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By Neils Hansen

The microstructure of dispersion-strengthened aluminum aluminum-oxide products containing from 0.2 to 4.7 wt pct of aluminum oxide has been examined by optical and transmission electron microscopy, and the flow stress has been determined at room temperature and at 400C by tensile testing. Products were examined as recrystallized and as high-temperature extruded, and the microstructures consisted of a fine dispersion of oxide particles in a matrix divided by respectively recrystallized grain boundaries and subgrain boundaries. The flow stress (0.2 pct offset) at room temperature of recrystallized dispersion strengthened aluminum aluminum-oxide products is the superposition of dispersion strengthening and grain boundary strengthening. This superposition has been found to be linear. The flow stress (a) can be related to the grain size (t) by the Petch equation: ing content of oxide and k is a constant independent of the oxide content. For extruded products a similar relation has been found by replacing the grain size by the subgrain size. The k-value is of the same order for the two types of structure, which shows that the subgrain boundaries are as effective slip barriers as grain boundaries. Tensile testing at 400C of re-crystallized and extruded products shows that oxide dispersion strengthening is very effective, whereas the strengthening effect of grain boundaries and subgrain boundaries is small. THE microstructure of dispersion-strengthened products consists of hard particles finely distributed in a metal matrix. The strengthening effect of the dispersed phase has been fairly well established,1 and it has been found that the size and volume fractions of the dispersed particles are important structural parameters. However, in many dispersion-strengthened products which have been worked and heat-treated during manufacture the matrix is divided into well-defined grains or sub-grains, which may also have a strengthening effect. A model of the matrix strengthening in dispersed products worked during manufacture has been proposed,2 introducing the energy of the structure as a strengthening factor, especially at low temperatures. A difficulty in this model is, however, to relate this (stored) energy to the structural parameters directly observable as for instance grain size. The strengthening effect of the matrix grain size after recrystallization has been in- vestigated for nickel-thoria (TD-Nickel) products3 and for copper aluminum-oxide products. Conclusive results were, however, not obtained as the grain size of TD-nickel was constant. 5 to II , after recrystallization at temperatures from 700 to 1200°C and as the copper products containing 5 to 1 wt pct of aluminum oxide could not be recrystallized even after severe cold reduction and heat treatment at 1050C. For aluminum aluminum-oxide products containing from 1 to 5 wt pct of aluminum oxide it has been shown that the tensile strength at room temperature decreases when an extruded product is cold-worked and recrystallized. The matrix in the extruded products is divided into well-defined subgrains of micron size, and as the grain size of the recrystallized products is about two orders of magnitude higher, it is obvious that grain boundary strengthening occurs. Preliminary results8 have indicated that the flow stress containing no grain boundaries, A is a constant and t is the subgrain size. At elevated temperatures the effect of boundaries is more complex; it has been shown11 that recrystallized products having an oxide content of about 3 wt pct are more creep resistant than extruded material in the temperature range 400° to 600°C, whereas on application of a higher strain rate the tensile flow stress (0.2 pct offset) is higher in extruded than in recrystallized aluminum—5 wt pct aluminum oxide products at temperatures from room temperature to 427°C (800), Finally it has been shown12 that the Brinell hardness at 350°C of extruded products having about the same content of aluminum oxide increases with decreasing grain size, determined by X-ray line-width measurements. The present study was undertaken to obtain a quantitative relationship between the tensile strength and the grain size of aluminum aluminum-oxide products in the recrystallized as well as in the extruded state. The tensile testing was performed at room temperature and at 400uC. The grain size of the recrystallized products was varied by changing the degree of cold-work preceding the recrystallization heat treatment. In extruded products grain (or subgrain) size variations were obtained by high-temperature heat treatment after extrusion. EXPERIMENTAL a) Materials. Aluminum aluminum-oxide products have been manufactured by consolidation of aluminum powder covered with a layer of aluminum oxide formed during powder manufacturing. The products examined were manufactured from atomized powder containing

