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By Rafael Fernandes Reis, Leonardo José Silva de Oliveira, Rodrigo Seara Martins

Alterações na cristalização dos pós fluxantes durante o processo, devido variações de composição química pelas reações metalúrgicas na interface metal/escória ou pela incorporação de compostos exógenos, afetam o fluxo de calor no molde de lingotamento contínuo. Um dos compostos importantes é o ZrO2, proveniente do desgaste da válvula submersa. A proposta do trabalho foi investigar o efeito deste composto, utilizando simulação laboratorial, na cristalização do pó fluxante e no fluxo de calor do molde. Os resultados demonstraram que quando há o incremento do teor de ZrO2 o fluxo de calor na região do menisco também se eleva. Tal efeito é crítico para formação de defeitos, uma vez que a região do menisco é crucial para a solidificação inicial do aço.

Oct 1, 2019

By W. Bendaikha, S. Larbi, A. Ramdane

An oolitic iron ore from Gara Djebilet, Algeria was characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive spectrosopy and the phosphorus distribution between various phases studied. Two ore types were identified – a haematite-dominated, oolitic type and a more massive, magnetite-dominated type. The haematite-dominated ore had a higher phosphorus content, up to 0.6% in the iron oxide minerals, than the magnetite-dominated type (0.3% P). Owing to the very fine-grained texture of the gangue minerals, reducing the phosphorus content to levels suitable for steelmaking (below 0.05% P) by conventiobal means would entail an energyintensive process with a high carbon footprint. Preliminary leaching test work using a sulphurous geothermal water as lixiviant, assisted by solar thermal acceleration, gave very promising results, removing 0.13% of the residual P (or 21.7% removal of total P) from the high-phosphorus oolitic ore.

Mar 14, 2024

By Richard Kunter

INTRODUCTION Additional work has been done on the CIP circuit at Creede, and a brief description of this work is presented in this paper. DREDGE The original dredge for the Bulldog was built by Al Hack, Inc. of Denver. The dredge cutter head is mounted on a boom made of 6-inch diameter pipe which is raised and lowered by a cable-pulley system. Maximum cutting depth is 8 feet. Slurry from the dredge flows through a floating 6-inch diameter pipe supported on 55-gallon drums which runs from the dredge to the shore and then to a trash screen and pumping system. See Figures 1 and 2. The cutter head, suction pump, winches for dredge movement, and all other operations are controlled from a small operations house located toward the rear of the dredge. All of the basic dredge equipment is mounted on a chassis about 8 ft x 16 ft in size. Additional buoyancy was originally provided by sealed 55-gallon drums supported along the sides of the chassis by a small wooden framework. Additional framework and barrels on the front of the chassis on either side of the cutter boom provided additional stability, particularly when digging in hard material. The dredge was quite stable, but two problems were apparent. For one, it could have been sunk by someone from the shore firing a rifle into all of the barrels. In prime deer-hunting and sportsman country

Jan 1, 1983

By R. P. Adams, R. A. Beall

The Bureau of Mines developed a method to melt and cast specimens of hafnium- carbon alloy and studied their properties . A rotating - ladle vacuum or inert atmosphere arc furnace was designed , special electrodes and molds were developed , and operating procedures were worked out for casting small shapes . The cast specimens were evaluated according to their carbon content for melting point , density , microhardness , electrical resistivity , and oxidation resistance . Lattice dimensions were determined , and metallographic specimens were prepared . Photomicrographs were taken of specimens containing 2.72 , 5.50 , 6.47 , 9.97 , 12.8 , and 15.7 weight - percent carbon , and their grain structures were compared .

Jan 1, 1963

By Denilson de Camargo Mirim

Corte, furação e texturização são alguns dos processos que utilizam laser na produção industrial comercial. São processos bem estabelecidos, que contam com equipamentos dedicados e metodologias bem estabelecidas. Apesar de eficientes e de certa precisão, são processos térmicos com inconvenientes intrínsecos como rebarbas, material ressolidificado, zona afetada pelo calor e certa imprecisão dimensional. A utilização de pulsos laser ultracurtos, de largura temporal da ordem de algumas dezenas de femtossegundos torna possível a realização destes processos sem a produção de calor, como no caso de dielétricos, ou com geração desprezível de calor para o caso de metais. Neste trabalho, utilizou-se o aço AISI 1045 para o estudo da interação com pulsos laser de femtosegundos, com o intuito de obter as condições de processo em que a produção de calor seja minimizada ou até mesmo eliminada. Os parâmetros de processo variados foram a largura temporal dos pulsos laser, 25, 87 e 124 fs, a densidade de potência e o número de pulsos sobrepostos. A técnica D-Scan foi utilizada para a determinação dos limiares de ablação em função deste número de pulsos sobrepostos. Foram analisadas a microestrutura das regiões vizinhas à região ablacionada, com o intuito de identificar as possíveis transformações de fase que poderiam estar correlacionadas à produção de calor pelo processo. Condições de mínima produção de calor foram obtidas com minimização de produção de rebarbas e de material ressolidificado.

Aug 8, 2018

By Matheus Soares Siman

A soldagem GTAW tem importância fundamental para a indústria não só pelo excelente controle do aporte térmico, como também ao fato de proporcionar, repetitividade e reprodutibilidade. No entanto, este apresenta uma série de desafios, principalmente em relação à determinação de algumas variáveis e como essas podem afetar a resistência das juntas soldadas. Neste trabalho, investigou-se a influência de diferentes procedimentos de soldagem em tubos de aço SAE 4130 sem costura com e sem a deposição e com a aplicação ou não de pré-aquecimento. Após procedimentos de soldagem, as propriedades mecânicas e a microestrutura da junta soldada, zona fundida, zona termicamente afetada e metal base, foram avaliadas por meio de ensaios de microdureza, de dobramento e análise metalográfica. Foi possível avaliar a influência da aplicação do pré-aquecimento e analisar as propriedades mecânicas e microestrutura das juntas soldadas. Os perfis de microdureza revelaram a importância do pré-aquecimento. O ensaio de dobramento possibilitou a avaliação das juntas de maneira qualitativa. Porém, um ensaio quantitativo, como o de tração, possibilitaria mais informações.

