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By R. G. Stickney

INTRODUCTION The Basalt Waste Isolation Project, conducted by Rockwell Hanford Operations under contract to the U.S. Department of Energy, is assessing the feasibility of the disposal of commercial radioactive spent fuel/high-level waste in deep geologic formations in basalts beneath and within the Hanford Site in southeastern Washington State. The Basalt Waste Isolation Project mission is to identify and characterize a potential geologic repository site in basalt and to develop associated facilities and technology required for the potential permanent isolation of radioactive wastes in basalt formations. In support of the Basalt Waste Isolation Project, a laboratory testing program was conducted to evaluate the performance of the Council for Scientific and Industrial Research's "Doorstopper" biaxial strain cell. To support site characterization studies and the design of repository openings, in situ stress measurements will be conducted within the reference repository horizon (~970 m). The Doorstopper is one of the instruments being considered for use in these measurements. It was selected because it requires only a small volume of work to achieve stress relief, which is important in a closely jointed basalt. Also, test durations are short, permitting a large number of measurements to be made within a given time to increase confidence in the results. Within the reference repository horizon, temperatures are expected in the range of 40º to 60°C with a humidity of up to 100%. For this testing program, test conditions were selected to closely resemble those expected within the repository horizon. The Doorstopper test, mainly developed by Leeman (1964), is a strain rosette relief method of measuring rock stress in situ. The Doorstopper consists of a four element, 45º strain gage rosette

Jan 1, 1984

By E. C. Tveter, L. A. Roe

The authors present a general outline of the theory and development of heavy-liquid application to mineral processing. Patent literature and processes are reviewed with special emphasis on liquid recovery systems which have been employed or proposed. Advantages and disadvantages of the process are discussed together with the recent developments which have revived interest in this old concentration method. The most important single factor in this resurgence of interest is concluded to be the narrowing gulf between chemical engineering and mineral dressing which has opened the field for new concepts of mineral plant design. A partial summary of patents on heavy liquid separations is included. In spite of the fact that heavy-liquid separation with organic liquids has been used in the laboratory for over 50 years, this process has never graduated to large scale commercial use for any extended period. However, a variation of this process, the sink-float or heavy-media separation process has found wide acceptance and is used to separate minerals from diamonds to gravel. Materials used to increase the specific gravity of the pulps used as heavy media include sand, clay, barite, magnetite, galena, hematite, atomized lead and ferrosilicon. Because of the greater ease of recovery, the magnetic materials, magnetite and ferrosilicon, are the preferred media today. In the U. S. alone, heavy-media iron ore plants with a capacity of over 10 million tons of concentrate per year are in existence. Heavy-media separation involving use of solid, inorganic particles suspended in water rapidly found a wide range of commercial use with the introduction of magnetic media. The minerals engineer is experienced in working with suspensions and quickly learned to develop and control such media at a cost compatible to the type of separation desired. The natural superiority of a heavy liquid with uniform chemical and physical properties has never been questioned since its first use in laboratory mineral separatory procedures. It offers the only method for gravity separation of fine particles of relatively close specific gravity. The most important early attempt to make heavy liquid separations commercial were made by the DuPont Co. which began experimental work on Virginia limonite in 1904. The appended "Partial Summary of Patents" compiled by W.L. O'Connell of The Dow Chemical Co. demonstrates the quantity and sequence of this work. Both inorganic and organic parting liquids were investigated and numerous patents were issued on the use and recovery of these liquids. The work culminated in the heavy liquid plant of the Weston Coal Co. at Shenandoah, Pa. Chemical engineering design of this plant was the responsibility of Francis I. and Hubert I. DuPont. Heavy-liquid separation of coal almost achieved commercial status at this plant which actually processed over 20,000 tons of coal. The liquids used were tetrabromethane, pentachloroethane and trichlo-roethylene, with liquid losses ranging from 8.9 to 12.4 oz per ton of cleaned coal. The reasons for failure of this plant are not clear but probably involved toxicity problems as well as other problems in chemical engineering. Excellent economics were reported. A more recent pilot plant was built in 1954-55 by Norris Goodwin for the Inerto Co. to treat hectorite clay. This plant employed carbon tetrachloride in jigs with liquid recovery by evaporation. Although good separation was achieved, incomplete removal of the CCl, from the clay prevented commercial operation. The only present operations known to the authors employing heavy liquids for gravity separations are limited to the use of calcium chloride in certain coal washers and bromochloromethane in a small batch operation (one ton solids per day) for the separation of beryllium metal particles from slag materials. This is not strictly a minerals beneficiation problem but it has demonstrated the feasibility of such separations. PROBLEMS Critics of early attempts to commercialize heavy-liquid separation of minerals summarize the draw-