Jan 1, 1970

By Carlos G. Valenzuela

The value generally accepted for stacking-fault energy, of copper has been approximately 40 ergs per sq cm based on Fullman's2 value for the coherent twin-boundary energy and the assumption that is twice the twin boundary energy However, Thornton and coworkers8 determined that the lower limit of for copper is approximately 60 ergs per sq cm, based on measurements of dislocation-node radii. They suggested that the assumption of = 2t is invalid. It is the purpose of this note to present results which indicate that the values of obtained by measurement of twin-grain boundary intersections and the values obtained by measurement of dislocation-node radii are actually compatible. The most reliable values for of the a brasses, based on electron-microscope observation of dislocation nodes, are probably those values reported by Smallman and Green6 who applied the Siems correction (1961) to data obtained by Howie and Swann.3 These values shown in Fig. 1 give an extrapolated value of approximately 70 ergs per sq cm for pure copper. In the present work, Fullman's method for determining the stacking-fault energy of copper was extended to the a brasses. High-purity copper (99.999 pet) and high-purity zinc (99.999 pet) were mixed in proportioned amounts and melted in sealed and evacuated quartz tubes. The alloys were homogenized for a week at 750°C and chemically analyzed by means of X-ray fluorescence. These alloys, along with a specimen of pure copper, were rolled to 98 pet reduction and a thickness of 0.009 in., resealed, and annealed for 40 hr at 715°C. Values for the ratio of twin-boundary energy to the grain-boundary energy, it gb, were obtained from measurements of dihedral angles formed at the intersections of twin boundaries and grain boundaries by using Fullman's2 mechanical analogy of surface tensions acting at the intersection of an annealing twin and a grain boundary. The angles between the twin traces and the grain boundaries were measured for a large number of twin-grain boundary intersections at a magnification of X500 using a rotating mechanical stage on a Reichert metallograph. The rotary stage has a calibrated angle scale with vernier so that measurements can be made to 0.1 deg. The mean twin-grain boundary energy and standard deviation were calculated for copper and each of the brasses by the use of an IBM 7072 computer. It was found that the mean value of gb stabilized after approximately 100 twin-angle measurements. This was determined by plotting the mean against the number of angles measured. Since the measured angles deviate from true dihedral angles, a correction factor for grain orientation, discussed below, was applied. The stacking-fault energy was then calculated from these values and the values of grain-boundary energy derived by Taylor.7 The data obtained are tabulated in Table I. Values for stacking-fault energy are plotted in Fig. 1. The value of gb for the specimen of 1.03 pet Zn is close to the value obtained by Fullman2 for OFHC (99.98 pet) copper, 0.045. It is believed that the purity of the copper affects gb significantly. The 99.999 pet purity Cu used in this investigation yielded a value of yt/ygb, 0.76, which is much higher than that obtained by Fullman. Additional evidence suggesting that the purity of

Jan 1, 1965

By R. S. Kinasevich, D. D. Crabtree, D. W. Fuerstenau, T. P. Meloy, A. L. Mular

The effect of such variables as feed size, particle shape, cleavage, and hardness on the relative proportion of impact, abrasion, and chipping events in a tumbling mill is demonstrated. The concept of an average event, which is a combination of the three comminution mechanisms, is introduced. It is postulated that the average event in a particular mill determines not only the size distribution but also the energy-size reduction relationship for the comminution process. Fragmentation of particles in tumbling mills appears to result from a combination of impact, abrasion, and chipping grinding.' The relative rates of size reduction attributable to any of the basic grinding mechanisms must depend upon a number of variables, such as feed size, particle shape, hardness, and the number and kind of particles in the mill. The purpose of this paper is to show experimentally how these variables in the properties of materials affect the size distributions obtained by grinding the material's in a laboratory tumbling mill. The resulting size distributions will be intetpreted in terms of a combination of three comminution mechanisms. METHODS AND MATERIALS In this study, minerals of widely differing properties were ground either separately or as mixtures in laboratory mills using rods or balls for grinding media. The materials used include quartz, Tuolomne, limestone (99.8% CaCO3), barite, corundum, galena, pyrite, glass beads, and crushed glass. The mill used was 8 in. in diam. and 9-1/4 in. long. For the ball milling tests, 17.6 kg of steel balls (36: 7/8 in. balls, 178: 1 in. balls, and 44: 1-1/8 to 1-1/4 in. balls) were used. For the rod milling experiments, 17.6 kg of steel rods 9-1/16 in. long (25: 5/8 in., 10: 3/4 in., and 5: 7/8 in. in diam.) were used. In each test, 1 kg of solids were ground wet at 60% solids at 77 rpm. In all cases except where otherwise specified, the feed to the mill was 4 x 8 mesh material. Size distributions of the ground products were determined by a wet-dry sieving procedure with Tyler series sieves. Size distributions of mixed products containing limestone were determined by dissolving the limestone with acid and sizing the residue. EXPERIMENTAL RESULTS AND DISCUSSION If the size distribution of the product from a tumbling mill depends upon the relative proportion of impact and attrition (abrasion and chipping) events, altering the grinding conditions may change these proportions and consequently alter the size distribution of the product. Data to illustrate this point can be taken from Gaudin's classic 1926 paper.2 In one series of experiments, Gaudin ground quartz of different initial sizes for four hours in a laboratory ball mill with 7/8-in. balls. In Fig. 1, his data are reproduced as the cumulative fraction finer than the stated size for the following initial feed sizes: 13.3 x 9.4 mm, 6.7 x 4.7 mm, 2.6 x 1.6 mm, and 0.83 x 0.59 mm. As the feed size was decreased, a dramatic change in the shape of the size distribution curves took place, even though the amount of minus 100-mesh

