l) planes positioned 31.5 to 90 deg to the basal plane in Zircaloy-2. The present investigation was concerned with the hydride habit in Zircaloy-4 in relation to that in zirconium and the possible change in habit when precipitation occurs under stress. The latter consideration was prompted by the stress-orientation phenomenon originally reported by Marshall and Louthan.7, 8 I) EXPERIMENTAL Materials and Specimens. Chemical analyses of all materials are given in Table I. The zirconium specimen was a 1 by 4 in. section cut from wrought crystal bar that was hot-rolled at 790°C to 0.300 in. and cold-rolled to a final thickness of 0.095 in. All surfaces were mechanically polished and then chemically polished with a solution of H2O, HNO3, and HF (10:10:l by volume) prior to annealing. Grains as long as 0.25 in. were grown by thermally cycling the specimen three times (in 10-5 mm Hg vacuum) between 825" and 1000°C at approximately 125°C per hr. The specimen was isothermally annealed at 825°C for 24, 40, and 120 hr after each cy-

Jan 1, 1968

By P. B. Crawford, W. L. Huskey

A study has been made to determine the effects of random vertical fractures existing in a reservoir matrix on the effective matrix properties and producing characteristics of a well. The study indicated that short vertical fractures may distort the isopotentials by 1 percent in the vicinity of the fracture. A correlation was developed which showed the effect of fracture density on the producing capacity of a well. The correlation indicated that fracture shape had little effect on producing capacity, but that total fracture length was closely correlated with the producing capacity. Effective values of reservoir permeability were found to correlate closely with fracture density when measured parallel to the direction of flow. INTRODUCTION In reviewing the petroleum literature, it is found that in most analytical solutions of hydrocarbon reservoir behavior the assumption is made that the rock is uniform throughout although core analysis and well logging surveys indicate that substantially all reservoirs are heterogeneous and some are fractured. Only in recent years have investigators studied the effects of reservoir hetrogeneity. Russell1 discussed the effect of fractures in reservoirs. The literature indicates that fractures greatly affect the exploitation of man reservoirs. This is described by Elkins and Skov2 and Little-field et al. 3 Several types of reservoir heterogeneity have been studied by unsteady-state methods. In 1959, Landrum et al. 4 showed that transient phenomena in hydrocarbon reservoirs could be studied by thermal models. pickering5 studied the flow of heat in stratified linear reservoirs consisting of plates of different metals separated by sheets of rubber which were suddenly exposed to a low-temperature source at one end. Cotman6 studied both laterally and vertically heterogeneous thermal model reservoirs with special reference to cross flow. Another type of reservoir heterogeneity involves the presence of highly permeable, circular lenses around or near the wellbore which was studied by Miesch7 using a thermal and a steady-state model. Many studies have been made of the effects of induced hydraulic fractures on well performance. 8-10 Work regarding vertical fractures that exist initially in the reservoir was reported by Givens, et al.11 Since there appears to be little published work on the importance and influence on reservoir performance of fractures that exist out in the rock matrix, this study was conducted to determine the effects of vertical fractures on pressure distribution, producing capacity and the effective permeability of the reservoir rock. The analogy between the flow of electrical current through a conducting body and the flow of fluid in a porous medium provides a convenient method of studying various aspects of petroleum reservoirs. For electrical radial steady-state flow,12 For steady-state fluid flow, With the above analogy, it is only necessary to establish the ratio of the values of the electrical units in terms of the corresponding flow units to make the analogy quantitative. The ratios are shown below.