Jan 1, 1963

By Warren Blauvelt

IN VIEW of the enormous wastes of natural resources, of labor and of capital, due primarily to the economic environment, established by legislation, the general neglect of this phase of the problem of the elimination of waste is difficult to understand. In such a study, the engineering method of attacking a problem should be employed. The engineer does not try to solve his problem by disregarding natural laws, but by utilizing them. The successful engineer establishes an environ-ment in which forces, acting in harmony with natural laws upon an object or objects, will produce the desired results. The engineer who notices that the water level in a vessel, into which a gallon of water per minute is flowing, is two feet higher than the level in an adjacent vessel, connected therewith by a 6-in. pipe, does not assume that the law of gravity has ceased to work, or that water no longer seeks its level; he examines the connecting pipe for obstacles which prevent the free flow of water. Some editors, many reformers and most politicians tell us that the law of supply and demand no longer works; hence governmental control of commerce is necessary. Governmental control may temporarily-that is, until trial proves its futility- "insure domestic tranquility" and "promote the general welfare;" but it cannot "secure the blessings of liberty" which it cur-tails, nor can it "establish justice" which it violates.

Jan 9, 1922

By Parke A. Dickey

POTENTIAL differences between strata of shale and sandstone have been recognized for about 15 years, and they form the basis of the electrical logging of oil wells. Hitherto these potentials have been ascribed solely to electrochemical reactions caused by the disturbing effects of the water in the drill hole through which they are generally measured. Observations by the author in wells empty of water and in a mine shaft suggest that potential differences between sandstones and shales are natural and specific properties of the rocks, although they are modified to measurement by the disturbing effects of the water in the drill hole. The cause of these potentials probably is to be sought in the relative polar adsorptive capacities of quartz and clay particles.

Jan 1, 1944

By Chester T. Sims

RECENTLY, a new type of superalloy material called TD Nickel* has been marketed.' It is a sim- ple, two-phased alloy, consisting of thoria particles dispersed in nickel of rather high purity (Ni-2 pct Thoz). Its mechanical properties appear relatively superior to previous experimental material attempting to use the oxide nonmetallic dispersion concept (except SAP), and superior to conventional nickel-base alloys at high homologous temperatures. This is derived from an interesting method of creating the dispersion, arising during chemical processing of the nickel and thorium salts in solution while reducing the nickel to metal. An evaluation of the thoria phase was conducted at this laboratory. Material and Procedure. TD Nickel was made available, consisting of several inches of 0.470-in. rod, extruded at a ratio of 64: 1, straightened, and centerless ground. Property determinations on this rod by the supplier at 1800°F showed an ultimate tensile strength of 11,400 psi, yield strength of 9600 psi, and 6 pct elongation. Specimens were removed from the rod for as-extruded metallography, and two 1/2-in. lengths supported on high-purity Al2O9 bricks were placed in a laboratory muffle furnace for exposure at 2000° F. The furnace door was left cracked to allow a slight amount of circulation. One specimen was removed at 200 hr for examination; the other was left for 2000 hr. Metallography. The micro structures obtained for the three conditions of exposure are shown in Fig. 1. Elongation of the grain structure in the extrusion direction is readily evident. The grains appear to be up to 0.001 in. (0.003 cm) long, with a length/width ratio of about 10: 1. Allowing for modest local in-homogeneities in structure, no significant change in thoria particle size or nickel alloy grain size occurred during the 2000°F exposure. However, etching depth varies slightly from one specimen to another, changing the number of particles visible. The thoria dispersion appears to be in the order of 0.01 (min) to 0.5 (max) p diam. The minimum diameter is difficult to estimate at X10,000, and may be less. Interparticle spacing appears to be about 0.1 p. Etching effects can be seen, depending upon grain orientation. A cubic etch-pit pattern appears in certain grains, apparently when etching is started by an anodic particle of thoria, Fig. l(c). The cubic pattern appears related to crystallographic orientation, and is prominent when the [ l00 ] direction is perpendicular to the plane of polish. The grains which present a ridged appearance in the photograph appear to be oriented with the [110} direction perpendicular to the plane of polish. Analysis. The thoria particle size was measured by a line intercept method perpendicular to the extrusion direction. Only particle sizes measuring 0.001 in. at X10,000 or larger could be extimated. Within limits of experimental error, particle size distribution appears to be unaffected by exposure, Fig. 2. To check structural stability further, a grain-growth evaluation was made. The number of grain-boundary intersections was counted at X500 on each of several traces normal to the extrusion direction for each condition. It can be seen from Table I that grain diameter appears unchanged by the 2000°F exposure. The slightly finer grain diameter after 200 hr may be attributed to variations in grain size from area to area in the original extrusion. From the present rather limited study of Ni-2 Th on, it appears that: 1) for time-temperature exposure up to 2000 hr at 2000°F (Larsen-Miller parameter = 57, homologous temperature = 0.8) thoria particles of the size studied are highly thermally stable; they do not significantly react, agglomerate, or diffuse; and