Jan 1, 1964

By G. W. Sheary

At Bethlehem's Grace mine's 6000-tpd pelletizing plant a cascade control system is utilized to approach a constant magnetite filter cake moisture, a critical factor in obtaining quality green pellets. Variables being controlled by instrumentation are filter feed solids, filter tub level, first and second stage pump sump levels and thickener sludge level, all at varying feed rates. Startup difficulties, modifications and contemplated additions to obtain closer control of the moisture are discussed. Situated 45 miles west of Philadelphia and 50 miles southwest of Bethlehem Steel Co. 's Beth-lehem plant, the integrated Grace mine facilities produce 4000 tpd of high-quality iron ore pellets. Startup of the Grace mill was in November 1958, and iron concentrates were shipped until March 1960, when the pellet plant went into operation. The underground mine, when fully developed, will hoist about 9000 tpd, including development rock. The crude ore, which has an iron content of approximately 42%, is magnetically cobbed and crushed in closed circuit with %-in. slotted vibrating screens. The ore is washed and screened in the mill and the 1/4-in. screen product is again cobbed prior to feeding to the rod mills. Grinding is done in rod mills, and in ball mills that are in closed circuit with 30-in. cyclones, to 1% on 100 mesh and 65% -325 mesh. The ground ore is magnetically concentrated by three-drum permanent-type finisher magnets to 67% Fe. The magnetite concentrate is pumped from the mill to a 50-ft thickener in the pellet plant. The thickened magnetite concentrate is relayed to the filters through a two-stage pump arrangement. The filter cake is fed by belt from filter concentrate bins to mixer-muller belts where it is intimately mixed with bentonite and a slight amount of water for moisture control. The fluffed concentrate then drops into balling cones. The green pellets from the balling cones are fed in a prescribed feed pattern to shaft furnaces through the use of shuttle car mechanisms. The green pellets are dried, heated to 2500°F and cooled to 1200°F as they descend through the furnace and into pellet coolers where the pellets are further reduced in temperature to 250°F. Heat is recovered in the cooling process through the use of air-to-air heat exchangers. The cooled pellets discharge on a rubber conveyor belt and are transferred to 6000-ton pellet railroad loading bin. The final pellet product consists of 90% +'1/4 in. material (after tumble testing1) and contains 66% Fe plus 3% silica. It has been the usual practice to maintain constant filter tank level by pumping an excess constant volume and using a moveable fishtail splitter to divert the desired amount of slurry to the filter tank. The excess from the fishtail and from the filter overflow pipe, which maintains a constant level, is returned to the source. At the Grace mill, tremolite builds up in the pipelines when pumping heavy magnetite concentrate slurries, making it necessary to use polyvinyl

Jan 1, 1962

HeRbeRT Haas,—(communication to the Secretary*).—Fig. I plainly shows that the comparison of the steam-turbine and Diesel-engine plants was made on a basis of 6,000 kw. continuous operating load. The tabulation of costs for an 8,000-kw. load is merely done to show the relation of increased output on the unit power costs. Both plants would sacrifice their reserve capacity, which is to insure continuous operation, if operated to generate 8,000 kw. continuously; unless Mr. Hawkins advocates the operation of one of the turbines at 33.33 per cent. overload, retaining the other as a standby, which, besides overtaxing the turbine, results in a great loss of efficiency. It would be well for Mr. Hawkins to qualify certain of his statements. Thus, under the caption "Diesel Engines, Selection of Units," he says that '(two of the largest Diesel-engine builders take the position that, in the present state of the art, they would not attempt to put out units over 1,000 kw.;" he should qualify it by saying that "two of the largest American Diesel-engine builders take the position that, in the present state of the art in the United States, they would not attempt to put out units over 1,000 kw." The reason that American manufacturers restrict themselves at present to units of that size is to be found not so much in a lack of experience in building large units as in a lack of a sufficient demand for them in the United States to justify the heavy capital outlay connected with the development of such engines. There are relatively few localities in the United States where fuel prices are as high as they are in the South-, west, and regions of high fuel prices are sparsely settled and have a very limited demand for power. Where low fuel prices obtain, steam turbines are active competitors of Diesel engines for large power plants, particularly when the station load factor is low. As most of the American manufacturers of Diesel engines work under license agreements with European manufacturers, which limit their market to the United States and its possessions and Canada, a further limitation is imposed upon them, leaving to European firms practically the entire world as a market. The greater number of power plants range in size from 300 to 1,000 hp.; the average size of the central station, on a basis of all central stations in the United States, not greatly exceeding 500 kw.; in these sizes it is hard for steam engines to compete with Diesel engines, unless fuol oil prices are excessively high, and coal prices very low, or the exhaust steam is used for heating purposes.