By G. L. Hassler, E. Bruner

An apparatus and method is described whereby the relation between saturation and capillary pressure under decreasing saturation can be quickly determined for small core samples. The initially saturated core is cen-trifuged at increasing rates and the average saturation is measured at each rate with the aid of a stroboscope device. A theory and calculation procedure is given whereby the accelerations and saturation values can be converted into a true curve of capillary pressure versus saturation. The present work differs from previously described use of the centrifuge to obtain capillary-pressure curves of core samples3 in that the core is centrifuged alone, so that the whole range of saturations required by the properties of the sample and the radially varying centrifugal force occurs within the sample. The calculation procedure nevertheless secures correct results from simply obtained values of the average saturation. The apparatus described was developed in connection with studies of capillary pressure and wetting of oil-field rocks, and the paper provides the apparatus background for a previous publication' dealing more fully with the uses and implications of the data in petroleum engineering. The method is applicable, however, to general combinations of immiscible fluids and porous or comminuted solids, and may be useful in other fields. Introduction The importance of capillary phenomena in determining the behavior of liquids in porous media has long been recognized. The concept of capillary Pressure was early formulated, and in recent Years discussions of the application of the laws of capillarity to oil field problems have appeared.l-3 One reason why progress in the application of capillary phenomena to the solution of problems of reservoir mechanics has not been more rapid has been the lack of a, satisfactory technique for measuring the capillary pressures in reservoir rocks. It is the principal purpose of this paper to describe a method by which the relation between capillary pressure and saturation can be determined for small consolidated core samples which have been extracted and resaturated, Capillary Diaphragm Perhaps the most direct way to measure the capillary pressure in a rock is to make piezometric contact with the wetting liquid through a diaphragm of porous material with high displacement pressure saturated with the liquid in question.3-6 The liquid in the diaphragm assumes the pressure of the liquid in the core, which can then be measured with a manometer, while the atmospheric air is prevented by capillarity from entering the diaphragm and affecting the pressure measurements as long as the displacement pressure of the diaphragm is not exceeded. With an apparatus of the type illustrated schematically in Fig. I, the relation between capillary pressure and saturation can be measured for a small core sample by starting with the core saturated 100 per cent, applyillg successively greater suctions

Jan 1, 1945

By Lester W. Strock

METALLURGISTS handling lead and zinc ores have long been familiar with the spectrograph as a routine analytical tool, as its earliest regular use by American industry was in controlling impurities of zinc metal and its alloys. This application has been extended to other metal industries on an extensive scale, accompanied by refinements of procedure to such an extent that a large part of some metals produced, especially magnesium, aluminum and steel, are checked only by spectrographic methods for conformity to specifications. The spectrographic analysis of ores and other poorly conducting powdered solids presents difficulties not encountered with metallic samples, which can be arced or sparked as self-electrodes or can be readily dissolved, so that their solutions can be analyzed, as in the American Society for Testing Materials standard methods for zinc and zinc-base alloys. Spectra of powdered solid samples can be prepared by using carbon electrodes provided with a crater of suitable size, into which the sample is packed. Ore samples and many other powdered solid materials usually analyzed in the chemical and metallurgical laboratory are more complex and varied in composition than samples of metals produced in large tonnages. More preliminary work therefore is usually necessary in devising a spectrographic method for analyzing a given type of powdered sample than for analyzing metal samples, in order to use that method with confidence. The knowledge that the standard samples and unknowns produce equivalent line intensities at equal concentration is the fundamental basis of any quantitative spectrographic method. On the other hand, powdered samples have an advantage over metals in that any desired number of chemical compounds can be mixed dry in any desired ratio to produce a synthetic standard. Experience has shown, however, that spectra of elements in finely divided compounds introduced into a standard in preparing a synthetic ore sample do not always behave in the electric arc in a manner that produces spectral line intensities similar to those observed at the same concentration in a natural mineral. In ore samples minor elements frequently are contained in the crystal lattice of larger particles of an abundant ore mineral. Their dissociation and volatilization from the sample into the arc then proceeds differently in the standard and sample, with resultant differences in intensity. During the past 10 years I have devised and applied several quantitative spectrographic methods for determining various elements in rocks and minerals in connection with studies on their geochemistry,1 but the incentive has gradually changed since the summer of 1940 to the specific practical problem of searching for domestic sources of rare and strategic metals. The