Oct 30, 2017

By W. S. Fyfe

Gold is mobilized and precipitated in a wide variety of environments ranging from those of weathering and biological phenomena, to pluton emplacement to deep metamorph ism . But it appear that pervas ive leaching of large rock volumes fo llowed by the focussed di charge of typically low salin ity flu ids is frequently involved. There are great gaps in our knowledge, particula rly with re pect to gold in very high temperature fl uids generated at near Moho depths. But uch flu id may play an important part in Archaean pluton associated lode gold deposits whe re ultra high temperature fluids, rich in C02-CO-COS, may be associated with magma underplating and crustal assi mil ation processes (sag subduction) associated with very den e ult ramafic magma . Other environment with great potential include those of major thru t fau lt and strike slip fa ult s where large quant ities of fluids are mobilized .

Jan 1, 1986

By Yuanbo Zhang, Guihong Han, Guanghui Li, Tao Jiang, Zengqing Sun, Yanfang Huang

"Because of small specific surface area and poor ballability, vanadium/titanium-bearing magnetite is difficult for production of oxidized pellet. A novel organic copolymer binder, modified humic acid (MHA), has been authorized recently in China. Effects of the novel MHA binder on the quality of V/Ti-bearing magnetite pellets are studied in this paper. Experimental results show the MHA binder can obviously improve the strength of green pellet. Because of better heat endurance, the MHA binder pellet has a higher strength than Peridur pellet under the same preheating conditions. Moreover, TFe grade of pellet with the MHA binder is much higher than that of the bentonite pellet. The strength of preheated pellet containing MHA binder of 0.25%~1.0% meets the requirements of oxidized pellet production by grate-kiln process. Comparatively, MHA is a promising orgainc binder for iron ore pellets. Its price is only one tenth of Peridur price and about 3 times of bentonite price.IntroductionThe iron-making practices show that the use of pellet is beneficial to blast furnace life, productivity and fuel savings. Therefore, many iron-making plants have expanded the production of oxidized pellets in order to meet the needs of modern large-scale blast furnaces [1]. Presently, bentonite is widely used to improve the quality of iron ore pellets. The negative effects of using bentonite include decreasing total iron (TFe) grade and degrading the metallurgical properties of the final products [2, 3]. Many studies, therefore, have been conducted on the application of organic binders to overcome the weakness of the inorganic bentonite. In comparison with inorganic binders, one of the biggest strengths of organic binders is low residual silica content [4]. However, those studies showed that the economics of foreign organic binder addition into pellets was not attractive. For example, the compression strength of preheated pellets and roasted pellets are both too low, resulting in powder generation and ring formation in the industrial rotary kiln [3, 4]."

Jan 1, 2011

By G. Venturello, C. Antonione, G. Della Gatta

Results from work on the effect of inferstitials on recovery and recrystallization of' very pure iron (99.995 pet) doped with nilrogen up to 400 ppm are reported. Nitrided specimens were obtained by heating the iron in a static atmosphere of NH3 + H2. The samples were cold-rolled 80 pet, subjected to a series of isochronal and isothermal anneals, and submitted to examination by X-rays, micrographs, and hardness tests. Small additions of nitrogen show a strong effect in reducing recovery of' the mechanical properties of high-purity iron. At the temperatures of. the experiments, this effect proved greater than in the case of carbon. At 400°C pure iron recovers more than 50 pet of the total hardness increase, carburized iron vecovers 25 pet, and nitrided iron only 10 pet. On the other hand. the addition of nitrogen has, similarly to carbon, a very small effect on recrystallization; the effect is, however, slightly higher than that of carbon. When the concentration Of nitrogen is above the solubility limit in a iron at the temperattue of the experiments, an increase in the frequency of nu -cleation is also observed. THE object of the present work is to improve knowledge on the effect of interstitials both on recovery and on primary recrystallization of pure iron. In fact. at present there are no available data on the effect of nitrogen on high-purity iron. The only work which at present can be somewhat related to this problem is a work of Leak et al.1 in which grain boundary internal friction at high temperature in the presence of increasing amounts of nitrogen is studied by a torsion pendulum. The present work is a continuation of a previous one2 on the effects of carbon. EXPERIMENTAL PART Preparation of the Material. Pure iron was prepared following the same methods used in the pre- vious work2 and was nitrided using controlled quantities of ammonia in an apparatus similar to that used for carburizing. The apparatus consists essentially of a gas-tight quartz tube containing the specimens. The tube, maintained at constant pressure by means of a mercury seal, is placed in a resistance furnace. For nitriding, the NH3 + H2 atmosphere with a suitable concentration of NH3 was introduced into the tube, which had been previously carefully evacuated and degassed by heating at 600°C. The hydrogen used was carefully purified by passing it through a palladium filter. The ammonia required was prepared with the following reaction: CaO + 2NH4CI —CaCl2 + H2O + 2NH3 by heating the mixture of CaO and NH4C1 in a glass flask and then collecting the ammonia in a graduated Hempel burette. For each nitriding program a given amount of NH3 prepared by this method was introduced together with the H2 into the tube previously evacuated. Nitriding of the sample was then performed at 570°C for 48 hr. After this, to ensure a homogeneous distribution of nitrogen, the samples were further heated for 72 hr at 800°C. With this method which uses a static nitriding atmosphere, carefully controlled conditions of purity are obtained. Contrarily, with the conventional continuous-flow methods, using large quantities of circulating gas, there is a greater risk of introducing impurities into the samples. Furthermore, the required nitrogen concentration in the specimen is easily predetermined and obtained. A plot of the relation observed between the initial concentration of NH3 in the gas and the quantity of nitrogen introduced into the iron samples is given in Fig. 1. The data refer to samples of 1.2-mm thickness and to the nitriding conditions previously described. Furthermore, as a comparison, the data relative to two 0.5-mm-thick samples are reported. The presence of a reservoir in the cold zone of the reaction bulb made possible the gradual dissociation of ammonia on the sample in the hot zone. Internal-friction methods were used to determine the content of nitrogen dissolved in the iron samples. Some analyses were also carried out with chemical methods. The following table, Table I, shows a comparison of data obtained with chemical and internal-friction methods. The correspondence between chemical methods and internal-friction