Jan 1, 1917

By B. D. Cullity

Gold and beryllium form an intermediate phase composed of the two metals in equal atomic proportions and having the formula AuBe. According to Winkler,' this phase probably exists in two modifications: beta, stable below about 600°C, and alpha, stable between 600°C and the melting point, about 740°C. Only the low-temperature beta form will be considered in this paper. Experimental Procedure The gold used had a fineness of 999.75 to 999.85, balance mainly silver, and the beryllium purity was better than 99.8 pct. AuBe was prepared by melting the constituents in a beryllia crucible in an evacuated induction furnace. After melting and thorough mixing, the alloy was allowed to solidify in the crucible. No difficulty was encountered in obtaining a homogeneous ingot. Both chemical analysis and microscopic examination of the ingot showed that the alloy was essentially one phase, containing 50 at. pct gold. The alloy was quite brittle and powder samples could easily be prepared by grinding in an agate mortar. The X-ray diffraction patterns were made with CuK-alpha radiation in a Debye-Scherrer powder camera 57.3 mm in diameter. The film was placed unsym-metrically in the camera in order to afford a basis for film-shrinkage corrections. A sample homogenized at 500°C gave the same diffraction pattern as a sample taken from the as-melted ingot. General Results The diffraction pattern of AuBe was readily indexed on the basis of a simple cubic lattice with ao = 4.659 + 0.001kX. If the unit cell is assumed to contain four AuBe "molecules," the calculated X-ray density is 13.46 grams per cc as compared with the measured density of 13.55 gm per cc. The only missing reflections in the diffraction pattern are (100) and (220) (see Table I). Since these missing reflections are not those characteristic of body or face centering, the lattice of AuBe must be simple cubic. To locate the positions of the atoms within the unit cell, two possibilities had to be considered: I. The structure was disordered and there were eight positions to be filled by an LCaverage" gold-beryllium atom. That the structure was disordered seemed unlikely since the lattice parameter did not vary with composition in alloys containing sornewhat more and somewhat less than so at' pet gold, indicating a fixed composition for AuBe.

Jan 1, 1947

By B. D. Cullity

Gold and beryllium form an intermediate phase composed of the two metals in equal atomic proportions and having the formula AuBe. According to Winkler,' this phase probably exists in two modifications: beta, stable below about 600°C, and alpha, stable between 600°C and the melting point, about 740°C. Only the low-temperature beta form will be considered in this paper. Experimental Procedure The gold used had a fineness of 999.75 to 999.85, balance mainly silver, and the beryllium purity was better than 99.8 pct. AuBe was prepared by melting the constituents in a beryllia crucible in an evacuated induction furnace. After melting and thorough mixing, the alloy was allowed to solidify in the crucible. No difficulty was encountered in obtaining a homogeneous ingot. Both chemical analysis and microscopic examination of the ingot showed that the alloy was essentially one phase, containing 50 at. pct gold. The alloy was quite brittle and powder samples could easily be prepared by grinding in an agate mortar. The X-ray diffraction patterns were made with CuK-alpha radiation in a Debye-Scherrer powder camera 57.3 mm in diameter. The film was placed unsym-metrically in the camera in order to afford a basis for film-shrinkage corrections. A sample homogenized at 500°C gave the same diffraction pattern as a sample taken from the as-melted ingot. General Results The diffraction pattern of AuBe was readily indexed on the basis of a simple cubic lattice with ao = 4.659 + 0.001kX. If the unit cell is assumed to contain four AuBe "molecules," the calculated X-ray density is 13.46 grams per cc as compared with the measured density of 13.55 gm per cc. The only missing reflections in the diffraction pattern are (100) and (220) (see Table I). Since these missing reflections are not those characteristic of body or face centering, the lattice of AuBe must be simple cubic. To locate the positions of the atoms within the unit cell, two possibilities had to be considered: I. The structure was disordered and there were eight positions to be filled by an LCaverage" gold-beryllium atom. That the structure was disordered seemed unlikely since the lattice parameter did not vary with composition in alloys containing sornewhat more and somewhat less than so at' pet gold, indicating a fixed composition for AuBe.

Jan 1, 1947

By Persifor Frazer

For various reasons I have not specified the locality where the research indicated in the following pages was undertaken. It will suffice to say that it was on the grounds of a villa once remote from, but now completely surrounded by, its neighboring city, and in close proximity to an industrial establishment of great extent and importance manufacturing many kinds of steel articles and employing upwards of thirty chimney-stacks for power and process work. The problem was to discover the cause or causes of the mortality to trees and plants on the place, and to trace these causes to their origin. Before undertaking this experimental work, the bibliography accompanying this paper was compiled and studied. It appears from an examination of the careful scientific work performed by the ablest French, German, and English chemists during the last 25 years that they are unanimous in assigning the principal—in fact, the overwhelmingly predominant— cause of the destruction of vegetation to sulphur oxides, resulting either from direct oxidation of sulphur in oil of vitriol works, etc., or from the oxidation of the sulphur from the minerals associated with commercial coal. Schroder and Schertel showed in 1884 that the sulphates deposited upon the leaves are not injurious to the plants; and Freytag proved that free sulphuric acid could not be found

Jan 1, 1908

By Joseph G. Debanné

Foreword The three case histories and the liquid fuels planning scenario presented in this paper span a twenty year period, from the pioneering days of computers in the petroleum producing industry during the mid-fifties, to the energy crisis era of the seventies. Inasmuch as two of the main actors, Ian McKinnon and I, are featured in all three case histories, while I am currently involved in the fossil fuels scenario, this paper provides four related and personal spot readings along an evolutionary path: from the one dimensional technical domain to the multi-dimensional techno-socio-economic domain of computer applications in the petroleum industry. Coincident with this evolution in the direction of increasingly comprehensive and powerful computer applications, the evolution in hardware/software capability and in analytical power are also kept in perspective. The three case histories are: 1. The Bonnie Glen-Wizard Lake Case (Calgary, Alberta, 1955-1957); 2. The TransCanada-Great Lakes Gas Transmission Case (Ottawa-Washington, 1966); 3. The Westcoast Transmission - El Paso Pipelines Gas Export/ Import Case (Ottawa-Vancouver-Washington, 1966-1967). The liquid fuels planning scenario is a demonstration exercise rather than a case history; however, it represents an important point on the evolutionary curve and, provides a concrete example of tech-