Jan 1, 1963

By L. C. Uren

Field studies and laboratory research have established the fact that the expulsive force which drives petroleum into wells, from the reservoir sands in which it is stored by nature, is primarly an expression of the energy latent within compressed natural gas dissolved or occluded in, or otherwise associated with the oil. Each barrel of oil produced is forced into the recovery well by the expansive energy of a certain volume of compressed gas, originally stored with the oil in the pores of the reservoir rock; and each cubic foot of gas so produced with the oil and expanded to atmospheric pressure reduces by so much the total natural energy available for oil expulsion. This relationship between the volumes of gas and oil produced has seemed so important that petroleum production technolo-gists have come to regard the "gas-oil ratio," or the "gas factor" as it has been more conveniently termed, as a measure of oil-production efficiency. Different methods of oil recovery and production devices are now Com pared on this basis and estimates of ultimate recovery obtainable through their use are considered by many to be inversely proportional to the values of their respective gas factors. The writer has been among those who have given support to a widcspread movement toward a proper recognition of the significance of the gas factor as a guide in the control of producing oil wells, and does not wish to oppose its more extended application. It seems necessary, how-cvcr, in view of the almost elemental faith with which the principle of the gas factor has been received in many quarters, to point out that it is a most complex factor, and one which cannot be regarded as an absolute index of production efficiency without due regard to other contributing factors by which it is influenced to an important degree. Variables Influencing Gas Factor The mere recording of a low gas factor, obtained through the use of some method or device, does not necessarily imply efficient oil production; and conversely, a high gas factor does not always signify inefficient recov-

Jan 1, 1928

By Renato G. Bautista, Robert A. Hard

A comparative study has been made of the ex-tractability of several of the transitim metals from thiocyanate sohtions using methyl isobutyl ketone as the organic solvent. Extractions were made of scandium (III), chromium (III), manganese (II), iron (III), and cobalt (II), of which only the scandium , iron, and cobalt were readily extracted. All extractions were made at pH 2 and at 25.5 °C. A series of extraction experiments was made on scandium, iron, and cobalt to determine the effect of thiocyanate cmcentration added as the ammonium and also as the calcium salt. Also determined was the effect of metal ion concentratim and ionic strength on the distribution ratio. Analyses of the organic extracts indicated the scandium and iron were extracted principally in the uncharged trithiocyanate form, while the extractable form of the cobalt contained the cobaltotetrathiocyanate anion. THE chemical separation of metal complexes in solution by solvent extraction has in recent years been developed for large scale separation as well as bench scale work in the laboratory. It has also found increased application in analytical chemistry. Its extension to extractive metallurgy as a unit operation is best illustrated in the recovery of uranium and vanadium from their leached liquor.5-8 The extractability of some thiocyanate systems have been extensively investigated. The rate earths have been separated from one another using butanol as a olvent. Scandium was effectively extracted in ethyl ether using ammonium thiocyanate as the com-plexing agent.'' Similarly, the separation of hafnium from zirconium has been reported using ether""' or hexone13 as the organic solvent. The extractability of various metal thiocyanates in ethyl ether is given by 0ck.l Sharp and Wilkinson15 prepared nickel-free cobalt slats by thiocyanate extraction. The mechanism of extraction of titanium (IV) thiocyanate with methyl isobutyl ketone was determined by elafosse.''" The characterization of cobalt (TI) thiocyanate complex using methyl isobutyl ketone as the solvent at near neutral aqueous solution and the spectrometric studies of the ex-tractable cobalt complex has been made by Hard." It is noteworthy to mention at this point that the fundamental characteristic of ketone (oxonium) solvent extraction is that the extractable species are uncharged ion pairs solvated by the ketone molecules, but probably still partially hydrated.