Jan 1, 1964

By F. C. Bond, J. T. Wang

H. J. Kamack (E. I. du Pont de Nemours & Co., Inc., Wilmington, Del.)—Rittinger's law usually is stated to the following effect: "The work (or energy) consumed in particle size reduction is proportional to the new surface area produced." The law has been stated substantially in this way by Taggart20 Berry21 Dalla Valle22 Coghill and DeVaney,23 Richards and Locke," Gross,25 and many others, and, according to Gaudin,26 was originally expressed by Rittinger in the same form. Consequently there can be little doubt that this is the understanding of the law among most workers in the field of particle size reduction. Bond and Wang, however, express the law in the form "the useful work accomplished . . . ." (italics theirs). The distinction is critical, for in the form used by Bond and Wang the law becomes, as they themselves remark "merely a more or less arbitrary definition of useful work," while in its usual sense the law expresses a physical hypothesis which has been verified experimentally within certain limitations. Considering the way the law has been used, it might be stated more explicitly as follows: "In a given machine operating under a given set of constant operating conditions, the work consumed in the particle size reduction of a given material is proportional to the new surface area produced." Or, as Coghill and deVaney have said,27 "the (Rittinger) law holds only when the tests being compared are made under analogous conditions." There are occasions when the law transcends these limitations; for example, the surface area produced per unit energy consumption for a given material in a ball mill does not vary much over a fairly wide range of operating conditions. But by and large, the surface area production per unit energy consumption will vary with the operating conditions, the type of machine, and the material. The essence of Rittinger's law is that the surface area production per unit energy consumption is independent of the particle size, and this has been verified experimentally by numerous workers for numerous materials, within certain limits. An important limitation is that when one grinds to very small particle sizes, agglomerative forces may tend to interfere with size reduction so that the surface area increases less rapidly than Rittinger's law would predict. Within such limitations, Rittinger's law can be regarded as empirically established. The law has, however, certain theoretical implications, and it seems to be chiefly against these that Bond and Wang direct their criticism. Solids are believed to possess surface energy which is proportional to surface area. Thus, Rittinger's law implies a proportionality between surface energy produced and mechanical energy expended (for a particular material in a particular machine). It does not imply that all or most of the mechanical energy is transformed into surface energy; in fact it is known that most of the mechanical energy is transformed into heat. Bond and Wang assert that most of this heat arises from the damping of elastic vibrations of stressed particles. This may possibly be true for crushing (with which they are chiefly concerned), although in grinding it is probable that much of the heat arises from friction between particles. However, the fact that the surface energy is small compared to the heat energy does not invalidate Rittinger's law, which implies merely that they are proportional. The authors also criticize Rittinger's law on the grounds that "this theory cannot be justified mathematically, since work is the product of force times distance, and the distance factor is ignored," and "energy input must be the product of force times distance, and the Rittinger theory completely ignores large variations in the distance (strain dimension or deformation) throughout which a force must act to produce breakage of different materials." However, the quantities force and distance as such are irrelevant to Rittinger's law, which considers energy input as an integral quantity. The fact that different materials require different forces and strains (hence, different amounts of energy) to break them is incontrovertible but again is irrelevant to Rittinger's law, which, as mentioned before, applies -only to a single material. Even in theory, it would not be expected that the surface area produced per unit energy consumption would be the same for different materials, because the surface energy per unit area is presumably specific to each material. Bond and Wang advance another argument of a

Jan 1, 1952

By J. F. Pierce, S. M. Enterline

Since January 1959 a zinc refiner of novel design has been in operation at Blackwell, Okla., producing 99.995+ zinc from the output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyro-metallurgical unit with principal dimensions horizonhl permitting one floor operation. It is very ruggedly constructed. Furthermore it is not subjected to deterioration from high concentrations of iron in the feed metal because the boiling units are separate from the rectification columns and constructed with silicon carbide brick arches through which the heat is transferred radiantly to the zinc. A zinc refiner of novel design has been in operation since January 1959 at the Blackwell, Okla. plant of the Blackwell Zinc Co., Inc., a wholly owned subsidiary of American Metal Climax, Inc. Developed by the company's technical and operating staffs, the new refiner produces special high-grade zinc (nominally 99.995+ pct Zn) from the prime western1 slab output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyromet-allurgical, high-capacity unit employing fractional distillation to separate zinc from its impurities, consisting principally of lead, cadmium, and iron. In prime western slab, these elements may vary in concentration from 0.005 to 1.6 pct. Table I shows the impurities usually encountered in the Blackwell prime western metal fed to the refiner together with their boiling points and vapor pressures at 907oC. The commercial pyrometallurgical smelting processes for extracting zinc from ore include distillation from retorts and a limited degree of refining can be accomplished by redistillation in similar retorts. To achieve special high-grade purity, an impractical number of batch redistillations would be required, however, with an accompanying loss of much metal. A continuously operated and integrated unit is required in which fractional vaporization and condensation can take place in a large number of stages. The first commercial continuously operated unit was developed by the New Jersey Zinc Co.4 In the separation of any two substances the degree of separation is limited if a mixture exists having a constant boiling point. The Zn-cd5 and Zn-pb6 systems contain no constant boiling points and hence these metals may be separated to any degree of purity. Basically, the pyrometallurgical refining of zinc involves three steps: a) iron, copper, and other metals having no appreciable vapor pressures at 907ºC concentrate in the bath when the impure zinc is boiled, b) lead, bismuth, antimony, and other metals having boiling points above but closer to that of zinc are selectively condensed from the vapor boiled from the bath, and c) cadmium and other metals having lower boiling points than zinc are fractionally distilled by reboiling and subsequent condensation of the zinc from the vapor. The boiling and condensation of zinc must be conducted in vessels constructed of materials which are refractory at the temperature involved (907 ºC) and it is highly desirable that they also be resistant to attack by the various metals. This requirement dictates construction from relatively small, simply shaped pieces which limits the pressures which may be employed to avoid leakage through the numerous joints. Stresses induced must be limited essentially to compressive ones and suitable provision must be made to permit thermal expansion of the components in order to minimize these stresses. Where heat is to be added for boiling or removed for condensation, refractory material through which the heat flows must have a high thermal conductivity. Silicon carbide is highly conductive but is subject to attack by iron and is expensive compared to other commonly employed refractories. A hard, dense aluminous fireclay is well suited to contain these metals where high thermal conductivity is not required. Zinc will penetrate the pores of fireclay brick but only to a limited depth in an exterior wall and has little effect other than an increase in weight and conductivity. The design objectives of the Amax refiner were: a) to achieve a long life by heavy, rugged construction and by employing silicon carbide refractories only where required for heat conductivity and not in contact with liquids of high iron concentrations, b) to simplify operation, manning and control by essentially horizontal construction, and c) to obtain high capacity in a single unit. DESCRIPTION Flow of metal through the Amax refiner is shown diagrammatically in Fig. 1 and schematically in Fig. 2.