Jan 1, 1977

By Horace Pops, Jorge E. Kittl

In a recent study' of the martensitic transformation of Cu-Zn ß-phase alloys, it was noted that the MS temperature at the surface was raised due to the loss of zinc by volatilization. It seems likely, therefore, that the MS temperature may serve as a guide for the measurement of composition. From a knowledge of the dependence of the transformation temperature on composition, 2 it should be possible to detect variations in zinc content which are less than 0.1 at. pct by measuring the MS temperature throughout the sample. It is unlikely that an electron microprobe analysis could detect accurately such small zinc losses because the presently accepted limits of accuracy of the micro-probe analysis in simple ternary systems are of the order of 2 to 5 pct of the amount present.3 In the present study, a composition gradient was produced by precipitating the a primary solid solution, and reheating for a very short time within the ß-phase field. The nominal composition, in atomic percent, of the ternary ß-phase alloy used, 64.2 Cu, 34 Zn, 1.8 Si, was selected because it had an MS temperature of +4°C, thereby simplifying the experi-

Jan 1, 1968

By John Wulff, David A. Stevenson

The solubility of iron and cobalt in liquid lead, the solubility of chromium in liquid tin, and nickel in liquid silver were determined up to 1300°C in an atmosphere of hydrogen. Liquid samples were taken at different temperatures and analyzed. The data obtained were plotted to show the relationship between log mole fraction of solute and the inverse of the absolute temperature. Resulting values for the differential heat of solution (AH) and the excesspartial molar entropy (S)are: for the iron-lead system = _24,200 cal per mole and AT = 5.0 e.u. for the a phase, and AH = 18,300 and S = -0.1 e.u. for the y phase; for the cobalt-lead system AH = 16,500 cal per mole and AS =0.7 e.u.; for the chromium-tin system AH = 15,600 cal per mole and AS = 8.5 e.u.; for the nickel-silver system AH =18,000 cal per mole and AS = 4.0 e.u. RECENT developments in coating, brazing, and heat transfer have focused attention on specific cases of solid-liquid interaction in metal systems, particularly those involving dilute liquid solutions. One fundamental quantity of interest in such systems is the equilibrium phase distribution between solid and liquid phases. In any effort to fully understand such interactions, one must be able to describe the equilibrium state precisely. Furthermore, in order to develop genera! relations for such systems, one must know the equilibrium state in a number of different cases. This investigation was devoted to a study of the equilibrium phase distribution in four binary systems: solid iron-liquid lead; solid cobalt-liquid lead; solid chromium-liquid tin; solid nickel-liquid silver. The iron-lead system was previously studied by Shepard and parkman' and later by Fleischer and Elliott2 with differing results. Both investigations were carried out by sampling the saturated liquid, and analyzing it chemically. The cobalt-lead system was previously reported by Pelzel,3 who noticed no discontinuity near the transformation. A limited investigation of the chromium-tin system was made by Wlodek and wulff4 using a weight loss method. This work was done in conjunction with the development of a process for coating molybdenum with chromium from tin solutions. To more fully under- stand the kinetics of the process, a more accurate determination of a solubility was desirable. No significant data were found in the literature on the nickel-silver system. Data on the latter system were, however, relevant to the investigation of the corrosion kinetics of copper-nickel alloys in liquid silver as carried out by Harrison and wagner,5 EXPERIMENTAL APPARATUS AND PROCEDURE Of the techniques available for the study of such systems the most effective appears to be that of liquid sampling,2,6,7 which is the method used in the present investigation. A schematic diagram of the sampling furnace is given in Fig. 1. Large pieces of solute metal, in excess of saturation solubility, were added to 200 g of the solvent metal, and the entire charge placed in an alundum crucible. Analytical reagent or materials of chemically pure grade were used in all investigations. The crucible was contained in a zircon muffle tube positioned vertically in the uniform hot zone of a Globar resistance furnace. The tube was provided with a number of ports which permitted sampling at temperature and in controlled atmospheres or vacuum; the ports were also useful for evacuation and introduction of gases as well as for thermocouple measurements. A chromel-alumel thermocouple Sheated in a porcelain tube was used for temperature measurements. A purified hydrogen atmosphere was employed in all experiments reported in this paper. The hydrogen was purified by passing it first over hot copper gauze to remove oxygen and then through a molecular sieve immersed in

