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By P. Greenfield, C. C. Smith, A. M. Taylor

The Mg-Zr alloy ZA and Mg-Mn alloy AM503(S) are shown to have a markedly improved resistance to creep deformation after suitable heat treatments. This improvement makes them suitable for certain stress-bearing fuel element components in nuclear reactors. The extent of strengthening is described and an explanation of the behavior of both materials is given, based on a combination of strain-aging and grain growth. The increase in operating temperatures of fuel element components in Calder Hall type nuclear reactors has necessitated the development of magnesium base alloys with a very high resistance to creep at temperatures up to 500°C. Such alloys are not required for fuel element cans, which require high-creep ductility rather than strength, but for can supporting and stabilizing components, which are needed to support the imposed loads without deforming more than about 1 pct in times of up to 40,000 hr. The amount and type of alloying addition made to magnesium for these parts is limited by the necessity of keeping the cross-section to thermal neutrons as low as possible. The alloys must also possess a high resistance to oxidation in CO2. Alloys which have been developed for this application include ZA, an alloy of magnesium with 0.5 to 0.7 pct Zr and AM503(S), an alloy of magnesium with 0.5 to 0.75 pct Mn. In the as-extruded condition these alloys are very weak and ductile in creep but it has been found that they can be strengthened to a significant extent by heat treatment. This paper describes the method of developing a high-creep resistance in ZA and AM503(S), the extent of the strengthening produced and discusses the probable mechanisms of strengthening. TEST MATERIALS Specimens were taken from typical casts of ZA and AM503(S) alloys extruded into 2 1/4-in.-diam bars, supplied by Magnesium Elektron Ltd. Typical analyses of the bars were as follows: The as-extruded mean grain diameter was 0.001 to 0.002 in. for the ZA alloy and 0.003 in. for the AM503(S) alloy. EXPERIMENTAL METHODS Extruded bars of ZA alloy, 2 1/4 in. in diameter and 9 in. long, were heat treated in electrical resistance furnaces in an atmosphere of flowing CO2 containing 50 to 300 ppm water, thereby reducing the extent of oxidation compared with that which would have occurred in air. Heat treatments were carried out at 600oc for times of 8, 24, 48, 72, and 96 hr and material was subsequently both furnace cooled and water quenched. In order to measure the effect of time of heat treatment, specimens were creep tested at 400°C and 336 psi for about 1000 hr. Subsequently, the behavior of material heat treated for 96 hr at 600°C and furnace cooled was tested at a variety of stresses from 200° to 500°C. Tests were also conducted at 200o and 400°C on material in the as-extruded condition for comparative purposes. With the AM503(S) alloy, only the effect of heat treatment at 565°C for 4 hr was examined. It has been shown1 that such a heat treatment produces marked strengthening in this alloy. Tests on this material were conducted at a variety of stresses at 200°, 300°, and 400oc with comparative tests on as-extruded material at 200o and 400°C. The creep tests were carried out on machines using dead-weight loading and direct micrometer strain measurements on specimens 5 in. long and 0.357 in. diameter. At temperatures of 400° C and below, the creep tests were conducted in air, but at higher temperatures an atmosphere of CO2 was used. Grain size measurements were made on ZA in the extruded and heat treated states and on each specimen after creep testing. This was done by a line count of a minimum of 20 grains in two or three random fields in the longitudinal and transverse directions. The same method was used for measuring the grain size of as-extruded AM503(S), but the grain size of the heat treated material was so large that this method could not be employed. For heat-treated AM503(S) the large grained characteristics (between 0.1 and 1 in.) were confirmed by the measurement of individual grains. In the case of the ZA alloy, specimens taken from various stages in the program were analysed for hydrogen by a combustion method. Material in various states was also analysed for the soluble and insoluble zirconium content by dissolving in dilute hydrochloric acid. This technique has been useda for the determination of amounts of zirconium present

Jan 1, 1962

By C. Gatlin, F. Armstrong, K. E. Gray

This paper presents some preliminary results of two-dimensional cutting tests of dry limestone samples at utmospheric pressure. Cutting tips having rake angles of + 30°, + 15", 0°, - 15" and - 30" were used to make cuts on Leuders limestone samples at six depths of cut ranging from .005 to ,060 in. at cutting speeds of 15, 50, 109 and 150 ft/min. The vertical and horizontal force components on the cutting tips were recorded with an oscilloscope equipped with a polaroid camera. Motion pictures of the cutting process at camera speeds of 5,000 to 8,000 frames/sec were taken at strategic points in the variable ranges. The movies provide considerable insight into the brittle failure mechanism in rocks. It appears that chip-generating cracks usually have an initial orientation which is related to the resultant of the externally applied forces. The latter part of the crack curves upward toward the free surface being cut, this part being governed by some type of cantilever bending or prying. The linear and angular motion of the loosened chips also indicate the tensile nature of brittle failure. Analyses of the forces on the cutting tips indicate that: (I) relatively small increases in vertical loading result in large cut-depth increases for sharp tips (rake angles 2 0"); (2) tool forces increase at an increasing rate as the rake angle decreases, particularly for rake angles < 0"; and (3), for the range of this study, rate of loading had little effect on the maximum forces. Both the movies and visual inspection of the cuttings indicated that the volume of rock removed by chipping was much larger than that by any grinding mechanism, even for tips having negative rake angles. Cutting size increases with increased cut depth and rake angles, and decreases slightly at high cutting speeds, the depth of cut having by far the most influence. The amount of contact between the rock and the cutting tip was always less than the depth of cut and rarely exceeded 0.010 in. even for cuts of 0.060 in. INTRODUCTION The planing (or slicing) of various materials with a fixed blade has long been practiced by workers in many industries. For example, the farmer&apos;s plow, the carpenter&apos;s plane and the housewife&apos;s paring knife all employ this basic action. The casual observer might suspect that something so common must be quite simple; however, as in all problems involving the failure of materials, such is not the case. Industries concerned with the machining of metals have long studied these problems, and their literature on the subject is voluminous. Despite these efforts, basic knowledge is not very advanced, as may be noted from recent and comprehensive analyses of their literature.12 Metals are more subject to analysis by classical theories of elasticity and/or plasticity than are rocks, since their elastic constants and strengths are reasonably well established in many cases. In spite of this relative "simplicity", Hill9 refaces his discussion with an admission that the mathematical solution to the machining problem is not known. Photoelastic studies of both machining and milling have been performed and are discussed thoroughly by Coker and Filon.4 Rotary drilling of rocks with fixed blade or drag bits has long been practiced by the mining and petroleum industries, and considerable study has been given to defining their cutting action in terms of the pertinent variables. Essentially all the published mechanistic research on drag-bit drilling has been performed by mining engineers and has been concerned only with rocks in the brittle state. Fairhurst5-7 has worked extensively in this area and employed photographic techniques quite similar to those reported here, except at much lower speeds. His studies showed the periodic or cyclical nature of the brittle failure mechanism, in which instantaneous loads on the bit varied from some maximum value to near zero. Goodrichs has presented further data on the subject as well as a qualitative description of the process. Again the postulated mechanism is cyclical, with alternate chipping and grinding periods. The ploughing of coal is a practiced method and has been studied in some detail by English mining engineers."" Their findings have considerable general application to drag-bit drilling. Evans," in particular, has extended Merchant&apos;s metal-cutting theory" to brittle materials with some success, although certain aspects of his theory are open to question. Fish13 has recently summarized nearly all the published works concern-