Jan 1, 1963

By J. J. Pfeiffer, A. A. Oming, J. W. Myers

The method used to process washery refuse for use as a building material aggregate is described. Results of studies made in investigating this process are summarized. The Bureau of Mines, in cooperation with two commercial coal producers, studied the feasibility of using coal washery refuse in manufacturing lightweight aggregate for building materials. Lightweight aggregate is used in making masonry products of lower bulk density than can be produced from conventional aggregate such as sand, gravel, and crushed rock. Among the advantages of lightweight masonry are reduced deadweight loads which reduce materials cost, lower cost of construction labor, and improved thermal and sound insulation. A process for making lightweight concrete aggregate from coal-washery refuse appeared attractive because of the availability of raw material which contained sufficient fuel to carry out the processing. Vast quantities of such refuse have accumulated throughout the coal-producing areas of the U.S. Generally it is stored in unsightly piles, creating a problem of air pollution and using space that could be devoted to other purposes. Conversion of the refuse to lightweight aggregate could remedy these conditions and effectively utilize a material normally considered waste. The first part of the program was conducted in cooperation with the Truax-Traer Coal Co. to determine the feasibility of utilizing refuse from the company's coal preparation plant at Ceredo, W. Va., in manufacturing lightweight aggregate. The aggregate was to be used in making cement blocks comparable to those known in the building trades as cinder blocks. This project was completed in 1954. Based on the results of this work, the cooperator began commercial development and formed the Trulite Corp. for this purpose. A plant capable of handling 120 tpd of refuse was constructed for approximately $120,000. It began operating on June 1, 1955.' In 1959 a similar study was made, under a cooperative agreement with the Carbon Fuel Co. of Charleston, W. Va., to rrscertain the suitability of refuse from its plant for conversion to lightweight aggregate. Under this program various modifications of equipment were made, and the investigation of process variables begun in the previous project was extended. PROCESSING METHOD The formation of lightweight aggregate from coal-washery refuse js governed, in part, by the fusion characteristics of the mineral constituents of the refuse when heated above their softening temperatures. The heat required for this purpose is supplied by the combustihle matter in the refuse. Some of this combustible matter is coal with high ash content, but most of it is carbonaceous shale. Whereas the density of aggregate prepared from clay or shale depends largely on expansion, the density of aggregate made from refuse is reduced by burning out the combustible matter and, to a lesser extent, by expansion of the residue in the fuel bed. A chain-grate stoker with an updraft air system was chosen for the conversion process in preference to a downdraft sintering machine or a rotary kiln. In down-draft sintering, which operates on the overfeed burning principle, the volatile matter from the refuse would distill off without burning, resulting in inefficient combustion and interfering with proper operation of the equipment. The rotary kiln is designed primarily for processing material that lacks, or is low in, combustihle matter with the heat of reaction supplied from external sources. Washery refuse, which is relatively high in carbonaceous material, could burn at the wall of the kiln causing clinker formation with resultant decrease in throughput and increase in production cost. With an up-draft air stream on a chain or traveling-grate stoker, the volatile matter would be carried into the ignition and burning zones where the heat could be utilized more efficiently. The combustion procedure in this type of unit may be considered as consisting of four periods: 1) initial ignition of the top of the bed by furnace radiation, 2) ignition travel through the bed until the whole bed is ignited, 3) burnout of the combustible material with high air rates to fuse and expand the residue, 4) a cooling period. Investigation of the process required a study of the variables that affect both