Jan 1, 1962

By S. F. Frederick, W. A. Bailey

The relationship between microstructure and mechanical properties of cast 356-type aluminum alloys was studied to determine the cause of the variations in properties resulting from differences in solidification rate. It was found that variations in strength are a consequence of variations in ductility and that ductility is inversely proportional to the dendrite cell size. A mechanism is proposed to account for this correlation based on the fracture strain of the inter-dendritic silicon particles and the differential strain across dendrite cell boundaries. IT has long been assumed that permanent mold castings of aluminum are superior to sand castings because of their finer grain structure and reduced porosity.' A systematic variation of static properties was noted during unpublished studies of fatigue-strength variations with solidification rate of A356-T6. Of particular interest was the observation that for a given composition and heat-treatment, both ductility and the ultimate strength increased with higher solidification rate. Because the A1-Si system forms the basis of many alloys used for castings and welding wire, a study was initiated to determine the details of how higher cooling rates improved mechanical properties of these alloys. The results of this study are presented here. EXPERIMENTAL PROCEDURE Specimens were prepared from 356-T6 to supplement the A365-T6 alloy data from earlier studies. This allowed a comparison of behavior of alloys with substantially different strengths but with only small differences in alloy composition. The composition and heat treatment of both alloys are given in Table I. The specimens were cut from a chill plate casting,' which is a 6 by 9-in. plate, 1 in. thick, which has one end heavily chilled, and a large riser at the other so that solidification is essentially unidirectional from the chill end to the riser. Although not measured here, solidification times measured on similar specimens by embedded thermocouples are a few seconds at the chill end and up to 5 min near the riser. Specimens were obtained by cutting slabs from the plate, parallel to the chill; these represented different cooling rates, with essentially the same composition. For the tests, either 0.125 or 0.250-in. thick slabs were cut for standard 2-in. gage length specimens. The thicker specimens were tested to failure at 2000 lb per min while the thinner specimens were tested in an Instron machine at a constant cross-head speed of 0.02 in. per min. These thin specimens were intended for trans- mission electron microscopy. Some thin specimens were tested to failure while the remainder were given various amounts of prestrain. Dendrite cell sizes were measured by the linear intercept method on photomicrographs at either X100 or X50, depending on the cell size. It was assumed that the dendrite cells were outlined by the silicon particles. Determinations were made on two mutually perpendicular planes and an rms average taken. Electron fractographs of representative tensile specimens were made in the conventional manner using the two-stage replica technique.3 Samples for transmission electron microscopy were prepared by chemical milling followed by electropolishing. RESULTS AND DISCUSSION The results of the tensile tests and the dendrite cell-size determinations are given in Figs. 1 and 2. All data show the same trends, namely, a decrease in ultimate strength and elongation with increasing distance from the chill (and solidification time), and a corresponding increase in dendrite cell size. The yield strength remains essentially constant. The constancy of the yield strength was particularly significant since it indicated that variation in the solidification rate does not affect the stress required to initiate plastic flow. By plotting true stress-true strain curves as in Fig. 3, it can be seen that both

Jan 1, 1969

By R. Schuhmann

The expression "unit process " comes up with increasing frequency in discussions among metallurgists and mineral engineers, especially among those concerned with training the next generation. The unit process approach characterizes a significant advance along the road from metallurgy as an empirical art to metallurgy as a branch of engineering. The purposes of this paper are to define and list the unit processes in specific terms, to indicate the scientific and engineering principles basic to all the unit processes, and finally to show how these ideas have been applied to a reorganization of instruction in chemical metallurgy. Unit Operations and Unit Processes Metals are extracted from ores and other raw materials by stepwise procedures. In general, each metallic element is extracted by a different procedure. For many of the metals there is a choice of several flowsheets. However, the procedures all have steps in common. In fact, the many different flowsheets are all made up of a relatively small number of steps which are combined in different groups and sequences. For example, crushing, screening, roasting, sintering, melting, and gaseous reduction are steps which each appear in the Bowsheets for extracting the majority of the metals. The individual steps or flowsheet units can be designated as unit operations or unit processes. These terms are well established in the field of chemical engineering, as the American Institute of Chemical Engineers' definition of chemical engineering shows: " Chemical engineering is that branch of engineering concerned with the development and application of manufacturing processes in which chemical or certain physical changes of materials are involved. These processes may usually be resolved into a coordinated series of unit physical operations and unit chemical processes. The work of the chemical engineer is concerned primarily with the design, construction, and operation of equipment and plants in which these unit operations and processes are applied. Chemistry, physics, and mathematics are the underlying sciences of chemical engineering, and economics its guide in practice."'1a In this definition, the distinction between unit operations and unit processes is that the unit operations are physical while the unit processes are chemical. Table I gives a list of the principal unit operations and unit processes of chemical engineering, taken from Shreve.1b Table 2 lists the principal unit operations and unit processes used for metal extraction. The division between unit operations and unit processes is similar to the chemical engineers' distinction and also correspollds approximately to the division of labor bctween mineral dressing and chemical metallurgy which has been customary in the past. Furthermore, it will be noted that in the proposed classification the unit processes primarily involve chemical reactions and/or changes in state of aggregation; the unit operations primarily do not involve either bulk