By Lawrence H. Van Vlack, Otta K. Riegger

Periclase-type oxides were examined microscopically after being exposed to siliceous liquids. The rate of grain growth was found to be inversely proportional to the grain diameter. Grain growth proceeds more rapidly at higher temperatures, but is retarded by increasing liquid contents. aMag-nesiowiistites with higher MgO contents grow less rapidly than those with higher FeO contents. The growth rate is reduced by the presence of a second solid phase. The silica-containing liquid penetrates as a film between the individual magnesiowus tite grains. This is independent of time, temperature, amount of liquid, or the MgO/ Fe0 ratio. When present, olivine and spinel-type phases can provide a solid-to-solid &apos;&apos;bridge" between magnesioustite grains. THIS paper presents the results of a study of the microstructures of periclase type oxides in the presence of a silicate liquid. The purpose was to learn more about the effect of service factors such as 1) time, 2) temperature, and 3) liquid content upon A) grain growth, and B) liquid location among the solid grains. This study was prompted by the fact that periclase refractories are known to have very little solid-to-solid contact when the phases which are present are limited to periclase and liquid. Such a micro-structure gains industrial significance because it permits fracture during service when stresses are applied at high temperatures. The details of ceramic microstructures have not received extensive attention. This is in contrast to the extensive attention given to a) the phase relationships pertaining to refractory compositions, and b) the details of the microstructures of comparable metallic materials. A brief review will be made of the pertinent phase relationships and microstructural considerations in general, as well as of refractory compositions. a) Phase Relationships. This investigation was limited to those compositions in which (Mg, Fe)O was the solid phase. MgO and FeO form a complete series of solid solutions. Pure MgO has the name of periclase. The related FeO structure is called wustite. Both have the NaC1-type structure: however, wustite possesses a cation deficiency so that the true composition is Fe<10 even in the presence of metallic iron. The phase relationships involving solid (Mg, Fe)O and a silicate liquid are shown in Fig. 1. In this case. the liquid is saturated with (Mg, Fe)o. There-fore its SiOz content is below that encountered in orthosilicate liquids. As a consequence the liquid phase specie:; are primarily the following ions: and 0-&apos; plus occasional Fe+ ions. Two features are of importance: a) the liquid contains relatively small species and b) the liquid contains large quantities of the same species as the solid. viz., Fig. 2 shows the system, FeO-SiOz, which will be used in some of the discussions that follow. This diagram is the right side, vertical section of Fig. 1. Here, as pre\iously, the composition at the FeO end of the diagram is nonstoichiometric, varying from Feo.950 when the liquid oxide is in contact with the solid iron, to about Fe 0, when the solid oxide is in equilibrium with an atmosphere of equal proportions of CO and C02 at the solidus temperature. The Fe/O ratio will be maintained in wustite in the presence of SiO,. However, the FeM/Fe++ ratio in the liquid will be lower because of the effect OIF the SiO, on the activity of the FeO. With the addition of MgO to wustite, the over-all composition (IvZg, Fe)@, has a value of x lying between 0.9 and 1.0 when the COz/CO ratio is 1.0&apos;. b) Microstructures. In general, published attention to refractory microstructures has been directed toward the phase analyses that accompany compositional variations. This is illustrated by Harvey6 in his work on silica brick and by wells7 in his work on periclase brick. In each case, a series of altered zones is encountered which provides a sequence of phase associations. If due consideration is given to reaction kinetics, such an examination reveals phases that are compatible with equilibrium studies. Admittedly, however, it is often necessary to determine more complicated polycomponent systems to account for all the phases present.8 Relatively little attention has been given to microstructural geometry in ceramic materials. Certainly less attention has been given to this aspect of ceramic microstructures than to the size, shape, and distribution of the constituent phases in metals. Burke has pointed out that the grain size of oxides follows the same growth rules as for metals, viz.,

Jan 1, 1962

By H. R. Thresh

An oscillational vis cometer has been constructed to measure the viscosity of liquid metals and alloys to 800°C. An enclosed cylindrical interface surrounds the molten sample avoiding the free surface condition found in many previous measurements. Standardization of the apparatus with mercury has verified the use of Roscoe&apos;s formula in the calculation of the viscosity. Operation of the apparatus at higher temperatures was also checked using molten lead. Extensive measurements on five different samples of zinc, of not less than 99.99 pct purity, indicate i) impurities at this level do not influence the viscosity and ii) the apparatus is capable of giving reproducible data. The variation of the viscosity ? with absolute temperature T is adequately expressed by Andrade&apos;s exponential relationship ?V1/3 = AeC/VT , where A and C are constants and V is the specific volume of the liquid. The values of A and C are given as 2.485 x 10-3 and 20.78, 2.444 x 10-3 and 88.79, and 2.169 x 10-3 and 239.8, respectively, for mercury, lead, and zinc. The error of measurement is assessed to be about 1 pct. Prefreezing phenomena in the vicinity of the freezing point of the zinc samples were found to be absent. AS part of an over-all program of research on various phases of melting and casting nonferrous alloys, a systematic study of some physical properties of liquid metals and their alloys was undertaken in the laboratories of the Physical Metallurgy Division.1,2,3 The most recent phase of this work, on zinc and some zinc-base alloys, was carried out in cooperation with the Canadian Zinc and Lead Research Committee and the International Lead-Zinc Research Organization. One of the properties investigated was viscosity and the present paper gives results on pure zinc; the second part, on the viscosity of some zinc alloys, will be reported separately. Experimental interest in the viscosity of liquid metals has virtually been confined to the past 40 years. The capillary technique was already established as the primary method for the viscosity of fluids in the vicinity of room temperature; all relevant experimental corrections were known and an absolute accuracy of 1 to 2 pct was possible. Ap- plication of the capillary method to liquid metals creates a number of exacting requirements to manipulate a smooth flow of highly reactive liquid through a fine-bore tube. Consequently, the degree of precision usually achieved in the high-temperature field rarely compares with measurements on aqueous fluids near room temperature. However, the full potential of the capillary method has yet to be explored using modern experimental techniques. As an alternative, many investigators in this field have preferred to select the oscillational method. Unfortunately, the practical advantages are somewhat offset by the inability of the hydrodynamic theory to realize a rational working formula for the calculation of the viscosity. In attempting to overcome this restriction many investigators have employed calibrational procedures, even to the extent of selecting an arbitrary formula for use with a given shaped interface. However, where calibration cannot be founded on well-established techniques, the contribution of such experiments to the general field of viscometry is questionable. A critical appraisal of the viscosity data existing for pure liquid metals reveals a somewhat discordant situation where considerable effort is still required to establish reproducible and reliable values for the low-melting point metals. The means of rectifying this situation have gradually evolved in recent years. Here, the theory of the oscillational method has undergone major advances for both the spherical and cylindrical interfaces. The basic concepts of verschaffelt4 governing the oscillation of a solid sphere in an infinite liquid have been adequately expressed by Andrade and his coworkers.5,6 Employing a hollow spherical container and a formula, which had been extensively verified by experiments on water, absolute measurements on the liquid alkali metals were obtained. The extension of this approach to the more common liquid metals has been demonstrated by culpin7 and Rothwel18 where much ingenuity was used to surmount the problem of loading the sample into the delicate sphere. Because of the elegant technique required to construct a hollow sphere, the cylindrical interface holds recognition as virtually the ideal shape. On the other hand, loss of symmetry in one plane increases the complexity of deriving a calculation of the viscosity. The contributions of Hopkins and Toye9 and Roscoe10 have markedly improved the potential use of the cylindrical interface in liquid-metal viscometry. The relatively simple experi-

Jan 1, 1965

By A. R. Orban, R. B. Engdahl, J. D. Hummell

The initial phase of a research program on smoke abatement from Bessemer converters is described. In work sponsored by the American Iron and Steel Institute, a 300-lb experimental Bessemer converter was assembled to simulate blowing conditions in a commercial vessel. Measurements of smoke and dust were also made in the field on a 30-ton commercial vessel. During normal blows the dust loading from the laboratory converter averaged 0.51 lb per 1000 lb of exhaust gas. This was similar to the exhaust-gas loading of a commercial vessel. The addition of hydrogen to the blast gas of the laboratory converter caused a decided decrease in smoke density. Smoke was also reduced markedly when methane or ammonia was added instead of hydrogen. The research is continuing on a bench-scale investigation of the mechanism of smoke formation in the converter process. DURING the past 2 years, on behalf of the American Iron and Steel Institute, Battelle has been conducting a research program on the control of emissions from pneumatic steelmaking processes. The objective of the research program is to discover a practical method for reducing to an unobjectionable level the emission of smoke and dust from Bessemer converters. PRELIMINARY INVESTIGATION Although conceivably some new collecting technique may be devised which would be economically practicable for cleaning Bessemer gases, no such system based on presently known principles seems feasible because of the extremely large volume of high-temperature gases involved. Hence, the research is being directed toward prevention of smoke formation at the source. A thorough review was first made of former work to determine the present status of the cleaning of converter gases. No published work was found on work done in the United States on collecting smoke or on preventing its formation in the bottom-blown, acid-Bessemer converter. In Europe, however, a number of investigations have been made on the basic-Bessemer converter. Kosmider, Neuhaus, and Kratzenstein1 conducted tests on a 20-ton converter to obtain characteristic data for dust removal and the utilization of waste heat. They concluded that because of the submicron size of the dust, special equipment would be necessary to clean the exhaust gases. Dehne2 conducted a large number of smoke-abatement experiments at Duisburg-Huckingen in a 36-ton Thomas converter discharging into a stack. A number of wet-scrubbing and dry collectors were tried unsuccessfully. A waste-heat boiler and electrostatic collector with necessary gas precleaners was felt to be the best solution for this particular plant. Meldau and Laufhutte3 determined that the particle size was all below 1 µ in the waste gas of a bottom-blown converter. Sel&apos;kin and zadalya4 describe the use of oxygen-water mixtures injected into a molten bath in refining open-hearth steel. They claim that with use of oxygen-water mixtures the amount of dust formed was reduced between 33.3 and 20 pct of its previous level, and emission of brown smoke almost ceased. Pepperhoff and passov5 attempted unsuccessfully to find some correlation between the optical absorption of the smoke, the flame emission, and the composition of the metal in a Thomas converter in order to determine automatically the metallurgical state in the melt. In a recent U. S. Patent (NO. 2,831,762)&apos; issued to two Austrian inventors, Kemmetmuller and Rinesch, the inventors claim a process for treating the exhaust gases from a converter. By their method the inventors claim that the exhaust gases from the converter are cooled immediately after leaving the converter to a degree that oxidation of the metal vapors and metal particles to form Fe2O3 is inhibited in the presence of surplus oxygen. Gledhill, Carnall, and sargent7 report on cleaning the gases from oxygen lancing of pig iron in the ladle. They claim the Pease-Anthony Venturi scrubber removed 99.5 + pct of the smoke, thereby reducing the concentration to 0.1 to 0.2 grain per cu ft, which resulted in a colorless stack gas after the evaporation of water. Fischer and wahlster8 developed a small basic converter and compared the metallurgical behavior of the blow with that of a large converter. Later work by Kosmider, Neuhaus, and Hardt9 on the use of steam for reduction of smoke from an oxygen-enriched converter confirmed that the cooling effect of steam is detrimental to production. From review of all of the published information on the subject, it was concluded that a practical solution to the smoke-elimination problem had not been found. Accordingly, it was deemed desirable to investigate the feasibility of preventing the initial formation of smoke in the converter.