Jan 1, 1945

By C. S. Smith

The partial persistence of grain size and grain shape on melting and resolidifying crystalline substances, as well as the general effects of pre-solidifi-cation and of superheating on nuclea-tion rate, have been attributed to the presence in the liquid of crystalline impurities bearing some structural relation to the principal solid and hence capable of serving as nuclei for its crystallization. That such lattice matching does sometimes occur is well established, but it is surely improbable that a compound possessing both high-temperature stability and the requisite structural similarity should be naturally available in almost every system. It is now suggested that a mechanism for producing appropriate nuclei exists in the crystallization of all but absolutely pure substances. Impurities can he of many kinds. Some will give rise to compounds that are less soluble in the solid crystal than in the liquid. A . crystal forming from a melt or solution containing these will be supersaturated in some degree, and the foreign atoms will commence to segregate during or after solidification. They do not necessarily form pure, unstrained, crystals of the precipitating compound with its normal composition and structure. Generally—at least in the metallurgical examples that have been most studied —the first recognizable nuclei have lattice coherency with the surrounding matrix and have practically the same crystal structure and lattice spacing as the material in which they form, differ- ing only in composition. An extremely thin oxide layer formed under appropriate conditions on or in a solid metal will tend to be coherent with the metal lattice, and the first few atom layers of the oxide in contact with the metal will differ in both composition and structure from massive crystalliue oxide. It will resemble the metal more closely than the oxide. If it did not subsequently change on melting, such an oxide film would constitute an almost perfect "template" or two-dimensional matrix to hold a few atoms of the primary metal in the exact array needed to form a nucleus for solidification. Any precipitating material will adopt the correct spacing over a few atom diameters, and with appropriate substitution of other atoms of the correct sizes a precipitate can match the parent lattice over large areas of cohererlce without excessive strain. In metals, the componentsof a host of oxides, silicides, borides, nitrides, carbides, sulphides, and other compounds are always present in minute amounts. Some of these will be eliminated because of extreme insolubility in the liquid, while others will remain soluble in the solid; occasionally, however, particles will be formed in the solid by coherent precipitation—not of pure substances, but of whatever assortment of atoms best satisfies the joint requirements of availability, affinity, and appropriate average atom size. Of these, many will disappear on melting, but a few will persist unmelted as little rafts of complex composition, maintaining in the liquid a surface of the exact geometry needed to nucleate the solid on subsequent cooling. Their number and size distribution will determine the resulting grain size; the dimensions of the largest will determine the degree of undercooling that can occur before solidification commences. A similar process may operate in the case of phase transformations in solids. The coherent precipitation of supersaturated minor constituents in a low-temperature phase should facilitate the nucleation of this phase on subsequent cooling after transforming into another phase at higher temperatures. At first sight this hypothesis may seem little different from the older ones. It should therefore be emphasized that it does not depend on chance to provide the right compound to form a nucleus, but postulates that every crystal, containing minute amourlts of any of a wide range of impurities, automatically engenders particles having the correct surface structure to serve as nuclei for subsequent solidification. It could operate in any system, metallic, organic, or inorganic. The suggested mechanism is closely analogous to the production of antibodies from antigens in living organisms—indeed, it was a description of the matrix theory of this process that suggested to the writer its crystalline analogue.

Jan 1, 1950

By Michael B. Bever, Carl F. Floe

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

Jan 1, 1944

By Carl F. Floe, Michael B. Bever

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

Jan 1, 1944

By L. J. Howell, R. C. Sommer, H. H. Kellogg

WORK described herein was undertaken with the aim of determining some of the physical-chemical properties of electrolytes suitable for the electrodeposition of pure zirconium metal. In this paper the phase diagram, vapor pressure, and activities in the melt are considered. In a companion paper,' the electrolytic conductivity of some of these melts is reported. The melts studied were mixtures of NaCl and/or KC1 with ZrC1,. Chloride melts were chosen for study because 1) if the electrolyte is to be useful for industrial electrodeposition of zirconium, the chlorides will be preferred to the relatively costly bromides and iodides; 2) fluoride melts were being studied in another laboratory (Horizons Inc., Cleveland); and 3) melts containing oxygen, in any form, are unsuitable for preparation of pure zirconium, because of the great affinity of this metal for oxygen. Unlike electrodeposition from aqueous solution, the fundamental behavior of fused-salt electrolysis is poorly understood. In most cases, such basic electrochemical information as the phase diagram of the melt system, activities in the melt, conductivity, the nature of the current-carrying ions, the equilibrium electrode potentials, and the overvoltage behavior of the electrodes is unknown to the researcher who would develop a new electrodeposition process employing a fused salt. This research project was designed to supply information about some of these basic physical-chemical properties so that an intelligent choice of electrolyte for electrodeposition studies could be made. Experimental The experimental difficulties-encountered in this work result from the properties of zirconium metal and ZrC1,. ZrC1, is a solid which sublimes at 334°C. It is rapidly hydrolyzed by moist air to HC1, ZrOCl,, and ZrO,. Unusual precautions were exercised in this work to prevent hydrolysis of ZrC1, and rigidly to exclude oxygen, nitrogen, hydrogen, and carbon from the melts under study. These elements are known to react with and contaminate zirconium metal. All melts were studied in vacuum systems, i.e., in the presence of ZrC1, vapor only. Transfer of ZrC1, to or from the melts was accomplished entirely by vacuum sublimation. In this way, neither the melts nor the ingredients thereof were permitted to