Jan 1, 1949

By C. H. P. Lupis, R. Hocine, G. Bernard

The necessary and sufficient conditions for the stability of a multicomponent phase with respect to infinitesinzal fluctuations are derived and transformed to be written in terms of activity coeffcients and mole fractions rather than in terms of the customary second deritlatives of the free energy. NECESSARY conditions for the stability of a multi-component system were derived by Gibbs as early as 1876.' However, as the usefulness of these conditions is greatly enhanced by the simplicity of their translation in terms of functions of common usage, the present contribution establishes these conditions in terms of activities or activity coefficients-and mole fractions. It was shown in another article2 that not only may these conditions be used for the prediction of the appearance of new phases, but they may also provide a check on the orders of magnitude of the interaction coefficients involved. "Spinodal" decomposition is said to occur when, at constant temperature and pressure, the system is unstable with respect to infinitesimal fluctuations in composition. As a result, the "phases" which appear may be attained through continuous changes in the system rather than discontinuous ones, and, consequently, the free energy of these phases may be described by a unique continuous free-energy function. For a binary system, the familiar curve of Fig. 1 illustrates the case we wish to extend to a multicom-ponent system. The conditions to be written pertain to the decomposition of a system of n moles into moles of phase moles of phase v, ...hen moles of phase 9, where the phases a, ...v, ...9 are—at least initially-arbitrarily close in composition to that of the original phase. Each A, is positive and since the total number of moles n in the system remains constant: Each phase v contains hv(nl +dnY) moles of component (I), ...xV(ni +dny) of component + dnk) moles of component (m). The total number of moles ni in the system remaining also constant, it is clear that:

Jan 1, 1968

By Arnulf Muan, Klaus Schwerdtfeger

Equilibrium ratios C02/C0 of a gas phase coexisting with selected phase assemblages of the system Fe-Mn-0 have been determined in the temperature range 1000" to 1300°C. The oxygen pressure for the "hfnO" +hfn30, equilibrium and for the "(Fe,hTn)O" + (Fe,Mnh 0* equilibrium at high manganese contents has been determined by electromotive force measurements using stabilized zirconia as a solid electrolyte. The notstoichometry 01' "hTnO" and of "(Fe, iM1z)O" solid solutions has been determined by ther-mog-/avi?netry and by wet-chemical analysis. The data obtained are used to derive activity-composition relations in "(Fe,hfn)O" and (Fe,Mn),O4 solid solutions. WUSTITE "FeO" and manganosite "MnO" form a continuous series of solid solution at high temperatures,' and so do magnetite Fe304 and the high-temperature, cubic modification of Mn304 (Ref. 2) (high hausmannite, -1170). The oxides "FeO" and "MnO" are cation-deficient phases.495 The nonstoi-chiometry of "(Fe,Mn)O" solid solutions has been studied by Engell and ~ohl' at two selected C02/C0 ratios at 1250°C. The two oxide end members of the spinel solid solution, FesO4 and Mn,04, however, are known to be close to stoichiometric under the experimental conditions used in the present investigation.''' The oxygen pressures of "(Fe,Mn)07' solid solutions in equilibrium with iron have been determined by Schenck and coworkers,8 by Foster and welch," and by ~n~e1l.l' The two former groups equilibrated the condensed phases in C02-CO atmospheres of lmown compositions, whereas Engell" used a galvanic cell with stabilized zirconia as a solid electrolyte. The results of these investigators are not in good agreement. Activities of FeO in manganowiistite as calculated from the results of Foster and Welch show ideal behavior, those of Engell yield a pronounced positive deviation, and those of Schenck et 01. show a moderate positive deviation from ideality. In the present work oxygen pressures for the iron + manganowiistite and manganowustite + spinel equilibria and the nonstoichiometry of manganowiistites have been measured. The data were used to calculate activities in the manganowiistite and spinel solid solutions. EXPERIMENTAL METHODS The COz/CO ratios at which manganowustite and iron are in equilibrium were determined by thermo-gravimetric and quenching methods. Experimental details are described in a previous publication.'2 In the thermogravimetric technique, incipient reduction of manganowiistite pellets to metallic iron was observed as a break in the weight vs log COZ/CO curve. In the quenching technique, manganowiistite samples were partially reduced to metallic iron, or the metallic iron of manganowustite + metallic iron mixtures was partially oxidized to manganowustite, in atmospheres of constant C02/CO ratios. After quenching the composition of the oxide phase was determined by X-ray lattice parameter measurements and comparison with a standard curve obtained from oxide solid solutions of known compositions. The nonstoichiometry of "MnO" and "(Fe,Mn)07' solid solutions was determined by chemical analysis of samples equilibrated in C02-CO atmospheres and quenched to room temperature, as well as thermo-gravimetrically by reducing (Fe,Mn),04 or Mn304 to manganowiistite or manganosite. The equilibrium between manganowiistite and (Fe,Mn),04 was measured thermogravimetrically by reducing (Fe,Mn),04 solid solutions having composition in the range of %„ l(NFe +NM) from 0 to 0.63. No experiments could be performed with this technique at higher manganese contents, because the equilibrium C02/C0 ratios are too large for accurate control. An additional difficulty arises at the higher manganese contents due to the strong increase in oxygen content of the manganowustite phase with increasing log Py near the manganowiistite-spinel boundary. Consequently a sharp break in the weight loss vs log C02/CO curve cannot be observed at the phase boundary. At high manganese contents of the manganowiistite, e.g., (NMn/(NF~ + NMn) > 0.9, electromotive force measurements with stabilized zirconia as a solid electrolyte were made to determine the equilibrium oxygen partial pressure. Experimental details are described in a previous paper.* Mixtures of "(Fe,Mn)O" and (Fe,Mn),04 were pressed to pellets, and the oxygen pressure of the equilibrated samples was compared to that of Ni + NiO mixtures in the cell The composition of the manganowiistite in the equilibrated two-phase mixture was determined by lattice parameter measurements and comparison with known standards. The oxygen pressure for the Ni + NiO equilibrium was taken from available data.l3~l4 No reliable results were obtained with the electromotive force technique on iron-rich oxides. The electromotive force drifted strongly with time in this composition range. An additional difficulty arises from the partial de-