Jan 1, 1962

By J. E. Burke, A. M. Turkalo

IN 1923 Desch¹ pointed out that the grains in a metal which is anisotropic with respect to its thermal coefficient of expansion would contract differently upon cooling, and that the stresses developed might approximate the plastic strength of the metal. More recently Boas and Honeycombe2-5 studied the behavior of several metals upon thermal cycling and observed that the stresses developed in arlisotropic metals are great enough to produce slip lines in individual grains and a roughening of the specimen surface. This phenomenon they have named "thermal fatigue." The mechanism they propose involves essentially a kneading of the grains, the deformation being alternately in compression and tension in a given grain as the temperature is changed in one direction and then the other. The present work was undertaken to investigate the possibility that an additional mechanism might operate to produce plastic deformation during thermal cycling—a "thermal ratchet" that depends upon a combination of grain boundary flow to relax the stress that develops between differently oriented grains upon raising the temperature and transcrys-talline slip to relax the oppositely directed stress which develops on lowering the temperature. Thus, thermal cycling should produce a nonreversible distortion such that certain grains will change shape differently from their neighbors with a simultaneous displacement being produced at the grain boundary. Temperature Dependence of Grain Boundary and Grain Strength The critical resolved stress for the initiation of slip in metal grains is only mildly affected by temperature." For example, in cadmium it decreases from 0.15 to about 0.05 kg per sq mm when the temperature is increased from 20° to 458°K and further temperature increase causes little further decrease. On the other hand, the work of KG1 indicates that the grain boundaries behave in a viscous fashion that can be described8 by the expression: t = BVexp(Q/RT) [1] t is the shearing stress on the boundary; B, a constant; V, the flow rate at the boundary; Q, the activation energy for grain boundary flow; R, the gas law's constant; and T, the absolute temperature. Eq 1 indicates that the stress necessary to cause a given grain boundary flow rate, V, decreases rapidly with increasing temperature. The value of the constant B is such that at sufficiently low temperature and ordinary strain rates deformation will occur preferentially by slip rather than by grain boundary flow. There is considerable evidence to indicate Consider the bicrystal shown in Fig. 1. In grain 1 the slip plane lies 45 " to the boundary while in grain 2 the slip plane is 90" to the boundary. The coefficients of expansion of the grains in a direction parallel to the length of the crystal are a1 and a, with a, > a2 for the orientations shown. The sequence of events that can occur upon heating and cooling this specimen is illustrated schematically in Fig. 2. Initially there is assumed to be no stress in the specimen (A). Upon heating, grain 1 attempts to become longer than grain 2, but is constrained by grain 2. Thus grain 1 is loaded in compression and grain 2 is loaded in tension, and a shearing stress is present across the boundary (B). As the temperature is increased, the stress will build up, and finally grain 1 will be plastically deformed by slip, since the greater stress is resolved on its slip planes. Any further heating will result in more slip and the stress will remain constant until some temperature T* is reached where the stress can be relaxed by grain boundary flow.† At this relaxation temperature (C) a step will appear between grain 1 and grain 2. Further heating above T* will cause grain 1 to become relatively longer, but no stress will appear because the grain boundary is too weak to support the stress (D). Upon cooling again, at T* (E), the grain boundary will again be able to support a shearing stress, and upon cooling further, grain 1 will be loaded in tension and grain 2 in compression (F). When the decrease in temperature below T* is sufficient to impose the critical shear stress upon the slip plane of grain 1, it will be stretched by slip.

Jan 1, 1953

By P. S. Kotva

Dislocation substructures in superalloy matrices of varyzng co)npositions have been studied. In general, it has been found that the alloys can be classified into ''high", ''medium", and "low" stacking fault energy classes based on the type of dislocation substructure observed in the matrix and that the substructure can be correlated to the stacking fault energy. The effect of different types of dislocation substructure and dislocation reactions on the intragranulur precipitation of carbide phases has been studied. In a Ni-Cv-Mo-Fe matrix, precipitation of MC carbides in association with stacking faults has been observed. In most superalloys, solid-solution strengthening and precipitation hardening are the chief mechanisms employed to achieve strength. The latter contribution to strength is usually achieved by the precipitation of / in certain wrought alloys. Insufficient attention has been given to the problem of obtaining strength in su-peralloys by controlling precipitation of carbides on imperfections within the matrix. The present work was undertaken to investigate the dislocation substructure in various superalloy matrices, to study the effect of such substructure on subsequent precipitation of carbides in the matrix, and to investigate whether certain modes of precipitation of carbide phases found in austenitic stainless steels2"4'6 would occur in nickel-base alloy matrices with dislocation substructures of the same type as those found in austenitic steels. 1) EXPERIMENTAL TECHNIQUES Five-pound heats of the various alloy compositions reported here were vacuum-cast. The ingots were given light deformation by rolling to break up the as-cast structure and then homogenized for 24 hr. HASTELLOY alloy X (nominal composition: Ni-2OCr-17Fe-8Mo-0.05C) was homogenized at 2150°F and In-cone1 625 (nominal composition: Ni-20Cr-5Fe-8Mo-3.5Cb-0.05C) was homogenized at 2280°F. Fabrication of 0.004-in. sheet was achieved by cold rolling with intermediate annealing treatments being carried out at the same temperature as those used for homogeniza-tion. Each solution anneal was followed by quenching. The aim of this procedure was to redissolve as much of the primary carbide phase as possible. Samples of the 0.004-in. sheet were cut and encapsulated in quartz capsules and then heat-treated in the tube furnaces. Thin foils were prepared using an ethanol-10 pct perchloric acid bath at 32°F and at a voltage of 22 v. A "window" technique was employed. Observations were made on a JEM-7 electron microscope operating at 100 kv. 2) EXPERIMENTAL RESULTS a) Types of Dislocation Substructure. Fig. 1 shows a schematic correlation between stacking fault energy, SFE, and the type of dislocation substructure observed in various matrices of nickel- and cobalt-base alloys. A precise quantitative determination of stacking fault energy is not implied in the figure but the correlation between stacking fault energy and the type of dislocation substructure obtained allows alloys to be divided into three classes in analogy with the classification employed by Swann and ~uttin~' for binary alloys of copper. Class I alloys are associated with a "high" SFE and show a cellular substructure of dislocations as typified by the micrograph of a thin foil of pure nickel deformed 4 pct at room temperature in Fig. 2. With decreasing SFE the tendency toward cell formation is lessened and dislocations tend to be arranged in coplanar groupings. Examples of this class of alloys with "medium" SFE are provided by the mi-crostructure of solution-heat-treated, quenched, and deformed thin foils of HASTELLOY alloy X, "Waspaloy" (prior to any aging), and Inconel 625. Fig. 3 shows a thin-foil micrograph of an alloy of Inconel 625 composition, solution-heat-treated, quenched, and deformed 5 pct at room temperatures. No evidence of any cell structure can be obtained in materials of "medium" stacking fault energy, Fig. 3, even after severe deformation. The stacking fault energy of the alloy shown in Fig. 3 is, however, not low enough to make the dissociation of dislocations visually obvious. As stacking fault energy decreases further, with successive addition of solute in the matrix, there is an increased tendency toward dissociation of dislocations and cross slip becomes progressively more difficult. Eventually, when the stacking fault energy is "low" enough, complete dissociation of dislocations is seen to occur as shown in Figs.