Jan 1, 1958

By Louis E. Toth, Alan W. Searcy

A modification of Le Claire's microscopic model for self-diffusion is developed in a form suitable for prediction of activation energies for diffusion in disordered substitutional solutions as well as in pure metals Bonding is considered as a localized interaction, and the energy of bonding between atoms of different types is taken as the arithmetic mean of the energies in the pure elements. The activation energies for vacancy formation and migration in substitutional alloys are shown to depend on the empirical constants developed for self-diffusion when the equations are adjusted for the mole fractions of the two elements. The differences in activation energies between alloys and pure metals are calculated and compared with the experimental differences. MaNY different correlations have been proposed for use in predicting activation energies for self-diffusion or diffusion in dilute alloys. Usually theories for self-diffusion cannot be applied to alloys nor can theories for dilute alloys be satisfactorily adapted to self-diffusion. We present here a correlation scheme which can approximate activation energies for diffusion, vacancy formation, and atom migration in substitutional-alloy systems of any concentration. The activation energy for self-diffusion QD has been correlated to the melting temperature Tm,1, 2 the sublimation energy L,,l the heat of fusion Lf,3 crystal structure, and valence.4 Working with mechanical parameters Le claire5 proposed that the activation energy for vacancy migration Qm could be related to appropriate shear moduli. He also proposed that the activation energy for vacancy formation 62, is proportional to Ls. THEORY We consider that Le Claire's expression for 4, is satisfactory. But an alternate expression for Qm in terms of the bulk modulus is just as satisfactory from a theoretical point of view for the prediction of the energy of vacancy migration in pure metals and can more easily be used for alloys. In order for Qm to be a minimum, not only the moving atom but also adjacent and nearby atoms must undergo distortions. These distortions are neither isotropic as is implied by a correlation with the bulk modulus nor unidirectional as implied by a correlation with a shear modulus, but are complex and multidirectional. A complete analysis in terms of the bulk modulus and all the shear moduli is not yet available. In a first approximation in which only one parameter is used, there is no obvious theoretical reason to prefer the shear modulus over the bulk modulus. The bulk modulus is a much more convenient parameter for use in predicting Qm. Shear moduli are known for less than half of the metallic elements while bulk moduli are usually available. Furthermore, because of the directional dependence of shear moduli, their estimation for alloys appears inherently more difficult than is the estimation of bulk moduli. We assume that the bulk modulus Bs reflects an average value of the shear moduli such that the strain energy at the point of maximum distortion of the lattice during vacancy migration can be expressed as

Jan 1, 1964

By C. P. Mangelsdorf

Introduction The use of frequency of vibration measurements to determine tension has long been accepted by industries that use electrical or stranded cables of wire ropes in their operations. In contemplating how to determine the tension in chords of a roof truss, it seems almost inevitable that a similar approach should be investigated even though there are some important dissimilarities in physical behavior between a chord of a rod-type Birmingham truss and a stretched wire rope. While the dominant feature of both types of behavior is the existence of tension, the bending resistance of the vibrating truss chord cannot be ignored. And it is common to have attached to the chord, pieces of hardware (turnbuckles, extension sleeves, wedge boxes) that represent concentrations of mass not usually found in a vibrating wire rope. Analytical solutions to the problem of vibrating wires or beams can be found in the literature on vibrations (Timoshensko, 1955; Den Hartog, 1956). But in every case, at least one of the ingredients of the vibrating truss chord is missing. The presence of axial tension, or bending resistance, of concentrated masses and of end conditions peculiar to truss chords is a combination that appears not to have been dealt with before, although the techniques for dealing with it are commonly known. The purpose of this note is to report the results of a project to measure and calibrate such frequencies. The work was conducted by the University of Pittsburgh under the sponsorship of the US Bureau of Mines. Field observations Tests were conducted on 24 different truss installations. The first 18 trusses were installed in shale roofs above Kentucky No. 9 seam and Illinois No. 6 seam. The remaining six were placed against the competent sandstone over the Pocahontas No. 3 seam in West Virginia. Chord tension was determined by two electrical resistance strain gages, in series, applied diametrically opposite to one another on the rod before tensioning. Due to the combined effects of inexact gage placement, rod bending and residual torsion in the chord due to tightening, errors in tension as high as 1780 N (400 lb) were reasonably possible. Due to faulty soldering or damage, three of the first 18 trusses and one of the final six were rendered completely unreliable. In addition to strain, the first natural frequency of vibration was observed to the nearest 0.1 Hz. Dimensions recorded included the span between contact points at the bearing blocks (Fig. 1) and the locations and amount of excess rod and rod gap at the wedge box and turnbuckle, respectively.