Jan 1, 1961

By M. Schwartz, S. K. Nash, R. Zeman

Knoop hardness in the rolling plane and in the longitudinal plane of hot-rolled and cold-rolled sheets of sublimed magnesiu?w was measured as a function of the angle between the long axis of the indenter and the rolling direction. These measurements were correlated with similar data taken on the (0001) and (1010) planes of a single crystal of magnesium where the hardness was measured as a function of the angle between the long axis of the indenter and the [1120] direction. The results were analyzed for compliance with the hypothesis of Daniels and Dunm to account for slip, and with a similar hypothesis to account for twinning. Some hardness anisotropy data are also presented for magnesium-indium and magnesium-lithium solid solution alloys. It is well known that the hardness of a crystalline specimen is different for its different surfaces, and also that the hardness is a function of direction within a single surface. Variations in hardness for single crystals have been found to be much larger than those for polycrystalline materials. Also, materials having low crystal symmetry were found to have a greater anisotropy of hardness than those of high symmetry. 0&apos;Neill1 and Pfeil,2 using a 1-mm Brine11 ball, studied single crystals of aluminum and iron, respectively; and they found a variation of hardness of about 10 pct between readings taken along the principal crystallographic faces. Daniels and Dunn3 found that the Knoop hardness number varied about 25 pct as the long axis of the indenter rotated on the basal plane of a zinc single crystal. The variation on the (1450) plane was about 100 pct, and the average hardness on this plane was about twice that of the basal plane. They also studied the variation of hardness within the (loo), (110), and (111) faces of a single crystal of silicon ferrite and found variations of about 25 pct although the average values for these planes were almost identical. Single crystals of zinc were also studied by Meincke.4 He found that the Vickers hardness numbers varied about 30 pct depending on whether the axis of the indenter was parallel or perpendicular to the (1010) and (1110) planes. Mott and Ford,5 using a Knoop indenter, found a 25 pct variation in hardness on the basal plane of zinc. Crow and Hinsley6 studied heavily cold-rolled bronze, steel, brass, copper, and other metals. They found that the difference in hardness numbers based on the difference in the length of the diagonals of the Vickers indenter was from 5 to 12 pct. Some minerals and synthetic stones show a very large anisotropy of hardness. Robertson and Van Meter7 found the Vickers hardness of arsenopyrite to vary from 633 to 1148 kg per mm2. stern8 using the double-cone method on synthetic corundum found the hardness number to vary from 950 to 2070. And winchell9 reported a variation of hardness number from 184 to 1205 in kyanite. The variation of hardness as a function of direction in a given crystallographic plane in single crystals possesses a periodicity which is related to the symmetry of the lattice. Daniels and Dunn3 found a six-fold periodicity of hardness in the (0001) plane of zinc. They found that the hardness curves of silicon ferrite had a four-fold symmetry in the (100) plane, a two-fold symmetry in the (110) plane, and a six-fold symmetry in the (111) plane. Mott and Ford5 also reported a six-fold symmetry of hardness in the basal plane of zinc. And vacher10 found two-, four-, and six-fold periodicities of hardness in copper on the (110), (100), and (111) planes, respectively. The purpose of this paper is to report the results of an investigation on the anisotropy of hardness as a function of orientation in single crystals of mannes-ium, and samples of rolled magnesium, magnesium-indium, and magnesium-lithium solid solution alloys. The anisotropy of hardness of pure magnesium which had been hot rolled, and then cold rolled various amounts to fracture, was studied by means of Knoop indentation hardness numbers; and the results were correlated with the preferred orientation as determined by quantitative X-ray pole-figure data. A comparison was made of the hardness data obtained from the rolled sheets and those of single crystals of magnesium. In order to obtain a more fundamental understanding of the variation of hardness and of Knoop hardness testing, the data were analyzed by

Jan 1, 1962

By F. C. Schora, H. P. Meissner

Both a graphical and an analytical technique are presented for calculating stream compositions and temperatures in adiabatic staged systems in which solids travel countercurrently to a gas stream. Such a system might be a tower containing several plates, on each of which the descending solid is fluidized by the rising gas stream. Examples are presented in which chemical reactions occur, including the oxidation of SO, by a solid catalyst and the gaseous reduction of iron oxides. COUNTERCURRENT staged processes involving reactions between solid and gas streams are becoming more common. These operations are generally carried out in a series of beds of fluidized solids, with each bed or "plate" acting as a stage. Fig. 1 is a schematic diagram of such a series of stages located in a column, down through which a solids stream moves from stage to stage counter to a rising gas stream. Typical reactions carried out in such systems are the dehydration of aluminum trihydrate, the calcining of limestone, and the gaseous reduction of iron oxides. Calculation of the performance of these counter-current systems rapidly becomes more complex with increases in the number of stages and in the number of chemical reactions occurring. Calcula-tional procedures for isothermal operations of such systems have been described.4 Actual tower operations, however, are generally adiabatic, and in consequence far from isothermal. The object here is to present both graphical and analytical techniques applicable to such adiabatic towers operating continuously and in steady state. In this introductory discussion, the graphical techniques presented are of the McCabe-Thiele type, rather than of the Pon-chon type. In all the examples presented, it will be assumed that both thermal and chemical equilibrium are attained in each bed. The assumption that the gas and solid streams leaving each bed are at the same temperature as the bed is in accordance with the familiar behavior of actual fluidized solid systems. Chemical equilibrium, on the other hand, is not necessarily attained in any given stage between these two streams, even with deep beds, since reaction rates may be slow. In the last section of this paper, discussion is presented of methods suitable for use when chemical equilibrium is not attained. The adiabatic tower in Fig. 1 has "n" stages numbered from 1 to n, starting with the bottom stage as number 1. In analyzing this tower&apos;s performance, it is important to express gas flow rates in terms of a key component or element which remains completely within the gas stream throughout the tower. Similarly, solid flow is best expressed in terms of a key compound or element which remains within the solid phase throughout the tower. Thus, in burning limestone with a hot flue gas, the gas flow might be expressed as G, the pound mols of nitrogen flowing through the tower per unit time, while solid flow might be expressed as S, the pound atoms of calcium in all forms in the solid stream per unit of time. Defined in this way, both G and S are constant throughout the tower. The enthalpy of the gas and solid streams are now best expressed in terms of these key components. That is, the gas stream enthalpy H is expressed as Btu in the total gas per mol of the key component in the gas. Similarly, the solids stream enthalpy h is expressed as Btu in the total solid stream per pound mol (or pound atom) of the key component in this stream.