Jan 1, 1969

By Merlon C. Flemings, Theodoulos Z. Kattamis

Examination was made of the distribution of tnanganese and nickel in colutrrnar dendrites of a cast low-alloy steel; more limited work was corzducted on chromium. Corresponding "segregrction ratios" were calculnted and shown to be relntivelv insensitive to cooling rate (''segregation ratio" is defined (Is the ratio of maximum to minimum concentrations within a volume whose dimensions are the order of the dendrite-arm spacing). Isoconcentratiorl curves were determined by the electron micropvobe and by rt7etallografihic studies on specimens subjected to isothermal-transformation treatments. From construction of isoconcentration curves, morphology of columnar dendrites is descvibed as intermediate between Perfect rodlike and sheetlike morphologies. The study is extended to equiaxed dendrites and it is shown that the strcture of these dendrites is sittlilar in many respects to that of columnar dendrites. On the basis of tlze sheetlike morphology of dendrites, a simple model is pvoposed for calculation of honzogenization kinetics. Results of trzatllevlatical analysis brcsed on this utzodel are given. This analysis relates residual segregation to time at homogenization temperature; it is in agreement with experiment. Calculations are given which show that even for relatively rapidly cooled material (of 1-ine dendrite-artn spacing) treatmets at 1200°C or above are necessary to achieve slgxificant Izomogenization of elenlents other than carbon itz reasonable time (e.g., rnangclnese, nickel). Conlplete homogenization of carbon is obtnined at much lowev tenlperatures (below 870°C). IN dendritic solidification of castings and ingots, solute redistribution during freezing results in mi-crosegregation of most alloy elements. The micro-segregation is such that minimum solute concentrations occur at the center of dendrite arms and maximum concentrations occur between dendrite arms. Residual segregation after subsequent therma1 processing (homogenization) depends on maximum and minimum initial concentration, on the detailed geometry of the isoconcentration surfaces within interdendritic regions, on the diffusion coefficient of the solute, and on time of thermal processing. The objective of this work was to determine, for a low-alloy steel, maximum and minimum concentrations, and the geometry of isoconcentration surfaces, primarily in order to permit calculation of homogenization kinetics. Most of the work reported was conducted on Samples from a unidirectionally solidified, fully columnar ingot. This type of ingot is made by extracting heat during solidification from one face; techniques for accomplishing this have been discussed.' Samples were taken at several locations, up to 5.75 in. from the mold chill face; the bulk of the work was performed on samples at 5.75 in. Alloy cast was, nominally, 0.4 pct C, 1.8 pct Ni, 0.8 pct Cr, 0.7 pct Mn, 0.25 pct Mo, 0.3 pct Si, and the balance iron. Brief study was also made on samples from an ingot which solidified with equiaxed grain structure. SAMPLE PREPARATION AND ANALYSIS Samples for electron-microprobe analysis were incorporated in mounts that included pieces of electrolytic nickel, chromium, and manganese, in order to normalize the intensities of these solutes in the specimens; also, a piece of electrolytic iron was included to measure the background. All specimens were polished in the usual metallographic manner. After the microprobe traces were made, the path was revealed by etching the specimens with picral. All microprobe analyses were made by point counting, integrating for 30 sec. The distance between points was fixed from 2 to 10 p, according to the precision desired in each case, the fineness of the structure, and the concentration gradient existing in a given area. (The distance was chosen 2 to 5 p near the maximum-concentration regions and 5 to 10 p near the minimum concentration.) The "take-off" angle for the A.R.L.-Model No. 21000 microprobe employed was 52.5 deg. Samples for metallographic analysis of isoconcentration curves were prepared by austenitizing at 1540°F for 20 min, quenching to the nose of the TTT curves (1200°F), heat treating isothermally at this temperature for a given time 0, and then quenching to room temperature. Due to concentration gradients existing in a dendritic structure, no transformation will take place for a given time 0 of isothermal heat treatment in the regions where the a.lloy concentration is higher than a given limit. Thus, the dendrite appears limited by an isoconcentration curve and can be made to appear to grow by varying the time of isothermal heat treatment.

Jan 1, 1965

By B. C. Allen

Liquid surface tensions of copper and 18 Group IV-A to VIII transition metals (Ti, Zr, Hf, V, Cb, Ta, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt, Fe, Ni. Co) have been measured by the static pendant-drop and dynamic drop-weight methods on the same rod sample. The drops were formed by electron-bombardment heating in high vacuum. Application of necessary corrections enabled determination of surface tensions to k2 pct and agreement between methods to * 1 to 4 pct for all the metals studied. Evidence is presented that the liquid surface was well screened by metal vapor, suggesting negligible adsorption of gaseous impurities and that the surface tensions measured are characteristic of the metals involved. Correlations between liquid surface tension and melting point, molar volume, heat of vaporization, and atomic number are presented and discussed. Temperature coefficients of surface tension were calculated using Eötvös' law. SURFACE tension and interface energies of metals are the result of incomplete atomic coordination resulting in a force perpendicular to the boundary, tending to minimize its area. These energies are important in many phases of metallurgy, including microstructure, sintering, joining, electronic emission, and lubrication, which in turn affect many physical and mechanical properties of metals. Liquid surface tension refers to the interface between the liquid and its own vapor or nonreactive atmosphere, and is considered a physical property of the liquid. Since equilibrium shapes can be readily obtained with liquids, the units of surface tension (force per length) and interface energy (energy per area) are interchangeable. Thermo-dynamically, the surface tension ?LV is given by the change in free energy F with surface area A at constant pressure P, temperature T, and composition N: for commercially important refractory metals, vanadium, columbium, tantalum,13,14 molybdenum,14 and tungsten,l5 and none for the rare platinum-group metals and rhenium. Measuring the surface tensions of transition metals is difficult because of their high reactivity and melting points. Of the many techniques available,16-18 the pendant-drop 19-21 and drop-weight methods17,22 are considered superior because they can be modified to eliminate persistent sources of contamination such as supports and capillaries necessary in the popular sessile drop, capillary rise, and maximum-bubble-pressure techniques. The necessary modification is to melt a drop on the tip of a vertical rod, which provides support through a solid of the same composition.13,15 The object of the work was to study the surface-tension behavior of copper and transition metals, having reasonably low vapor pressures. Liquid surface tension of each pure metal was systematically determined by using a combination of the static pendant-drop and dynamic drop-weight methods on the same rod. Liquid drops were formed by electron-bombardment heating in high vacuum. EXPERIMENTAL WORK As indicated in Table I, the metals studied were high purity and generally were obtained in rod form. The exceptions were titanium and zirconium, which were machined from crystal bars, and molybdenum (tot 11, osmium, and ruthenium, which were sintered and arc cast into rods. All the metals were ground or swaged to desired sizes between 1- and 7-mm diam, and centerless ground round and smooth to a finish better than 50 µ in., rms. Each rod was thoroughly cleaned with steel wool, degreased, acid etched, and dried. In a typical run, the rod was vertically clamped in a modified floating-zone electron-bombardment furnace designed after Calverley23 and Carlson.24 The specimen was outgassed and maintained positive at several kilovolts in a dynamic vacuum of 10-5 to 10-7 mm. The bottom end was enclosed by a tantalum pillbox and heated by electrons emitted from a hot concentric tungsten filament mounted on a movable bracket. The bombardment power was slowly raised until melting was observed. Power requirements ranged from 30 w for copper to 1300 w for 4-mm tungsten. The stabilized and out-gassed drop of near-maximum size was photographed at 4. 1X on panchromatic film at desired time inter-