Jan 1, 1986

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

When one solid phase is generated from another, fixed and rational orientation relationships are observed to subsist between the parent and the new crystal. The principle has been proposed1 that the relationships obtaining between the same two phases are identical whatever the type of phase change involved, or whichever of the phases may act as parent. Many types of phase changes have been studied: allotropic transformations in pure metals, precipitation from solid solutions, eutectoid decompositions, peritectic reactions, the formation of oxide layers, and others2 Phase layers generated by diffusion of one metal into another constitute an additional type of reaction. This report provides new data on the orientation relationships occurring between phase layers formed by diffusion, in the Cu-Zn system,§ and furnishes further evidence in support of the principle. Materials and Methods The Cu-Zn system is especially suitable for these studies since the high vapor pres- sure of Zn provides an opportunity readily to create one phase poorer in Zn upon a parent phase richer in Zn by removing Zn by vaporization, or to reverse this process by adding Zn from Zn vapor; e.g., the beta phase can be found as a layer upon gamma by dezincing, or gamma can be found on beta by addition of Zn from Zn vapor. Since orientation relationships are to be sought, requiring crystals large enough for orientation determinations, it is convenient to prepare single crystals or large grains of the parent phase. The samples were prepared from oxygen-free high-conductivity copper and Horse Head zinc by melting under a borax flux in a graphite crucible. Large crystals of beta brass were grown by the strain-anneal method, in plates sectioned from the cast ingots, by the following procedure. Rockwell-hardness indents were made at I cm. intervals and with various loads, then the plates were annealed for 4 days at 700°C. in Nichrome boxes packed with beta-brass chips and graphite. Surface layers were removed by grinding and etching to a depth of about 1.0 mm., and individual grains were cut out. Crystals of alpha and gamma brass were prepared by freezing, by lowering a graphite crucible at speeds less than one inch per hour through a furnace held at a constant temperature above the melting point. Single crystals were cut out with a jeweler's saw, ground, polished and etched. Care was taken to remove cold-worked layers from the finished crystals

Jan 1, 1944

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

When one solid phase is generated from another, fixed and rational orientation relationships are observed to subsist between the parent and the new crystal. The principle has been proposed1 that the relationships obtaining between the same two phases are identical whatever the type of phase change involved, or whichever of the phases may act as parent. Many types of phase changes have been studied: allotropic transformations in pure metals, precipitation from solid solutions, eutectoid decompositions, peritectic reactions, the formation of oxide layers, and others2 Phase layers generated by diffusion of one metal into another constitute an additional type of reaction. This report provides new data on the orientation relationships occurring between phase layers formed by diffusion, in the Cu-Zn system,§ and furnishes further evidence in support of the principle. Materials and Methods The Cu-Zn system is especially suitable for these studies since the high vapor pres- sure of Zn provides an opportunity readily to create one phase poorer in Zn upon a parent phase richer in Zn by removing Zn by vaporization, or to reverse this process by adding Zn from Zn vapor; e.g., the beta phase can be found as a layer upon gamma by dezincing, or gamma can be found on beta by addition of Zn from Zn vapor. Since orientation relationships are to be sought, requiring crystals large enough for orientation determinations, it is convenient to prepare single crystals or large grains of the parent phase. The samples were prepared from oxygen-free high-conductivity copper and Horse Head zinc by melting under a borax flux in a graphite crucible. Large crystals of beta brass were grown by the strain-anneal method, in plates sectioned from the cast ingots, by the following procedure. Rockwell-hardness indents were made at I cm. intervals and with various loads, then the plates were annealed for 4 days at 700°C. in Nichrome boxes packed with beta-brass chips and graphite. Surface layers were removed by grinding and etching to a depth of about 1.0 mm., and individual grains were cut out. Crystals of alpha and gamma brass were prepared by freezing, by lowering a graphite crucible at speeds less than one inch per hour through a furnace held at a constant temperature above the melting point. Single crystals were cut out with a jeweler's saw, ground, polished and etched. Care was taken to remove cold-worked layers from the finished crystals