Jan 1, 1962

By J. A. Knox, R. M. Lasater, J. M. Tinsley

Chemical squeeze treatments have been used to provide temporary relief from certain production problems. The chemical fracture-squeeze technique, combining the effects of a fracturing treatment and a squeeze operation, has been more successful than conventional squeeze operations. Knowledge derived from well stimulation and reservoir engineering research provides a means for predicting the theoretical effective life of such a treatment. Analysis of theoretical equations and concepts developed allows selection of improved treatment techniques based on specific formation conditioins. Theory used in this analysis was developed as an extension of previous electrical model studies made to establish the expected flow and pressure profiles adjacent to a fracture system. The chemical fracture squeeze technique can be utilized in the economic application of corrosion inhibitors, emulsion breakers and paraffin and scale inhibitors. Application of this technique is shown to be effective. The slow return rate of injected chemicals, controlled by the resultant flow profiles and treatment variables, permits extended periods of chemical effectiveness. Results of field treatments are given, showing that the concepts outlined above for chemical fracture-squeeze treatments are valid and that applying this technique can help alleviate many current production problems. INTRODUCTION Much progress has been made in the last 10 to 15 years in developing chemicals for use in stimulating wells, maintaining production and protecting well equipment from damage due to corrosion. Not too many years ago, some wells seemed to dry up or wear out. In many cases the wells were produced as long as possible without any attempt at maintaining productivity. Even with the advent of new and better stimulation techniques, a rapid decline in production was observed. Methods of removing and, in some instances, preventing damage have been developed. Among thosc factors responsible for uneconomical production are scale, paraffin, corrosion, bacteria, water blocks and emulsions. Soluble scale-prevention chemicals have been developed1,2 that can be placed in a formation along with frac- turing sand. As the water produces back across this bed, the solid material dissolves slowly and can provide long-term protection from scale. However, bottom-hole temperature and salinity of produced water vary widely and both these factors influence the rate of solubility. Scale inhibitor composition is also a controlling factor. Some of the solid material may be crushed, increasing the surface area exposed to water and increasing the rate at which it dissolves. Some of the material may never be contacted by water and can be lost. However, this type of treatment has been very successful in many instances and has helped maintain economical production for extended periods of time. Liquid scale inhibitors, which are more widely applicable and more stable, have been developed in recent years; however, because they are liquids, their use has been restricted to treatment down the annulus, using metering pumps to provide proper concentrations in the produced fluid. This has prevented use in wells containing packers, in dually completed wells and in gas-lift and flowing wells. Wells that operate with an open annulus may also experience severe corrosion problems due to introduction of oxygen. Paraffin inhibitors3 have been developed that can be fractured into a well as particulate solids to be slowly dissolved in the produced fluid. These materials are not usually effective in wells with a bottom-hole temperature in excess of 120F since solubility rate may be too fast if that temperature is exceeded or if aromatic content of the oils is unusually high. Corrosion inhibitors have been developed that can be fractured&apos; into a well for long-term feedback, but development of a material with proper solubility or feed rate has been difficult. Corrosion inhibitors are available in many different forms. Liquids have been lubricated down the annulus or sticks or pellets dropped down tubing. Inhibitor squeeze treatments5 devcloped a few years ago led to development of inhibitors with particularly strong film-forming properties.6,7 This technique basically involves displacing a highly concentrated solution of the inhibitor into the formation through the tubing. Kerver and Hanson8 studied the adsorption properties of inhibitors on various types of formations. They showed that, even though the inhibitor was displaced radially into the true permeability, it could be produced back for a long period of time because of slow desorption from the rock. Methods developed for monitoring the return of these inhibitors generally have established 1 to 6 months as the effective limit before retreatment is necessary.9 Inhibitors displaced into the interstices of the formation sometimes cause emulsions that either hamper production or cause treating problems on the surface.

By H. R. Cooper, T. S. Mika

T. S. Mika (Department of Mineral Technology, University of California, Berkeley, Calif.) - Dr. Cooper&apos;s attempt to establish a correlation between process behavior and operational variables on the basis of a statistical analysis after imposing a reasonable process model is a very commendable improvement on the use of standard regression techniques. However, it must be recognized that the imposition of a model has the potential of yielding a poorer representation if its basic assumptions or mathematical formulation are invalid. It appears that at least two aspects of his treatment require some comment. First, the limitations on the kinetic law where xta represents a hypothetical terminal floatable solids concentration (cf. Bushell1), should be mentioned. Most current investigations2-9 appear to utilize the concept of a distribution of rate constants rather than a single unique value, k, to describe flotation kinetics. A distributed rate constant is certainly a more physically meaningful concept than that of a terminal concentration. The study of Jowett and safvi10 strongly indicates that xta is merely an empirical parameter, whose actual behavior does not correspond to that expected from a true terminal concentration. Rather than being a strictly mineralogical variable, as Dr. Cooper&apos;s treatment implies, it apparently represents the hydromechanical nature of the test cell as well as the flotation chemistry. The extension of batch cell kinetic results to full-scale continuous cell operation is a suspect procedure if the effect of such nonmineralogical influences on x,, remain unevaluated. There is evidence that introduction of a terminal concentration is necessitated by the inherent errors which arise in batch testing and are eliminated by continuous testing methods.&apos; Possible lack of validity of the author&apos;s use of Eq. 1 is indicated by two unexpected results of the statistical analysis of his batch data. The first is the apparent corroboration of the assumption that the rate constant, k, is independent of particle size, i.e., of changes in the size distribution of floatable material. This assumption directly contradicts numerous results 2,4,11-l8 for cases where first order kinetics prevailed and ignores the phenomenological basis for the analysis of flotation in terms of a distribution of k&apos;s. It must be recognized that, if the rate constant is size dependent, the lumped over-all k would be time dependent; Eq. 1 would then no longer be valid. Cooper&apos;s x,, is determined by batch flotation of a distribution of sizes for an arbitrary period of time. If the size dependence of k is artificially suppressed, x,, will become a function of the experimental flotation time used in its determination. Upon reviewing the rather extensive literature concerning batch flotation kinetics, there appear to be few instances where constant k and x,, adequately adsorb variations in floatability due to particle size. The second surprising result is the low values of the distribution modulus, n, determined. Contrary to Cooper&apos;s assertion, most batch grinding (ball or rod mill) products yield values of n > 0.6, which increase as the material becomes harder.&apos;&apos; It is likely that the values of n = 0.25 and n = 0.42 for Trials 1 and 2, respectively, are completely unreasonable, and even the value n = 0.54 obtained for Trial 3 is unexpectedly low. Possibly, this indicates inherent flaws in the three trial models considered, in particular the assumed particle size independence of the rate constant, k. The above does not necessitate that Eq. 1 (and the terminal concentration concept) is invalid; it could constitute a good first approximation. However, the qualitative arguments used by Dr. Cooper in its justification are somewhat frail and require verification, particularly since much of the flotation kinetics literature is in opposition. Apparently, no effort was made to test these hypotheses on the actual data; in fact, since they pertain to a single batch test time, his data cannot be utilized to evaluate the kinetics of flotation. To evolve a control algorithm on the basis of this infirm foundation seems a questionable procedure. Another difficulty in his analysis arises in consideration of the froth concentrating process. As Bushel1 &apos; notes, for Eq. 1 to be valid it is necessary that the rate of recycle from the froth be directly proportional (independent of particle size) to the rate of flotation transport from the pulp to the froth, a restrictive condition." Harris suggests that it is more realistic to assume that depletion occurs in proportion to the amount of floatable material in the pertinent froth phase volume (treating that volume as perfectly mixed).12,21,22 The physical implications of

Jan 1, 1968

By Jei Y. Choi, P. G. Shewmon

The surfrrce-diffusion coefficients (DJ for Aulg8 on (100) and (111) surfaces of copper have been determined between 1050" and 780°C using a new avuzlysis imd experimental procedure. The results are: D, has also been determined fm cua4 at 870°C, and the values found are 4.5 times larger than those measured by the grain boundary grooving technique for the same surface orientations. This difference is felt to result from the approximate nature of the mathematical solution used in the present work. Attempts to measure D, for silver on copper and silver surfaces indicated a means of matter transport different from surface diffision was dominant in moving tracer from the source out over the surface. Cnlculations and experiment both indicate that this is the flow of silver through the vapor phase which completely masks the much smaller flow due to surface diffusion. The previous self-difhsion studies of D, for silver and copper are discussed in terms of our own analysis and found to yield values of D, factors of lo5 or more greater than those found by the grain boundary grooving tech -nique. UNTIL about 5 years ago it was widely believed that the activation energy for surface diffusion, AH, , was less than that for grain boundary diffusion, AHb,, which in turn was less than that for diffusion through the lattice, AHz.&apos; This was concluded from various evidence that D,> Db>Dl, and one tracer study of D, for silver on silver from which AH, was inferred.2 In 1959 Mullins and Shewmon demonstrated that D, could be determined from the kinetics of the growth of grain-boundary grooves.3 Using this procedure, Gjostein measured D, on copper between 800" and 1050°C and found that the activation energy was roughly equal to AHl .4 Subsequent work on copper,5" silver,&apos;,&apos; and goldg between the melting temperature T, and 0.87 T, confirmed that AH, as determined using the grain boundary grooving or scratch-relaxation technique was equal to or greater than AHz. During the same period, Drew and Pye again determined AH, for silver on silver using a tracer techniquelo and a mathematical solution similar to that of Nicker son and arker.&apos; Though the values of D, Drew and Pye measured at any given temperature were about 200 times smaller than those reported by Nickerson and Parker, they again found a low activation energy of about 10 kcal, or about one fifth that found at the higher temperatures with the mass transport technique. A distinguishing characteristic of these two previous tracer studies is that they have worked at low temperatures (-1/2 T,) where they felt volume diffusion was negligible and then analyzed these data as if all tracer atoms leaving the source flowed out into and remained in a homogeneous high-diffusivity surface layer of undefined thickness. This is totally different from the model used in the mass-transport studies or the studies of grain boundary diffusion, which assume the high-diffusivity surface layer to be only a few angstroms thick. If this latter model is applied to the earlier tracer studies, it is shown that the tracer has really pe!etrated into the lattice a mean distance of 1000A. Thus the tracer distribution observed after an anneal is thought to be due to the combined effects of surface and volume diffusion. Independent of the relative validity of the two models, it seems evident to us that any comparison of the values of D, as determined in these two ways is meaningless and misleading, since the values of D, and AH, obtained in these two ways would be totally different for the same physical distributions of tracer. Once the fundamental difference in the approaches of the two techniques is established, we are faced with the question of which model better approximates physical reality. Here all the evidence seems to be on the side of the &apos;&apos;thin surface layer" analysis. In fact, the authors of Refs. 2 and 9 do not argue for the "thick-layer model" we have described; they simply invoke it through the equation they use to calculate D, . The primary evidence for the thin-film approach is: a) grain boundary grooves and scratches widen in proportion to tU4 and Mullins&apos; rigorous analysis shows that this is only valid for a surface layer which is quite thin relative to the width of the groove;11 b) all accepted or seriously discussed models of solid-vapor interfaces and high-angle grain boundaries assume that the disturbed region of the interface is at most a few a0 thick. With the above in mind, it was desirable to determine D, using a radioactive tracer and a "thin-