Jan 1, 1963

By S. Brunauer

The hydration of portland cement is treated as a chemical reaction and the changes in matter, in energy and the rate of change of the process are discussed, Portland cement is a mixture of four major and at least as many important minor constituents. In the hydration process, the four major compounds (trical-cium silicate, dicalcium silicate, tricalcium alumi-nate and tetracalcium aluminoferrite), plus gypsum and water form five or six new compounds. In spite o the great complexity of the reaction, considerable progress has been made in its understanding, primarily with the help of such research tools as X-ray diffraction and electron microscopy. The rate of the reaction can be followed by direct and indirect methods of measurements. The effects o composition, particle size (or specific surface), temperature and water-cement ratio on the rates of hydration are discussed. The hydration of portland cement is a chemical reaction accompanied by such highly important physical phenomena as heat evolution, setting and hardening. It is a vast and complex subject, on which hundreds of papers have been published. At the time of the writing of this paper, in October 1962, a two-volume book, which alone contains dozens of papers pertaining to cement hydration appeared in print.' The present paper deals with a few aspects of this vast subject, and the selection was not easy. The work reported here deals with some of the most recent investigations in the field. In any chemical reaction, the physical chemist is primarily interested in three things: changes in matter, changes in energy and the rate of change of the process or the speed of the reaction. This is true also of the chemical reaction between portland cement and water, and all three aspects of the reaction will be discussed. These three aspects are of vital interest to the engineer as well. Portland cement is not a cementing material — the hydration products, the new materials which form in the reaction, have the cementing action. The energy changes manifest themselves in a considerable evolution of heat, which may be useful or harmful. It is useful, for example, in winter concreting, but in very large concrete structures like dams, a large evolution of heat, which cannot be easily dissipated, may produce distress in the structure. Primarily for such a purpose was the Type IV or low heat portland cement developed. The speed of the chemical reaction is important because it determines the time of setting and hardening. The initial reaction must be slow enough to permit placing of the concrete before setting occurs. On the other hand, after the placing of concrete it is often highly desirable to obtain as rapid chemical reaction as possible. For this purpose the Type 111 or high early strength portland cement was developed. CHANGES IN MATTER Portland Cement: In a basic investigation, before one begins to study a reaction, one either knows the quantities and compositions of the starting materials, the reactants, or one determines them. This is obvious; the chemist expresses the changes in matter that occur in a reaction by a chemical equation, which has the quantities and compositions of the reactants on the left side of the equation and the quantities and compositions of the reaction products on the right side. The first question is then what to put on the left side of the equation in the reaction between portland cement and water? It is not very easy to answer this question. Portland cement is not a single chemical compound but a mixture of many compounds. Four of these are considered the major compounds, and at least four of the minor compounds also play important roles in the hydration reaction. In order to avoid complicating matters, the present discussion will be restricted primarily to the four major compounds, which constitute usually more than 90% of a portland cement. The relative amounts of these compounds vary from cement to cement. Actually not only the amounts but the compositions of these constituents also vary to some extent, but the variation in composition of the individual components will be neglected for simplicity.