Jan 1, 1944

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

Vapor pressures of eight compositions of Mg-Cd have been determined by the Knudsen effusion technique. Measurements are made at several temperatures for each alloy and the results interpolated to a common temperature for the calculation of the activities. It is not possible to obtain values for the partial molar enthalpies because of the narrow temperature range spanned by the measurements. The results show less precision than those obtained for pure Cd which are also reborted. These alloys are extremely susceptible to corrosion which provides a possible explanation for the lack of precision. Nevertheless, the values of the activity are in good agreement with the results of electromotive force measurements previously reported for the Mg-Cd system. MAGNESIUM and cadmium are mutually soluble in all proportions in the solid state and form a single phase which has the hexagonal close-packed structure. X-ray investigations of this system1,2 have revealed a rapid variation in the relative dimensions of the unit cell occurring at approximately 50 at. pct. The rate of change of the c/a ratio with composition increases markedly for alloys containing more than 50 at. pct Cd. The purpose of this investigation was to determine the activity of Cd in the neighborhood of 50 at. pct and to discover whether or not the thermo-dynamic properties undergo a similar rapid change. The activities are calculated from vapor pressure data obtained by the Knudsen effusion method. Unfortunately the precision of the data from which the thermodynamic values are calculated is insufficient to establish unequivocally a departure from the normal trend. The results are reported primarily because they substantiate the only previously reported activity measurements3 and because they include values for pure Cd which in contrast to those of the alloys show excellent precision. The Cd-Mg system is known to contain several ordered phases. However, this investigation was made at temperatures considerably above the transition temperatures, and the alloys may be regarded as nearly random solid solutions. EXPERIMENTAL Apparatus—The effusion cells are machined from solid tantalum rod. The lids consist of threaded, flanged rings of tantalum onto which are welded shallow cups of 4 mil molybdenum foil. The orifice, which is located at its center, is made by grinding off a small dimple produced with a sharpened punch. Such an orifice has been mounted in plastic, sectioned, and the thickness of the orifice edge measured in a microscope. The maximum thickness is 0.00016 in., and the Clausing factor is consequently equated to unity. The area of the orifice is determined by tracing its projection on the screen of the metallograph at a known magnification and measuring the area of the tracing with a planimeter. Excellent temperature control is achieved with a 4 by 18-in. alundum core, gradient-wound, furnace

Jan 1, 1960

By Karl L. Fetters

In the process of making steel in the open-hearth furnace the refining of the metal during the working period of the heat is largely accomplished through the agency of the slag. From the birth of the process until the present day steelmakers have recognized the importance of the slag in determining the composition of the metal and the quality of the product. The general relationships between slag composition and metal analysis have long been known, at least in a qualitative or approximate fashion. For examples, the iron oxide content of the slag is higher on lower carbon heats; the more basic slags are higher in iron oxide for a given carbon content; certain amounts of iron oxide and lime arc required for phosphorus removal and a high lime-silica ratio is needed if the sulphur content of the metal is to be diminished. In recent years a number of quantitative relationships involving these and other variables have been developed through plant and laboratory studies by numerous investigators in this country and abroad. The direct comparison of laboratory and open-hearth data involves the question of the degree to which each approaches the conditions of chemical equilibrium, a question which, from the open-hearth standpoint, we are scarcely yet in position to answer. And, although a considerable body of dependable equilibrium data has been obtained in the laboratory, this work has not yet been extended to cover the ranges of slag composition encountered in basic open-hearth practice. In the present study we shall not attempt to draw comparisons between data from the two sources; nor do we attempt to draw conclusions as to the approach to chemical equilibrium in the open-hearth furnace. Many of the operating variables that are likely to be erratic or unrecorded during the earlier stages of the heat become more consistent and arc more readily subject to observation and control during later stages. For example, undigested lime or ore gradually goes into solution, the rate of carbon drop levels off, and the temperature of the metal is brought under control. For these and other reasons a greater degree of self-consistency is likely to be found among data obtained during the