Jan 1, 1964

By D. E. Thomas, C. E. Birchenall

ALTHOUGH Eoltzmann gave a mathematical solution for the diffusion equation (for planar diffusion in infinite 01. semi-infinite systems only) in 1894 allowing for variation of the diffusion coefficient with a change in concentration, it was not until 1933 that this solution was applied to an experimentally investigated metallic system. The calculation was carried out by Matano&apos; on the data obtained by Grube and Jedele3 for the Cu-Ni system. Since that time concentration dependence of the diffusion coefficient has been demonstrated for many pairs of metals. However, the nature of this dependence has never been fully elucidated. Many investigators have suspected that these variations could be related to the thermodynamic properties of the solutions, one of the earliest explicit statements being contained in a discussion of irreversible transport processes by Onsager&apos; in 1931. Development along these lines has been greatly retarded by the lack of reliable data on the variation of tliffusivity with concentration, the paucity of the thermodynamic data for the same systems at the same temperatures and compositions, and an incomplete understanding of the relation of the thermodynamic properties of the activated state for diffusion to the bulk thermodynamic properties. The last factor has been discussed by Fisher, Hollomon, and Turnbull.5 In many instances where data exist, it is difficult to know which are acceptable. This problem probably applies more strongly to diffusion data than to activity measurements. For instance, four sets of observers"-" have reported self-diffusion coefficients for copper. The average spread between extreme results is a factor of about four, though the individual sets of data are self-consistent to about 20 pct. Thus one or more factors are out of control, at least in these experiments, making estimates of internal error unreliable. The most reliable diffusion data in most systems have resulted from the use of welded couples with a plane interface from which layers for analysis are machined parallel to the interface after diffusion. The layers are analyzed, and the result is a graphical relation between distance and concentration, usually called the penetration curve. Given the same set of analytical data and distances and following the same procedure in computation, different observers will generally produce diffusion coefficients which vary appreciably, especially at the extremes of the concentration range. Experiments must be carefully designed so that the precision is good enough to answer a particular question unequivocally. In the first calculation of the dependence of the diffusion coefficient on concentration in the metallic solid solution Cu-Ni, Matano found that the coefficient was insensitive to concentration from 0 to 70 pct Cu, after which it rose more and more steeply to some undetermined value as pure copper was approached.&apos; The same behavior was reported for Au-Ni, Au-Pd, and Au-Pt.* The data used were those of Grube and Jedele which were very good at the time, but are not considered particularly good by present standards. Furthermore, the method of calculation makes the ends of the diffusion coefficient-concentration curve unreliable. For better reliability, the high copper end of the curve has been checked by incremental couples, where the concentration spread is 67.7 to 100 atomic pct Cu. The implication of the curves calculated by Matano was that diffusion is very concentration sensitive in one dilute range of this completely isomorphous system and hardly at all in the other. Matano&apos;s result is confirmed. Later Wells and Mehll0 published data on diffusion in Fe-Ni at 1300°C, which represent a thorough test of the shape of the concentration dependence curve. They ran couples with the following ranges of nickel concentration: 0-25 pct, 1.9-20.1 pct, 0-20.1 pct, 20.1-41.8 pct, 0-99.4 pct, and 79.3-99.4 pct. Although the trend of the data indicates an S-shaped concentration dependence, their curve was drawn to the pattern set by Matano. Their original data have been recalculated for the 0-99.4 and 79.3-99.4 pct couples. Wells and Mehl&apos;s points and two independent recalculations from the raw data are plotted in Fig. 1. What appears to be the best curve is drawn through them. This curve shows little sensitivity to composition in both dilute ranges with a strong dependence at intermediate composi-tions.? Similar experiments on the Cu-Pd system are reported here at temperatures where solubility is unlimited. These lead to the same type of concentration dependence for the diffusion coefficients as was found upon recalculation of the data for the Fe-Ni system. Experimental Procedure Cu-Pd: The concentration dependence of the diffusion coefficient may be determined by the use of

Jan 1, 1953

By S. J. Sindeband

Prior to discussing the metallurgy of sintered chromium borides, it is pertinent to outline some of the reasoning behind this investigation and the purposes underlying the work. This study was initiated as an aproach to the ubiquitous problem of a material for service at high temperatures under oxidizing atmospheres, and it was undertaken with a view to raising the 1500°F (816°C) ceiling to 2000°F (1093°C) or better. For the reason that no small, but rather a major, lifting of the high temperature working limit was being attempted, it was felt appropriate that a completely new approach be taken to this problem. A summary of the thinking behind this approach was published recently by Schwarzkopf.&apos; In briefest terms, it was postulated that the following requirements could be set up for a material which would have high strength at high temperatures. 1. The individual crystals of the material must exhibit high strength interatomic bonds. This automatically leads to consideration of highly refractory materials, since their high energy requirements for melting are related to the strength of their atom-to-atom bonds. 2. On the polycrystalline basis, high boundary strength, superimposed on the above consideration, would also be a necessity. Since this implies control of boundary conditions, the powder metallurgy approach would hold considerable promise. Such materials actually had been fabricated for a number of years, and the cemented carbide is the best example of these. Here a highly refractory crystal was carefully bonded and resulted in a material of extremely high strength. That this strength was maintained at high temperature is exhibited by the ability of the cemented carbide tool to hold an edge for extended periods of heavy service. Nowick and Machlin2,3 have analytically approached the problem of creep and stress-rupture properties at high temperature and developed procedures whereby these properties can be approximately predicted from the room temperature physical constants of a material. The most important single constant in the provision of high temperature strength and creep resistance is shown to be the Modulus of Rigidity. On this basis, they proposed that a fertile field for investigation would be that of materials similar to cemented carbides, which have Moduli of Rigidity that are among the highest recorded. The cemented carbide, however, does not have good corrosion resistance in oxidizing atmospheres and without protection could not be used in gas turbines and similar pieces of equipment. It would be necessary then to attempt the fabrication of an allied material based upon a hard crystal which had good corrosion resistance as well. It was upon these premises that the subject study was undertaken and at an early stage it was sponsored by the U.S. Navy, Office of Naval Research. Since then, it has been carried on under contract with this agency. Chromium boride provided a logical starting point for such research, since it was relatively hard, exhibited good corrosion resistance, and, in addition, was commercially available, since it had found application in hard-surfacing alloys with iron and nickel. That chromium boride did not provide a material that met the ultimate aim of the study results from factors which are subsequently discussed. This, however, does not detract from the basis on which the study was conceived, nor from the value of reporting the results which follow. Chromium Boride While work on chromium boride proper dates back to Moissan,4 there has been a dearth of literature on borides since 1906. Subsequent to Moissan, principal investigators of chromium boride were Tucker and Moody,5 Wede-kind and Fetzer,6 du Jassoneix,7,8,9 and Andrieux." These investigators were generally limited to studies of methods of producing chromium boride and detennining its properties. Some study, however, was devoted to the chromium-boron system by du Jassoneix,7 who did this chemically and metal-lographically. This system is not amenable to normal methods of analysis by virtue of the refractory nature of the alloys involved, and the difficulties of measurement and control of temperature conditions in their range. Dilatometric apparatus is nonexistent for operation at these temperatures. Du Jassoneix made use of apparent chemical differences between two phases observed under the microscope and reported the existence of two definite compounds, namely: Cr3B2 and CrB. These two compounds, he reported, had quite similar chemical characteristics, but were sufficiently different to enable him to separate them. The easiest method for producing chromium boride is apparently the thermite process, first applied by Wede-