Jan 1, 1963

By Harry Klemic

Zirconium and hafnium minerals are used industrially both as minerals valuable for their chemical and physical characteristics and as ores of zirconium and hafnium. The principal zirconium-hafnium-bearing minerals, their composition, and their ranges in content of zirconium and hafnium dioxides are listed in Table 1. The supply of zirconium and hafnium is based almost entirely upon the supply of the minerals zircon and baddeleyite. Eudialyte may eventually also be of importance as a source of these elements. Zircon, which generally contains nearly 49% zirconium and between 0.4 and 1.5% hafnium, is the principal industrial mineral of this group. Baddeleyite, a commercially important but less abundant mineral, contains as much as 73% zirconium and 0.4 to 1.7% hafnium. Eudialyte has a wide range in content of these elements, but analyses of material from several localities indicate values of 6 to 11 % zirconium and 0.07 to 0.4% hafnium. Zircon is a mineral consisting principally of zirconium, silicon, and oxygen that crystallizes from magmas during the formation of igneous rocks. Zircon also occurs in veins and in metamorphic rocks. It is in the tetragonal crystal system. It commonly forms as small well-developed prisms having pyramidal terminations but also occurs as irregular-shaped grains. Zircon has a hardness of 7.5 on the Mohs' scale. Its specific gravity is commonly between 4.68 and 4.70 (Dana, 1932), but the specific gravity varies somewhat depending upon com- position and state of alteration. Zircon has no good cleavage directions and is brittle, breaking with a conchoidal fracture. Zircon of the composition ZrSiO, would contain 67.2% Zr02 and 32.8% SiO2. However, in addition to about 1 % of hafnium, minor amounts of thorium, uranium, rare earth elements, yttrium, calcium, magnesium, iron, aluminum, phosphorus, and hydrogen, and trace amounts of other elements are commonly present in the mineral (Frondel, 1957). Radiogenic lead and other daughter products from the radioactive decay of uranium and thorium also accrue in the mineral. Radiation damage to the structure of zircons that contain appreciable amounts of uranium and thorium may alter the internal structure of the crystals to

Jan 1, 1975

By K. Y. Lo, R. S. C. Wai, R. K. Rowe, L. Tham

Laboratory tests for the determination of thermo-mechanical proper- ties of three rock types were performed at temperatures up to 400°C. Results showed that for the medium and coarse Granitic Gneisses, the coefficient of thermal expansion and Young's modulus are strongly temperature and temperature history dependent. A threshold temperature exists for each rock type above which material nonlinearity becomes important, and is associated with the progress of thermal cracking. Finite element computations were performed to illustrate the influence of material nonlinearity and boundary constraint on thermal stresses. Finally, a case history of thermal spalling was analyzed and it is shown that the results of analysis are consistent with field observations.

Jan 1, 1982

By Carl H. Beal

DURING the latter part of 1915 and the first half of 1916, the writer held the position of geologist in connection with the conservation work instituted by the U. S. Bureau of Mines, on oil and gas land belonging to the Indians of the Five Civilized Tribes in Oklahoma. The duty of the geologist was to correlate formations containing oil, gas, and water, and to determine the relations of these substances in the different formations so that the conservation agents might carry on their work most intelligently. On account of the rapid development of the Cushing field, which lies in the western part of the Creek Nation, much work was done there by the inspection force. In the course of the geologic studies a large amount of information was collected, which, on analysis, has disclosed some interesting facts worthy of publication. The report, of which the following remarks are an abstract, has been prepared and submitted to the U. S. Geological Survey for publication. This report is now (June, 1917) in the press and will doubtless be issued in a few weeks. Methods Used In addition to the structure maps showing the folding of the Pawhuska limestone, which crops out in several places in the Cushing field, separate structure maps of the three most important productive sands—the Lay-ton (Fig. 2)) Wheeler, and Bartlesville—have been prepared. These structure maps were prepared by obtaining the logs of nearly all the wells

Jan 1, 1918

By H. D. Hagen, C. E. Nelson

14.1-1. Coal Mining. CORPORATE STRUCTURE. Most coal companies that operate surface mines had their beginnings as basically one-man organizations, with all decisions and controls in the hands of the founder. At the early stage of the company development, it is usually quite possible for one man to handle all management functions as the mining operations generally are quite localized and the founder can have a first-hand knowledge of all facets of the operation. However, with continued growth, the entrepreneur finds that he must limit himself more and more to the top level of management and delegate the day-to-day operation to others. An organization must be developed that provides not only for current operations but also for continued growth of the company through acquisition of coal reserves in market areas that the company desires to serve. In general, a successful coal company engaged in surface mining must develop an organization consisting of the following departments or divisions: operations, sales, engineering, exploration, land, purchasing, financial, and legal. Of course, all of these departments are not required in the beginning. When the company is small, there is much overlapping of functions. For instance, the operating department will handle purchases and the engineering department will also handle exploration and land functions. A growing surface-mining company has generally evolved through the various stages of development into an organization that is typical of large mining companies. An examination of a typical company and its various departments and their functions should give an insight into the organizational trends of surface mining companies. Having begun as a typical one-man organization, a company of today can be highly centralized, with firm control of all phases of the company's operations in the executive offices. This is achieved by having all department heads (Fig. 14.1-I), as well as the senior management, based in central offices.