Jan 1, 1940

By Karl L. Fetters

In the process of making steel in the open-hearth furnace the refining of the metal during the working period of the heat is largely accomplished through the agency of the slag. From the birth of the process until the present day steelmakers have recognized the importance of the slag in determining the composition of the metal and the quality of the product. The general relationships between slag composition and metal analysis have long been known, at least in a qualitative or approximate fashion. For examples, the iron oxide content of the slag is higher on lower carbon heats; the more basic slags are higher in iron oxide for a given carbon content; certain amounts of iron oxide and lime arc required for phosphorus removal and a high lime-silica ratio is needed if the sulphur content of the metal is to be diminished. In recent years a number of quantitative relationships involving these and other variables have been developed through plant and laboratory studies by numerous investigators in this country and abroad. The direct comparison of laboratory and open-hearth data involves the question of the degree to which each approaches the conditions of chemical equilibrium, a question which, from the open-hearth standpoint, we are scarcely yet in position to answer. And, although a considerable body of dependable equilibrium data has been obtained in the laboratory, this work has not yet been extended to cover the ranges of slag composition encountered in basic open-hearth practice. In the present study we shall not attempt to draw comparisons between data from the two sources; nor do we attempt to draw conclusions as to the approach to chemical equilibrium in the open-hearth furnace. Many of the operating variables that are likely to be erratic or unrecorded during the earlier stages of the heat become more consistent and arc more readily subject to observation and control during later stages. For example, undigested lime or ore gradually goes into solution, the rate of carbon drop levels off, and the temperature of the metal is brought under control. For these and other reasons a greater degree of self-consistency is likely to be found among data obtained during the

Jan 1, 1940

By B. R. Banerjee

MATERIAL used throughout this investigation was high-purity aluminum (99.998 pct). The 1/2-in. cubes were cut out of a cold-rolled slab and annealed at 550°C for 1 hr before deformation. The single crystal specimen was 1 in. in diam x 0.33 in. thick, cut from a cylindrical crystal produced by cooling at about 55°C per hr in a furnace which had a convenient gradient of about 10°C in every 4.5 in. vertical crucible length. Specific data on the ten specimens studied are summarized in table I. Three types of deformation were employed: (I) compression in a hand-operated hydraulic press; (2) impact with a 7-lb sledge hammer; and (3) rolling, using a wedge-shaped specimen' to obtain a gradient of deformations varying from 0 to 50 pct along the length of the wedge. Specimens were either deformed at room temperature, or first cooled in a freezing mixture of dry ice and ether at a temperature of —72°C and then deformed between steel blocks cooled with dry ice. The specimens deformed at the low temperature were ground and polished through 000 emery paper and wheels impregnated with alundum and alumina No. 1. During this entire procedure the specimens were dipped frequently in the freezing mixture of dry ice and ether in order to maintain constantly a frosty surface as insurance against overheating. All specimens were given a final electrolytic polish, using two different electrolytes* to insure that the surface effects observed were not char- acteristic of the polishing technique. With both electrolytes, the annealed specimens gave even surfaces with good polish. Several standard etchants were tried without success. The best results were obtained with an immersion etchant, developed in this connection, containing: hydrofluoric acid, 4 parts; nitric acid, 1 part; glycerine, 3 parts. Discussion of Results Typical strain markings have been observed within deformation bands, as shown in figs. 1, 2, and 4. By stereographic plotting of metallographic measurements, the strain markings within a deformation band in a single crystal of aluminum deformed by compression were found to be traces of (111) planes within a maximum scatter of 6". The edges of the deformation band were found to be traces of the (100) planes also within the maximum scatter of 6" (in agreement with previous workers). At 30 pct deformation, this scatter was considered quite normal because of the fragmentation and rotation of the crystal. This solution, based on the traces on one plane of observation is not unique, but as the planes were observed to be those normally and logically to be expected, further work in this regard was not felt to be necessary. The study of strain markings in a wedge-shaped specimen, rolled to obtain a gradient of deformation from 0 to 50 pct, revealed prominent strain markings at 25 pct reduction in thickness (fig.5). Faint and weak strain markings were visually observable up to a minimum reduction in thickness of about 12 pct. Since strain markings have been observed in other face-centered cubic metals after much smaller deformations;1, 2 and since the rate of recovery in aluminum is high, it is believed that, at lower deformations, self-recovery removes the localized strains at the slip interfaces, thus removing the source of the etching effects that give rise to strain markings. At high magnifications, strain markings sometimes seem to appear as very thin, light-banded re-gions bounded by a pair of dark edges. This so-

Jan 1, 1951