Jan 1, 1950

By E. S. Bartlett, D. N. Williams

QUANTITATIVE values for the oxidation rate of unalloyed molybdenum in air at temperatures above the melting point (1460°F) of the characteristic oxide are contained in the literature as a result of previous investigations. Lustman&apos; reported values corresponding to 0.36 in. penetration per day (IPD) at 1500 and 1600°F in still air, noting essentially no variation in rate with temperature. Jones, Spretnak, and Speiser&apos; reported values corresponding to 0.14 and 0.13 IPD at 1500 and 1800°F, respectively, in still air, attributing the decreased oxidation rate at higher temperatures to a lesser accumulation of the corrosive molten oxide on the surface at the higher temperature as a result of increased volatilization rate. Harwood3 ecently summarized work in the field, presenting generalized data corresponding to 0.48 to 0.96 IPD at 1800°F and 0.55 to 0.83 IPD at 1700°F in slowly flowing air. In a recent program at Battelle, it became desirable to know more about the characteristic oxidation behavior of molybdenum under varying conditions of temperature and atmosphere. Using oxidation-test apparatus designed for dynamic, continuous recording of weight change during testing,&apos; values for the oxidation rate of molybdenum were obtained at temperatures from 1400 to 2150°F. In addition the effect of air flow on the oxidation rate was studied briefly at temperatures of 1600, 1800, and 2000°F. Exhaust of the contaminated atmosphere from the oxidation chamber was effected by an impeller pump attached to a 3/16-in.-diam opening in the oxidation chamber. The volumetric exhaust rate (cubic feet per hour) was normally maintained slightly in excess of the input rate to avoid condensation of MOO,,&apos; on the sample suspension rod. The entering atmosphere was preheated prior to admission to the oxidation chamber by a 1 1/2-in.-diam cup packed with shredded asbestos. The experimental data are presented in Table I. Comparing conditions 2 and 3 (taking into account the temperature difference) and conditions 8 and 9. shows that in the absence of forced exhaust an atmosphere of moving air results in greater oxidation rate than a stagnant atmosphere. The use of forced exhaust, as shown by comparing conditions 3 and 4 and conditions 14 and 15: resulted in an even greater increase in oxidation rate. By virtue of the size of the atmosphere input and exhaust openings, it was calculated that the exhaust velocity was about 60 times that of the input velocity for essentially equal volumetric flow rates. Because of the proximity (about 3/4 in.) of the exhaust port to the specimen, it is logical to assume that cleansing of the atmosphere immediately surrounding the specimen was accomplished much more efficiently by the exhaust flow than by the input flow at a constant-volumetric flow rate. Also, it can be seen by comparing conditions 4 through 7 and conditions 11 through 13 that increasing the rate of atmosphere flow (by increasing input velocity with a proportional increase in exhaust velocity) above some optimum value has little, if any, further effect on the oxidation rate. These results suggest that there is a maximum oxidation rate for molydenum at a given temperature which is obtained when conditions are maintained such that the partial pressure of MOO3 in the atmosphere surrounding the specimen is at a low value. By controlling the partial pressure of MOO, surrounding the sample, it is possible to control the rate of volatilization of MOO:, from the surface. This, in turn, affects the rate of oxidation, since the thickness of the MOO3 layer determines the amount of oxygen which will be able to reach the reaction surface.&apos; When the liquid oxide layer is less than some critical thickness, i.e., when the volatilization rate is high, enough oxygen is transported to the active surface to permit oxidation to proceed at the maximum rate allowed by the kinetics of the oxidation reaction. However, if the volatilization of MOO,, is suppressed, the thickness of the layer of MOO3 on the surface increases, and the diffusion of oxygen through the oxide layer becomes the rate-controlling step in the oxidation process. The lack of agreement between the present results and those of previous investigators is presumed to be due to differences in removal of the oxidation product (Moo,) from the immediate vicinity of the sample. By comparing conditions 1, 5, 10, 12 and 14, it is seen that when forced exhaust was used the oxidation rate of molybdenum increased with increasing temperature. A rapid increase was observed between 1400 and 1600°F, attributable to the effects

Jan 1, 1959

By E. S. Bumps

A series of macrographs are presented for the purpose of graphically recording the strain phenomenon that accompanies the energy transition in the Charpy impact testing of a mild steel that is susceptible to strain aging. STRAIN patterns in mild steel Charpy impact specimens were obtained in order to determine whether, on the first appearance of plastic strain during deformation, the initial fracture cracks appear in the region of plastic strain or in the elasti-cally deformed regions between. Although this attempt to locate the initiation of cleavage was not successful, the observed strain patterns illustrating various stress conditions in partially deformed Charpy specimens are presented along with a discussion of the possible dependence of transition energy on the yield phenomenon. Earlier work on the development of strain patterns in mild steel have been reported by Fry1 and later by Jevon.2 Harris, Rinebolt, and Raring3 observed characteristic strain markings on the surface of Charpy V-notch impact specimens fractured above and below the transition temperature which they presented schematically. It is intended that the strain figures presented here will add to the literature a graphic correlation of strain with transition energy in impact specimens. Samples of % in. round hot rolled, 0.20 pct C steel were machined to standard 0.394 in. sq, V-notch Charpy impact specimens. Preliminary testing involved determination of transition temperature, Fig. 1, using a Sontagg impact tester. These data were subsequently used to select temperatures above, within, and below the transition range at which specimens were partially deformed. Partial deformation was obtained by either varying the energy or the testing temperature, see Table I. Macroscopic strain figures shown in Figs. 2 to 19 were produced by several metallographic repolish-ing and etching steps. The macroetchant used was as follows:4 120 g HCl, concentrated; 100 ml water; and 90 g cupric chloride. Strain figures were obtained on the outer surface and on sections through the central portion of the impact specimens in order to determine an approximation of the volumetric strain pattern. In the tensile strain figures reported by Jevon, it was found that strain etching would not work immediately following strain unless the material was heated to 200°C. The impact strain patterns presented here were obtained without this heating, but the specimens were not etched until ten months after straining. This confirms a discussion of Jevon&apos;s paper, in which it was pointed out that strain figures can also be developed after aging for long periods of time at room temperature. Hardness of the strained and unstrained portions, revealed by the etched pattern, was explored using R, impressions converted to R, hardness values. Discussion of Results In the impact test, as in the tensile test, some parts of the specimen yield and deform plastically, while other regions are deformed only elastically. The plastic deformation bears a relation to the imposed stress pattern. In the strain figures presented here, the plastically deformed regions are the dark etching ones. The strain figures are always symmetrical because the stress state in the Charpy-type specimen under impact loading is symmetrical. The difficulties encountered to produce initial cracks are intimated in Figs. 2 and 4. At a temperature of —75ºF, the stress was not sufficient to pro-

Jan 1, 1953

By Carlos E. Roggero

The influence of high temperatures on the zinc roasting practice has been investigated by full-scale tests in fluid bed reactors operating at temperatures from 950° to 1150°C. It was definitely shown that, throughout the range, an increase in tem perature resulted in a 2 to 3 pct increase in zinc solubility because of decreased content of zinc fer-rite and lowered sulfide sulfur. The former is attributed to thermal decomposition of ZnFe,O,, and the latter to increased oxidation rates, ad longer retention times. Data on the gveatly increased volatilization of lead, cadmium, and silver above 1000°C, are presented. A considerable fraction of the iron present in the feed was also transferred at high temperatures from the coarse roaster discharge to the flue dusts. AS part of its metallurgical complex1-3 situated in a 12,000 it Andean valley at La Oroya, Peru, Cerro de Pasco Corp. (a wholly owned subsidiary of Cerro carp.) operates a 150 short ton per day electrolytic zinc refinery. Electrolysis is carried out at a cathode current density of 65 amp per sq ft with an electrolyte content of 55 g per liter of Zn and 150 g per liter of su lf uric acid. Due to the high iron content of the marmatitic concentrate used, a large fraction—about 15 pct—of the zinc reports in the leach residues. To minimize such losses, efforts have been exerted toward improving calcine solubility. One method, as noted in the literatre,, is to retard zinc ferrite formation by decreasing the roasting temperature. Unfortunately, such a procedure tends either to reduce the roaster throughput or increase the sulfide sulfur in the calcine. Consequently, this approach was discarded in favor of experimental work in the opposite direction, i.e., high temperature roasting. Full- scale tests were promising and resulted in the granting of a patent to Cerro de Pasco carp.&apos; After a brief account of plant equipment and operating procedure, this paper describes the tests made and attempts to assess the results obtained. GENERAL PLANT LAYOUT AND OPERATION The Roasting Plant, see Fig. 1, comprises an agglomerating plant feeding three fluid bed roasters with a combined capacity of 10,000 tons per month. The Peruvian patent rights on this process were purchased from the New Jersey Zinc Co. The concentrate, assaying: is pelletized to a -3 +14 mesh product and fed to the fluid bed roasters. The roaster exhaust gases pass through a waste heat boiler, cyclones, a fan, and an electrostatic precipitator. Approximately half of the dust collected in the cyclones returns to the pellet-izing plant as one of the binding ingredients, the remainder joins the cooled bed discharge (&apos;overflow&apos;) and is conveyed to the grinding plant. The -35 mesh product obtained, together with the dust collected in the electrostatic precipitator constitute the feed to the leaching plant. Batch leaches are made in vessels with mechanical and air agitation, the residues are separated and washed in Burt Filters, and pumped to storage ponds. THE FLUID BED ROASTERS Two reactors are as shown in Fig. 2, and the third,&apos; of about the same configuration, is approximately 40 pct smaller. The total grate and freeboard (just below the gas outlet) areas measure 170 and 426 sq ft respectively. The feed, continuously weighed and controlled by Merrick Weighto-meters fitted with variable speed motors, enters the reactors at the top of the expanded bed level. The coarse calcine overflows through the opposite end by