Jan 1, 1968

By G. W. Powell

ACCORDING to crank,' the accumulation equations for inter diffusion in a binary system whose molal volume is a function of concentration are

Jan 1, 1965

By W. H. Porter, M. E. Wadsworth, J. R. Lewis, K. L. Leiter

The oxidation of Cu2S in oxygen and the sulfating of Cu2O in oxygen-sulfur dioxide atmospheres was carried out under a variety of conditions. The oxidation of Cu2S was found to be retarded by entrapment of SO, and O2, which stabilized internal sulfates for long periods of time. The course of the reaction was followed by measuring weight changes and also by SO, evolution. Sulfating of Cu2O was a maximum at ratios of SO, to O2 approximating maximum SO, production. At elevated temperatures SO, was found to increase the rate of oxidation of Cu2 O to CuO even though sulfates did not form. All sulfating reactions followed the parabolic rate law indicating diffusion. MANY studies of the roasting of copper sulfides have been reported in recent years. Diev et al.1 investigated the roasting of chalcocite (Cu2S) in air, and oxygen enriched air. Lewis et al.2 also studied the oxidation of natural and synthetic chalcocite in air and oxygen atmospheres and their studies indicated that the maximum formation of water soluble sulfates occurred at approximately 450oC. Ashcroft3 reported that oxide production during the roasting of chalcocite resulted only from secondary decomposition of sulfates which were formed as primary products. peretti4 refuted this claim by showing that a layer of Cu2O appeared directly adjacent to the Cu2S during roasting of cylindrical briquettes of cupric sulfide, CuS. The linear advance of the Cu2S-Cu2O interface was used as a measure of the kinetics of the roasting reaction. The reactions proposed were: 2 CuS—Cu2S + 1/2 S2 [4-1] 1/2 S2 + O24 SO2 [4-2] cuzs +3/2 O2 4 Cu2O + SO2 [4-3] cu2o + 1/2 O2—2 cuo [4-4] At temperatures above 663oC, CuO was the only final solid phase reported. Below 663" C increasing amounts of sulfate were found mixed with the CuO. McCabe and Morgan5 investigated the roasting of discs of synthetic chalcocite and reported the following sequence of products beginning at the sulfide surface: Cu2O, a mixture of Cu2O and CuSO4, Cum,, CuO . CuSO4, and CuO. The principal reactions were reported to be: Cu2S + 3/2 O2-Cu2O + SO2 [5-1] CU2O + 2 SO2 + 3/2 O2—2 CUSO4 [5-21 2 CUSO4— CUO . cum, + SO3 [ 5-31 cuo . cuso4—-2 cuo + SO, [ 5-41 Eq.15-11 supports the claim of Peretti, Eq. [4-31, that CuzO is formed directly from Cu2S rather than as a secondary product from a sulfate as suggested by Ashcroft. On the other hand CuO was found to form as a secondary product from the decomposition of copper sulfate and basic copper sulfate, Eqs. [5-31 and [5-41. The formation of sulfates was explained by McCabe and morgan5 to be a direct reaction of Cu2O with 0, and SO, or SO, at distinct regions in which the partial pressures of each were such as to form the sulfate. Thornhill and pidgeon6 roasted both natural and synthetic chalcocite grains in air at temperatures between 420" and 550° C. They found a dense primary oxidation layer in contact with the sulfide. A secondary layer of porous oxidation products was found to expand with roasting time. The oxide products were leached away and the remaining core was studied by X-ray diffraction. The X-ray patterns showed an increased conversion of chalcocite to digenite with time. Digenite,7 a defect structure of cuprous sulfide, occurs naturally as Cu,-,S where x = 0.12 to 0.45, with an average analysis of Cu, ,S. The mechanism of digenite formation was proposed as: Cu2S + oxygen—Cu1-8S + 0.1 Cu2O [6-1] Cuj.eS + oxygen—0.9 Cu2S + SO2 [6-2] It is apparent from the above studies that the oxidation of Cu2S, ultimately ending in CuO, may be divided into ihree general stages (all of which may occur simultaneously): 1) primary oxidation to Cu2O; 2) secondary sulfate formation; and 3) sulfate decomposition. Consequently reactions of O2 and SO, with Cu20 constitute important aspects of the roasting of chalcocite. Virtually no studies have been made regarding sulfating reactions involving Cu,O. Mills and Evans8 noted the effect of sulfur dioxide on the oxidation of copper at low temperatures and low SO, partial pressures. They reported a measurable increase in the oxidation rate of copper when SO2, was present. Interest in the Cu2O-CuO-0, system has been limited predominantly to misciblllty studies and determinations of heats of formation by