Jan 1, 1963

By M. C. Flemings, T. Z. Kattamis

Dendrite morphology and grain size were studied in bulk samples of iron and nickel base alloys under-cooled up to 300°C. In the alloys studied, dendrite morphology gradually changes with increasing undercooling from the usual dendritic structure to a structure composed of cylindrical dendrite arms. At a critical undercooling of approximately 170°C in these alloys there is an abrupt transition to a fine-grained structure of spherical morphology. Final dendrite-arnz spacing of melts nucleated at less than the critical undercooling decreases with increasing undercooling and with decreasing distance from a chilled surface. Grain size of melts nucleated at greater than the critical undercooling decreases similarly with these factors. It is concluded that structure coarsening, with reduction of surface area as driving force, is the principal mechanism determining final dendrite-arm spacing in melts nucleated at small undercoolings and grain site in melts nucleated at large undercoolings. IN solidification of highly undercooled melts, nuclea-tion and growth of the solid is accompanied by a rapid release of latent heat of fusion. The heat release is sufficiently rapid in bulk specimens that it takes place essentially adiabatically with respect to the surroundings; hence the specimen heats up ("recalesces") to some maximum recalescence temperature. For bulk liquid metals and alloys, a simple thermal balance shows the undercoolings obtainable in bulk samples are not sufficient to lower the maximum recalescence temperature below the equilibrium solidus temperature. Hence, some liquid always remains at the end of recalescence; this liquid must solidify by rejection of heat to the surroundings. Metals, including iron and nickel base alloys, normally freeze with only a few degrees of undercooling. In general, nucleation begins on impurity particles present in the metal, at a "heterogeneous nucleation temperature" that is quite close to the equilibrium liquidus temperature. Very small droplets of metal can be undercooled considerably before nucleation occurs,1-4 presumably because subdivision of the liquid reduces the probability of solid impurity in a given droplet. Following early work on metal droplets,' a series of studies has shown that it is possible, without great difficulty, to undercool bulk samples of many metals and alloys. Undercoolings obtainable are approximately two tenths of the melting point for nickel, iron, copper, and other metals and alloys.5-9 Specimen sizes have generally been in the range of 50 to 500 g. Studies on undercooling to date have been concerned primarily with techniques of undercooling and with nucleation and growth kinetics. Only limited consideration has been given to dendrite morphology in under- cooled alloys. One such study, in bulk Cu-Ni alloy,8 showed that at small undercoolings a typical dendritic structure was obtained. At undercoolings the order of 175°C the structure of a Cu-40 pct Ni alloy became "ray or starlike", and a dense network of subbound-aries appeared. At still larger degrees of undercooling, of the order of 250°C, the structure became more random and included an ensemble of globular forms. Comparable results were obtained by walker10 on Cu-Ni alloys, and by Kamenetskaya et al.11 in research on Cu-Ni, Sb-Bi, Fe-Ni, and Fe-Cr alloys. In this work, study was made of the processing parameters influencing dendrite morphology and grain size in undercooled alloy melts. Experiments were specifically designed to show the effects of coarsening ("ripening") during solidification on final casting morphology. EXPERIMENTAL PROCEDURE Apparatus used was patterned after that of Walker,10 Fig. l(a). Melting was by induction under reduced pressure of helium. Two different types of crucible materials were used; there was no difficulty in obtaining substantial undercooling in both types of materials. Alumina crucibles were used for the bulk of the runs made, with a glass coating separating the metal from the crucible walls. Other runs were made using fused silica crucibles with or without slag coating. A graphite susceptor was employed around the crucible to aid in melting and to reduce melt stirring. The major portion of the experimental work was on

Jan 1, 1967

By Michael Taylor, Thomas W. BoBo

Currently two of the most important characteristics of construction aggregates are (a) the particle size distribution (psd) and (b) the “shape” of the aggregate particles. The long established test methods and standards for these properties require substantial resources and most suppliers can take samples and conduct tests at intervals measured in days (psd) or even months (shape). Furthermore these tests require time: so the results are available only after material has been stockpiled or shipped. In the rare cases where problems are found the out-of-spec material has often been shipped to points unknown. There are substantial advantages to be obtained if the psd and other geometrical properties could be obtained from the material as it moves through the production processes and if the results could be reported back within seconds or minutes to Plant Control Managers. This paper describes a single on-line system used to evaluate production of crushed material in a production quarry. The system consists of an enclosure (containing the camera and lighting etc.) mounted over a production belt. Images are fed by fiber optic cable to a nearby control room where the data are analyzed; stored; displayed; and made available for integration into a process control system. Numerous forms of display can be created according to the needs of the producer. Once programmed by an automation engineer all functions of operation are fully automated. The system has permitted over 400 tests per hour with a feed back time less than 2 seconds. Sufficient geometrical measurements are made so that many different “shape” factors can be computed on a similar time scale. The paper summarizes the results from approximately 100 shifts of about 8 hours each and compares the imaging method with the current standard hand methods. Study of the data generated showed that, when combined with additional plant information, the system can be used to generate additional useful control information.

Jan 1, 2005

By H. J. de Haan, L. Schenk

Scope for Thermal Recovery in Shell's Heavy Oil Fields in Venezuela The main heavy oil reservoirs on the East coast of Lake Maracaibo (Fig. I), known as "Bolivar Coast", initially contained some 20 billion bbl of oil in place with gravities in the range of 10 to 15° API. The current total production rate is about 400,000 B/D. Since the recovery to date is on an average only 12.5 percent of the initial oil in place, these fields offer a vast potential for secondary recovery methods. The reservoirs are characterized by moderate depth (generally 1,000 to 3,000 ft; maximum 5,000 ft), good formation properties such as net oil sand thickness (50 to 300 ft), high porosity (30 to 40 percent) permeability (1 to 3 darcies) and oil saturation (initially about 80 percent) and high oil viscosity (100 to 10,000 cp in situ), all of which are favorable for the application of thermal recovery processes. Since 1957, steam drive, steam "soak" and underground combustion have been tested or are being tested in this area.1-3 This paper deals with a major steam drive test in the Tia Juana field. The test was commenced in Sept., 1961, on the basis of encouraging results of laboratory experiments and pilot field tests, which will be discussed briefly. Early Laboratory Investigation of the Steam Drive Process In 1956 a series of model experiments was carried out in the Koninklijke/Shell Laboratorium, Amster- dam, to investigate the displacement of heavy oil by steam.' The prototype studied was a horizontal, un-consolidated heavy oil reservoir, subjected to a linear steam drive. The model, representing a slab from this reservoir along the main flow direction, consisted of a steel tube filled with oil-saturated sand, provided with layers of rock at the top and bottom to simulate conductive heat losses to cap and base rock. Lateral heat losses, perpendicular to the main flow direction, were minimized by insulating the sides of the model. Heat flow and viscosity and gravity forces were scaled by taking the steam injection rate and sand permeability inversely proportional to the geometric reduction factor of the model, and using materials (oil, steam, cap rock, etc.) identical with those of the prototype. The main feature of the process was a frontal displacement mechanism that was observed within wide ranges of injection pressure and rate, oil viscosity, initial oil saturation and sand permeability. The high stability of this front can be attributed to the high volumetric steam flow rates, combined with the reduction in oil viscosity. High recoveries were obtained due to the low residual oil saturation of about 15 percent in the zone swept by steam. The latter value pertains to the specific test conditions (heavy oil, uncon-solidated sand) and may be lower for light oil, due to the effects of steam distillation. The applicability of this experimental approach is limited, as it does not take into account the fact that

Jan 1, 1970