Jan 1, 1963

By R. M. Waterstrat

The phases occurring in the V-Mn system were studied by means of X-yay diffraction and metallo-paphic techniques, using are-melted alloy specimens annealed in the temperature range 800° to 1150°C and quenched. The bcc solid solution extends at 1250°C all the way from vanadium to 6-manganese. Below 1050°C the a-phase is formed, and the terminal a-manganese phase is stabilized up to about 900°C by vanadium in solid solution. IN the only previous general survey of the V-Mn system Cornelius, Bungardt and Schiedtl reported the existence of three intermediate phases corresponding to the approximate compositions VMn,, VMn, and V5Mn. The phase VMn8 has recently been identified as a o phase2 but the alloy VMn was found to have a bcc structure2 corresponding apparently to the vanadium solid solution rather than to the large cubic unit cell reported by Cornelius et al. 1 Subsequent work by Rostoker and Yamamoto3 has shown that the vanadium-base bcc solid solution extends to at least 15 pct Mn at 900°C. An alloy corresponding to the composition VMn, was examined by Elliott,4 who reported that the as-cast sample as well as samples annealed at 1200o and 1300°C had bcc structures, but that annealing at 1000°, 800") and 600°C produced two phases. One of these phases was apparently the bcc solid solution and the other resembled the o phase structure. Hellawell and Hume-Rothery5 established the phase relationships in manganese-rich alloys above 1000°C, and showed that the o phase in this system is replaced by the 6 Mn (bcc) solid solution at temperatures above 1050°C. These results suggest that a continuous bcc solid solution may exist above 1050°C between vanadium and 6 Mn. The present investigation was undertaken in order to develop more complete information in regard to this system. EXPERIMENTAL METHODS The alloys used in the present work were prepared by arc-melting electrolytic manganese having a minimum purity of 99.9 pct and vanadium lumps with a purity of 99.7 pct. The major impurities present in these metals were carbon, nitrogen, and oxygen and this would account for the small percentage of nonmetallic inclusions observed metal-lographically. The arc-melting was at first performed under a helium atmosphere and it was necessary to keep the melting times as short as possible in order to minimize the loss of manganese by vaporization. It was later found that the evaporation of manganese was considerably reduced when the melting was done under argon atmosphere. The final composition of each alloy was calculated by assuming that the total weight loss during melting was due to evaporation of manganese. Compositions which were calculated in this manner agreed reasonably well with the results of chemical analysis, as shown in Table I. Spectrographic analysis revealed the presence of contamination by tungsten, but in no case was the percentage of tungsten greater then 0.4 at. pct. The specimens were in each case broken in half and the fractured section was examined visually and microscopically for evidence of inhomogeneity. Each specimen was homogenized at temperatures near l100°C, as shown in Table I. After this treatment most specimens consisted of large columnar grains of the bcc vanadium solid solution. The etchant used in most of the metallographic work consisted of 20 pct nitric acid, 20 pct hydro-flouric acid, and 60 pct glycerine. It was found that this etchant would clearly delineate the phases present in these alloys although it does not produce any striking contrast between the phases. For certain manganese-rich alloys, a 1 pct aqueous solution of nitric acid was used. This etchant gave a brown color to the a-manganese phase, whereas the o phase was virtually unattacked and appeared very light as shown in Fig. 1. The etchants used by Cornelius et a1.l were found to produce spurious effects in some of these alloys. In particular, the vanadium-rich alloys etched in hot sulfuric acid often appeared to consist of two phases when both X-ray diffraction and etching with the glycerine-acid mixture indicated the presence of single phase bcc solid solution. A few percent of what appears to be an oxide or nitride phase was found at the grain boundaries and in the interior of the grains, especially in the vanadium-rich alloys. All alloys were annealed in sealed silica tubes containing 1 atm of pure argon and these tubes were then quenched in cold water. Although some manganese loss occurred during annealing, the loss seemed to be confined to the surface of the speci-

Jan 1, 1962

By J. R. Cahoon, H. W. Paxton

The mechanical properties of unidirectionally solidified A1(rich)-Mg and A1(rich)-Cu castings containing up to 15 wt pct solute have been determined with re -spect to the volume fraction of interdendritic eutectic. Pioperties were determined in the directions pumllel and Perpendicular to that of solidification; the volume fraction of eutectic was varied between the "as-cast" and equilibrizcm amounts by approperiate heat treatment following solidification. The principles of fiber strengthened composites and dispersion strengthened materials are adapted to explain the mechanical properties of these castings. It is generally accepted that castings often have inferior mechanical properties when con~pared to wrought products. However, there is little quantitative data available concerning the factors which make apparently sound castings weak and/or brittle. The relative ease and inexpensiveness of the casting process have always been attractive and, therefore, an understanding of the factors which contribute to the mechanical properties of castings would seem desirable. Such an understanding may lead to an improvement in the mechanical properties to an extent where castings would become competitive in applications where presently only wrought products are considered to have the requisite properties. Such an understanding could also improve the reliability of present cast products. Much of the recent research on castings has centered about determining the extent of segregation in cast alloys. Macrosegregation, particularly inverse segregation, has been studied in some detail 1-8 and a considerable understanding of microsegregation has been obtained.9&apos;10 The effect of solidification rate on dendrite spacing and on the amount of interdendritic eutectic in binary alloys has been established, particularly for Al(rich)-Cu alloys.""0 However, the extension of these ideas to relate the amount of interdendritic eutectic, concentration gradients, micro-segregation, dendrite spacings, and so forth, to the rnechanical properties has been limited. Dean and spear" have related the mechanical properties of an Al-Si-Mg alloy, A356-T62, to the dendrite spacing and have shown that the mechanical properties improve with decreasing dendrite spacing. Passmore et al.12 have shown that annealing at high temperature improves the mechanical properties of Al(rich)-Cu al- loys and Archer and Kempf 13 have shown that an Al-1 pct Mg-1.75 pct Si alloy behaves in a similar manner. Ahearn and Quigley 14 have shown that high temperature homogenization also enhances the mechanical properties of an SAE 4330 steel. However, in the above investigations, no underlying reasons were suggested for the improvement in mechanical properties. The purpose of the present investigation is to relate the mechanical properties of castings to some of the solichfication variables and to derive some equations by which calculations of the mechanical properties may be attempted. In particular, the effect of the amount of interdendritic eutectic and the effect of stress direction with respect to that of solidification on the mechanical properties will be considered. The Al(rich)-Mg and Al(rich)-Cu binary alloy systems were chosen for study. The A1-Mg system was chosen because its constitutional relationships are such that large volunles of eutectic (up to 24 vol pct) may be obtained in the as-cast condition and then be completely dissolved by subsequent heat treatment at about 440°C. This allows a comprehensive study relating the mechanical properties of castings to the amount of interdendritic eutectic. Also the Al(rich)-Mg eutectic is almost a single phase 15 which should make the experimental results more amenable to theoretical interpretation and calculation. The A1-Cu system was chosen for study because of the large amount of related information available concerning segregation, dendrite spacing, and so forth. Unidirectionally solidified castings were used throughout the investigation so that the effect of solidification direction with respect to the direction of applied stress could be determined. THEORETICAL It is well known that upon solidification of binary alloy castings, the nonequilibrium amount of eutectic which forms is given by 10 where fe o is the weight fraction of eutectic, Cs is the solid solubility of solute at the eutectic temperature, k is the equilibrium partition coefficient, and C, is the average composition of the alloy. In the development of Eq. [I], it is assumed that the effects of inverse segregation and diffusion in the solid are negligible, and that no porosity is present. If the casting is homogenized at a high temperature for a long period of time, some (or all) of the eutectic is dissolved and the amount of eutectic for this "equilibrium" condition may be calculated directly from the constitutional diagram. By appropriate intermediate annealing, the