Jan 1, 1961

I would like to congratulate the authors on an interesting paper and, in particular, on their justification of the use of superposition in treating gas wells. They state, however, that no theory has previously been developed lor treating the variable rate drawdown case. In a paper published a few years ago by my colleagues and myself, a method is described which allows a constant rate drawdown curve to be derived for any well. regardless of real rate variations. This method has the great advantage that it is not necessary to make any assumptions regarding the form or uniformity of the reservoir, and the derivation suggested by the present authors is simply an idealized case of our more general treatment. In the light of several years' experience in the derivation of constant rate drawdown curves: I would like to point out that the method proposed by Odeh and Jones may lead to confusing answers, particularly if applied over an appreciable time interval. The reason is that, if pressures are measured when a well is flowing, non-linearities in plots like Figs. 1 and 2 can arise due to either (1) changes in the skin factor with time and/or flow rate, or (2) an inhomogeneous reservoir. Separation of these two effects is only possible if some of the pressures used in the analysis are measured when the well flow rate is 0 or, in other words. during brief shut-in periods. REFERENCES 1. Arthur, K. B.. Metunomski, Z. G. and Ruche, Ms "Intetet ct methode d'utilisa tion des mesures de pression [)our Petude des gisemonts" Revue de T'I.F.P. (Nov., 1962) XVII, 1299. 2. Thomere, R. and Arthur, K. R.: "Analysis of the Pressure Bet~avior of a Production Well Subject to Interterence and Its Application to Reservoir Models", Paper SPE 1189 presented at SPE :Amund Fall Mecting Ireld in Denwer, Colo. (Oct. 3-6, 1965).

Jan 1, 1966

By G. R. Speich

The interlarnmelm spacing, growth rate, and degree of segregation that accompany cellular precipitation in four Fe-Zn alloys containing 9.7, 15.2, 23.5, and 30.5 at. pct Zn have been determined in the temperature range 400" to 600°C. The chemical free-energy change for the reaction was calculated from the available thermodynamic data and the known compositions of the phases. The fraction of the chemical free-energy change for equilibrium segregation that is converted into interfacial free energy decreases from 0.43 to 0.08 as the magnitude of this free-energy change increases from 35 to 270 cal per mole. At constant temperature the cellular growth rate is proportional to the cube of the dissipated free energy. At 600°C newly 100 pct of the equilibrium segregation is achieved during cellulm precipitation whereas at 400°C only 85 pct of the equilibrium segregation is attained. During cellular growth, mass transport of zinc occurs by grain boundary diffusion; excess zinc remaining in the a! phase after the completion of growth is removed slowly by volume diffusion. A modified Cahn theory of cellular precipitation predicts the observed interlamellar spacing within a factor of two. In cellular precipitation reactions such as pearlite formation or discontinuous precipitation, the basic problem is to predict the variation of growth rate G, interlamellar spacing S, and degree of segregation P with composition and temperature. To accomplish this we need three independent equations relating these quantities. One of these equations comes from the diffusion solution. To obtain two additional independent equations, some assumptions must be made. cahnl has suggested recently that two plausible assumptions are 1) that growth rate is proportional to the dissipated free energy and 2) that the spacing which occurs is that which maximizes the dissipated free energy. According to the first assumption, this spacing also maximizes the growth rate and the rate of decrease of free energy per unit area of cell boundary. The present work was undertaken to test these assumptions. To test the first assumption it is necessary to study a cellular reaction over a wide range of supersatura-tions to establish a relationship between G and the dissipated free energy at constant temperature. This is possible only in discontinuous precipitation reactions since in pearlite reactions constituents other than pearlite form if the composition of the parent phase deviates even slightly from the eutectoid composition. The Fe-Zn system was chosen for study because 1) discontinuous precipitation proceeds to completion over a wide temperature and concentration range, 2) the degree of segregation within the cell can be measured by lattice parameter measurements,2 and 3) the thermodynamics of this system have recently been determined by Wriedt.3 In this system the cells consisting d alternate lamellae of a and r phases form from supercooled iron-rich a phase. The a phase within the cells is bcc as is the original a phase, cia, but has a different orientation and a slightly lower zinc content than the original a phase. The r phase has a zinc content of about 70 at. pct and a crystal structure isomor-phous with T brass. EXPERIMENTAL PROCEDURE Four Fe-Zn alloys with 9.7, 15.2, 23.5, and 30.5 at. pct Zn were prepared from carbonyl-iron powder (400 mesh, 99.8 wt pct Fe) and zinc powder (200 mesh, 99.99 wt pct Zn). The powders were ball-milled together and cold-pressed under 60,000 psi to discs $ in. thick by $ in. diam. The cold-pressed discs of the alloys with 9.7 and 15.2 at. pct Zn were sealed in evacuated silica capsules and heated slowly to 1100°C over a period of 1 week (3 days at 600°C, then 3 days at 80O°C, then 1 day at 1100°C). The alloys with 23.5 and 30.5 at. pct Zn were treated similarly except that the final homogenization temperatures were 1000" and 85O°C, respectively, to prevent melting. The alloys were quenched in iced brine from the final homogenization temperature. Specimens of each alloy were subsequently aged in salt pots at temperatures of 400°, 450°, 500°, 550°, 600°, and 650°C for times that varied from a few minutes to several hundred hours. At a late stage of this work, an alloy containing 11.2 at. pct Zn was prepared by vapor-impregnation of iron foil with zinc vapor at 890°C. This alloy proved useful for electron microscope studies because it was free of porosity. The homogenization and aging conditions were based on the recent Fe-Zn phase diagram of Stadelmaier and Bridgers4 rather than the earlier diagram of ansen.5 They consist of a homogenization heat treatment in the homogeneous a field followed by an aging treatment in the two-phase a + r field. The aged specimens were metallographically polished and etched in 2 pct nital and the radius of the largest cell in the microstructure determined. This radius plotted vs time gave a straight line whose slope is the boundary migration rate or growth rate G of the cell. To determine the interlamellar spacing, specimens were examined by surface-replica and thin-section electron microscope techniques. Because of the irregular nature of the lamellae within the cell, the average interlamellar spacing S .of the cell was measured by the method of Cahn and Hagel,6 where S is defined by:

Jan 1, 1969

By Nicholas J. Grant, John Chipman

A full understanding of the behavior of sulphur in the basic open-hearth process has been delayed by lack of dependable data covering a wide range of slag conditions in the absence of other complicating factors that are likely to be present under operating conditions. It has been generally accepted that strongly basic slags will dissolve more sulphur than will those in which the acidic and basic constituents are more nearly balanced. It has been known that both slag and metal would absorb sulphur from the flame when the sulphur content of the fuel is high. It has been generally believed that manganese assists in the transfer of sulphur from metal to slag. Almost nothing has been known of the effect of temperature upon desulphurization;the data have been conflicting and there has been a tendency to depend rather heavily upon analogy with the better understood desulphurizing reaction of the blast furnace. Many attempts have been made to build up from open-hearth data a satisfactory theory of the chemical reactions involved in the process. That this has been an extremely difficult task is owing to two reasons that have been very generally recognized. The first is the parallel and simultaneous reaction of sulphur transfer between flame and bath. The second is the difficulty of distinguishing between the factors that ultimately limit the transfer from metal to slag—i.e., equilibrium conditions—and those whose influence is only upon the rate of transfer. It has been the object of the work here recounted to study the equilibrium distribution of sulphur between slag and metal in the absence of these complicating factors, with the hope that a better understanding of the equilibria involved would lead to a better control of the over-all process in the open-hearth furnace. A review of the literature on steelmaking reveals almost complete agreement with respect to the paramount importance of lime in promoting desulphurization. In expressing this effect in quantitative terms, however, and in formulating the relationships between the concentrations of other slag components and the desulphurizing power, there is little agreement. For instance, the "basicity" or basic strength of the slag is commonly measured by some kind of ratio of concentration of basic to acidic oxides. Of these, the following have been reviewed by Schenck:20 V radio = % CaO/%SiO, Körber and Oelsen's _ % CaO'. 100/% CaO + % SiO2 where (%CaO') = % CaO- 1.18% P2O5. Herty's B ratio = % CaO - (0.93 . % SO2) - (1.18% P205) Among others there appear the following: 20 References are at the end of the paper.

Jan 1, 1947

By Nicholas J. Grant, John Chipman

A full understanding of the behavior of sulphur in the basic open-hearth process has been delayed by lack of dependable data covering a wide range of slag conditions in the absence of other complicating factors that are likely to be present under operating conditions. It has been generally accepted that strongly basic slags will dissolve more sulphur than will those in which the acidic and basic constituents are more nearly balanced. It has been known that both slag and metal would absorb sulphur from the flame when the sulphur content of the fuel is high. It has been generally believed that manganese assists in the transfer of sulphur from metal to slag. Almost nothing has been known of the effect of temperature upon desulphurization;the data have been conflicting and there has been a tendency to depend rather heavily upon analogy with the better understood desulphurizing reaction of the blast furnace. Many attempts have been made to build up from open-hearth data a satisfactory theory of the chemical reactions involved in the process. That this has been an extremely difficult task is owing to two reasons that have been very generally recognized. The first is the parallel and simultaneous reaction of sulphur transfer between flame and bath. The second is the difficulty of distinguishing between the factors that ultimately limit the transfer from metal to slag—i.e., equilibrium conditions—and those whose influence is only upon the rate of transfer. It has been the object of the work here recounted to study the equilibrium distribution of sulphur between slag and metal in the absence of these complicating factors, with the hope that a better understanding of the equilibria involved would lead to a better control of the over-all process in the open-hearth furnace. A review of the literature on steelmaking reveals almost complete agreement with respect to the paramount importance of lime in promoting desulphurization. In expressing this effect in quantitative terms, however, and in formulating the relationships between the concentrations of other slag components and the desulphurizing power, there is little agreement. For instance, the "basicity" or basic strength of the slag is commonly measured by some kind of ratio of concentration of basic to acidic oxides. Of these, the following have been reviewed by Schenck:20 V radio = % CaO/%SiO, Körber and Oelsen's _ % CaO'. 100/% CaO + % SiO2 where (%CaO') = % CaO- 1.18% P2O5. Herty's B ratio = % CaO - (0.93 . % SO2) - (1.18% P205) Among others there appear the following: 20 References are at the end of the paper.