Jan 1, 1970

By R. W. Fountain, W. D. Forgeng, G. M. Faulring

Precipitation of the phase Co3Ti (Cu3Au type) from a Co-5 pct Ti a11oy has been investigated using single-crystal X-ray diffraction techniques. Oscillation and transmission Laue patterns of specimens aged for short-time periods at 600" C indicate the formation of titanium-rich and titanium-poor zones coherent with the {100} matrix planes. Longer aging times at 600° C establish that the equilibrium phase also forms on the {100} matrix planes as platelets. These observations are corroborated by electron metallography; electron diffraction studies show the phase Co3Ti to be ordered. A probable sequence of the precipitation reaction is discussed. A previous publication by two of the present authors reported on the phase relations and precipitation in Co-Ti alloys containing up to 30 pct Ti.1 The results of this investigation established the existence of a new face-centered cubic inter metallic phase, ranging in composition from about 17.0 to 21.7 pct Ti at temperatures below 1000° C The decomposition of the fcc supersaturated solid solution was studied employing hardness and electrical resistivity measurements. The changes in hardness upon precipitation in alloys containing 3, 6, and 9 pct* Ti were found to be associated with an initial increase in hardness followed by a plateau and then a second, more pronounced hardness increase. Investigation of this behavior by electrical resistivity measurements suggested that two different kinetic processes were involved, which, when interpreted in terms of the kinetic relation,2-4 indicated that initial precipitation was in the form of thin plates. On continued aging, the plates impinged during the growth process. The general features of these findings have been confirmed by Bibring and Manenc,5 while, in addition, they report the phase to be ordered. The present investigation was undertaken to provide more definite information on the structural relationships between the precipitate and the matrix. EXPERIMENTAL PROCEDURE Single crystals of a (20-5 pct Ti alloy were prepared from the melt employing the Bridgman technique. Poly crystalline rod, 1/2 in. in diam, prepared from vacuum-melted material, was machined to 3/8- in. diam to remove any surface contamination that may have resulted from hot-working. The crystals were grown under a purified hydrogen atmosphere in high-purity alumina crucibles heated by induction. Considerable difficulty was encountered in attempting to grow monocrystals because of the high melting point of the alloy and the high solute concentration. However, one crystal about 6 in. long was obtained which was essentially a single crystal except for one or two very small grains around the periphery. The as-grown crystal was solution heat-treated for 24 hr at 1200°Cin a purified argon atmosphere and water-quenched. One-quarter-in. slices were taken from each end of the solution heat-treated crystal for chemical analyses, and the remainder of the crystal was mounted and oriented by the back reflection Laue Method. The chemical analysis of the crystal was as follows: Pct Ti Pct 0 Pct C Pct N Pct H Pet CO 5.29 0.08 0.004 0.002 0.0003 Balance By proper tilting of the crystal, it was possible to obtain slices 1/32 in. thick of [loo] and [110] orientation. The solution heat-treated crystal slices were sealed in silica capsules for the aging treatments, with titanium sponge placed at one end of the capsule to act as a getter. All slices were water-quenched from the aging temperatures, the capsules being broken under the water to ensure a rapid quench. Thinning of the slices for transmission X-ray studies was accomplished by a combination of mechanical and electrolytic techniques, the final thickness being about 0.1 mm. Laue patterns of the solution heat-treated crystal indicated that no strain was introduced by the thinning technique. ELECTRON METALLOGRAPHY After X-ray examination, the structural changes attending the precipitation were followed by examination of direct carbon replicas of polished and etched surfaces of the single-crystal slices and extracted phases. The earliest indication of significant structural change was observed after aging at 600°C The structure of a heavily etched, solution-treated crystal is shown in Fig. l(a). Aside from the etch pit pattern, no regularity of background structure is observed. On the other hand, in the background of the specimen heated for 500 hr at 600°C, the etching pattern shows a directionality indicating the influence of minute precipitate particles, Fig. l(b). On electrolytic dissolution of this specimen in 10 pct HC1 in alcohol, a large volume of very small, flattened cubes

Jan 1, 1962

By George C. Stone

AS most of you probably know, Australia has had many strikes. The two places that had the worst reputation were the Broken Hill mines and Port Pirie, where the smelter was located. About four or five years ago, the smelter changed hands. The new proprietors - immediately endeavored to get on better terms with the men and made such progress in that respect that, the men came to them and said, "There is no use giving us any more money. You have just raised our pay one- bob a day, but the store-keeper and the boarding-house keeper have raised their prices. The boarding housekeeper raised our board three bob a week and the storekeeper took the rest of it and we are no better off." Learning that what the men needed most was firewood wood the company bought the wood on a tract of ground across Spencer&apos;s Gulf and- sent men over to cut it. The wood was brought to the works and given to a man to cut up. He thought he had an easy job and loafed, but when the committee representing the men discovered that his loafing added to the cost of &apos;the wood, it promptly disciplined him and made -him work as he had never worked before. The next question that arose was the distribution of the wood. The committee got bids from several cartmen whose prices varied from about two to five shillings. It gave the work to the next to the lowest bidder. The fact that if delivering the wood cost more, the user would have to pay for it, was an entirely new idea to the men.

Jan 1, 1920

By C. E. Richards, C. N. Reid

The influence of preferred orientation on the incidence of defbrtnation tuinning has been studied. High-purity iron with almost vandonz grain orientation was cotnpared uitll iron of the sa)ne grain size and composilion lza,ing a strong (110) fiber texture. As expected from published work on single crgslfls, /he ))lean stress for the onset of luitzning-, and the l,olu)nt. fraclion of twinned nzaterial obserlled in lension differed fron the 1-a1ue.s it2 co?nPression for tnolerial with a slrong texlure. The llinning stress of "rctndorrl " )zalerial did not 17ary with the sense of the aPPlied unin.via1 stress, but sirprisinglg the incidence of 1c)i)zning- was about three 1i))zes greater ill conzp?&apos;ession Illon in lension. These results (Ire attributed entirely to ovienbation and may be nderslood in ler?ns of the shear slresses acting on the allowed twinning syster)is. J. HE twins most commonly formed in bcc metals may be described as regions of the crystal in which a particular set of (112) planes is homogeneously sheared by 0.707 in the appropriate ( 111) direction. A similar twin-related crystal could be produced by a shear of 1.414 in the reverse (111) direction but twinning by this large displacement has never been reported. Thus, twinning is unidirectional and a shear stress which produces twinning does not do so when its sense is reversed. The sense of a shear Stress is reversed when the loading is changed from tension to compression, or vice versa. Consequently, for a given orientation of a crystal relative to a uniaxial stress, only a fraction of the twelve (112) twinning systems are geometrically capable of operating in tension, and the remaining systems may operate only in compression. Therefore, when twinning is involved, there are expected to be differences in behavior between crystals tested in uniaxial tension and those tested in compression. This has been verified experimentally by Reid et 01.&apos; and Sherwood el al.,&apos; although a critical stress criterion was not encountered. Furthermore, twinning stresses in colmbium," tungten, tantalum,&apos; irn,&apos; i-Fe,\ nd molybdenum7 single crystals have been shown to depend critically on orientation, although again twinning did not occur at a critical value of the macroscopic shear stress. However, when twinning occurs, it generally does so on the most highly stressed systems, 1--4&apos;6&apos;8&apos;9 implying that the stress level does have some relevance to twin formation. In view of the large orientation dependence of twinning in bee single crystals, it might be expected that such an effect would be present in poly crystalline material which possesses a recrystallisation texture. Indeed, riestner" showed that the twinning stress in tension is very orientation-sensitive it1 <&apos;grain-oriented, silicon-iron;" this material possessed a very strong t c m^ii a nnr x_____k . i-_ii__ ri_______j. _x r»i_._:__i preferred orientation obtained by secondary recrystallisation. Reid et a/.&apos; observed a marked difference in the tensile and compressive yield stresses of polycrys-talline columbium which was rationalised in terms of the effect of a preferred orientation on twinning. No other such illformation is known to the authors. Several investigations of twinning in polycrystalline bcc metals have been reported in which the possible existence of a preferred orientation was not even mentioned. It is the purpose of this paper to show that there is a strong effect of texture on twinning in polycrystalline iron, and to poilt out the difficulty in eliminating preferred orientation in recrystallised metals. 1. EXPERIMENTAL METHOD Material and Specimen Preparation. Low-carbon, high-purity iron was obtained from the National Physical Laboratory in the form of $-in. diam rod which had been cold-swaged from a diam of 1 in. The composition of the material is given in Table I. The as-received bar was cold-swaged directly to 0.185 in. diam from which cylindrical tensile and compression specimens were machined. Specimen geometry is illustrated in Fig. 1. The gage length was 0.30 in. long and 0.10 in. diam; it should be noted that, apart from the extra heads which are necessary for tensile loading, the geometry and dimensions of the two types of specimen are identical. The specimens were heat treated either by sequence A or B outlined in Table 11. The essential difference between these two treatments is that in one case the material was repeatedly cycled through the y- to a-phase change in order to produce grains of almost random orientation ("random" iron)

Jan 1, 1969