Jan 1, 1947

By S. W. Miller

DURING the examination of welds made in steel by the oxy-acetylene and electric-arc processes, the writer has met with some unusual structures, which he has not encountered elsewhere. They seem to be quite closely associated with the welding methods used, and characteristic of them, and would seem to be worth noting, especially as the references to them in the literature are few, and their explanation not clear or complete. An introductory word or two about fusion welding may not he out of place. The oxy-acetylene process is based on the great and very local heat generated by the burning of acetylene in the presence of commercially pure oxygen, the two gases being thoroughly mixed before combustion. The theoretical temperature is somewhat under 4000° C., but on account of various losses, the actual maximum temperature is probably about 3000° C. 1 The electric-arc process, using a metal electrode, which is also the filling rod, generates a still higher and more local temperature. The actual temperature of the positive crater of the carbon arc is given as 3500° C.2 No figures have been found for the temperature of the arc using a metal electrode, but it would probably not be very different from that of the carbon arc, and probably higher than that of the oxy-acetylene flame. The greater localization of the electric arc is due to the fact that it is not surrounded by a large envelope flame as well as to its higher temperature; while the oxy-acetylene white cone, or welding flame, in which the carbon of the acetylene is burned to CO, is surrounded and preceded by -a long envelope flame, itself of quite high temperature, in which the CO is burned to C02, and the hydrogen of the acetylene to

Jan 2, 1918

Jan 1, 1985

By Y. C. Liu, R. H. Richman

Deformation and recrystallization textures of the a solid solutions of Cu-P, Cu-As, and Cu-Sb alloys are examined as a function of composition. It is found that the deformation texture of copper is unckanged up to a composition of 0.43, 0.41, and 0.24 at. pct of phosphorus, arsenic, and antimony, respectzvely, and then the transition to the 70 : 30 brass type of deformation texture proceeds linearly as the logarithm of the solute content. Recrystallization textures consist of strong, new components that do not all bear the usual<111> rotational relation to the deformation components. The dependence of the deformation texture transitions and the recrystallization orientations upon composition and solute-element type is discussed. A systematic evolution of individual recrystallization components in the annealing texture of copper was portrayed as a function of germanium or tin content in a previous study.&apos; Similar patterns of tex-tural change have been observed with copper-zinc alloys,2 and in less detailed studies of other systems.3,4 In fact, most of the literature dealing with preferred orientations in copper alloys indicates that the influence of solute elements upon textures in copper is of one general type. As the alloy content of copper is increased, the deformation texture changes from the copper type to the 70:30 brass type, and the annealing texture undergoes a comparable change from the (001) [ loo] orientation of unalloyed copper to the {113} <211> type of 70:30 brass, with the notable exception of copper alloyed with Periodic Subgroup V-B elements.4-8 In almost every case it is possible to describe the reorientations after annealing as 30 to 40 deg rotations about <1ll> poles of the deformation components. Since there is apparently not much difference in the final textures of the copper binary systems already investigated, only a limited variety of preferred orientations has served as the basis for current theories of the origin of annealing textures. In order to test the validity of the proposed theories, and the possibility that the <111> rotations are not unique, it would be most desirable to study the reorientation relationships of additional, and heretofore unanalyzed, recrystallization components if such components exist. Examination of the literature reveals a good deal of uncertainty concerning preferred orientations in copper alloyed with elements in Subgroup V-B of the Periodic Table. Phosphorus is known to inhibit the cube texture in copper when present in amounts as low as 0.01 wt pct,8 but the recrystallized matrix that occurs instead of the cube orientation was reported as either random or weakly textured, with orientations not observed in Cu-Zn, Cu-Ge, or Cu-Sn alloys.4-9 A Cu-0.75 at. pct As alloy apparently contained, along with the (001)[100] and (113) <211> type of recrystallization components, {110} <112> and (110) <001> components, whereas an almost random distribution of orientations was found in alloys of higher arsenic content.4 A {110} <001> component also appeared in rolledand annealed Cu-Sb alloys, but otherwise the recrystallization textures of Cu-Sb alloys seem to con-

Jan 1, 1962