Jan 1, 1968

By Y. Oinouye, H. Ries

Of the several interesting physical properties of clay which have claimed the attention of investigators in recent years, none is more important than the behavior of the material when heated to temperatures above those of dehydration. Some of the problems to be solved are: 1. The mineralogical changes that take place in firing. 2. The relation between temperature and change in constitution, shrinkage, porosity, etc. 3. The importance of the time factor, as duration of firing, either in reaching a given temperature, or of exposure to a constant temperature. Mineralogical Changes As a result of fusion, reactions take place between the constituents of a clay, which result in a reorganization of the mass, and the formation of new compounds. Of the new minerals developed, sillimanite is the one usually recorded, and has been referred to by a number of observers.' There appears to be a difference of opinion, however, regarding the temperature at which it is formed. Thus Klein2 notes that sillimanite forms only above 1300" C., while Mellor claims that it can develop below 1200" C., the difference in results being conditioned by the time factor. In Klein's experiments the test pieces were fired in 12 hr., while in Mel-lor's, the temperature rose from 800" to 1180" in 24 hr., and occupied the same time in cooling back to 800".

Jan 1, 1918

By R. H. B. Jones

This paper reviews pertinent geology of the Biwabik iron formation, Mesabi Range, Minnesota. This iron formation is divisible into four members. Each member is distinctive and contains marker horizons, which are recog nizable throughout all phases of alteration from lean, fresh rock to high-grade iron ore. Some beds have a larger magnetite content than others. During the process of ore genesis, which is essentially an oxidation process, the magnetite content is lowered. Alteration from iron formation to ore includes both oxidation of iron minerals and silica removal by leaching and these distinct processes progress at variable rates for different locations and structures. Magnetic intensities, of each horizon of the iron formation are dependent chiefly upon its preoxidation magnetite content, upon the subsequent degree of oxidation, upon the character of the enclosing rocks, and on the extent of fracturing, folding, or faulting. The results of a number of magnetic surveys are described and are correlated with results of drill-hole and mine exploration and developmerit. The magnetic anomalies obtained are discussed in relation to phases of formation of ore within the iron formation. General Information One hundred years ago a party of surveyors, applying the principles of geophysical prospecting, discovered iron ore in the state of Michigan in the Lake Superior district. This event was officially reported as follows:' On Sept. 19 (1844) while running the east line of Town 47 North, Range 27 West, they observed by means of the solar compass remarkable variations in the direction of the needle, amounting to 87" from the normal. Ascribing this phenomenon to iron ore, they sought and found it in ledges or outcrops at several points. The solar compass referred to was invented by William A. Burt, deputy surveyor in charge of this party.2 It is used for determining the true meridian by an observation on the sun. Eight years later, on July 7, 1852, the first iron 're, consisting of 6 bbl. of Ore, was shipped from Marquette, Michigan. It was another 40 years before the first or> shipment left the Mesabi Range in Minnesota, in October 1892. It totaled 4245 tons. Fifty years later, 90 years after the original shipment, during 1942 the Lake Superior district shipped 93,495,392 gross tons of iron ore. Production came from Minnesota, Michigan, Wisconsin, and Ontario, Canada. Throughout the 90-Year period it was known that magnetic properties of most of the ore bodies, and of the iron formations in which they occur, affected the compass. This phenomenon, later to be made use of to outline areas of ground favorable for exploration, was at first a

Jan 1, 1949

By R. H. B. Jones

This paper reviews pertinent geology of the Biwabik iron formation, Mesabi Range, Minnesota. This iron formation is divisible into four members. Each member is distinctive and contains marker horizons, which are recog nizable throughout all phases of alteration from lean, fresh rock to high-grade iron ore. Some beds have a larger magnetite content than others. During the process of ore genesis, which is essentially an oxidation process, the magnetite content is lowered. Alteration from iron formation to ore includes both oxidation of iron minerals and silica removal by leaching and these distinct processes progress at variable rates for different locations and structures. Magnetic intensities, of each horizon of the iron formation are dependent chiefly upon its preoxidation magnetite content, upon the subsequent degree of oxidation, upon the character of the enclosing rocks, and on the extent of fracturing, folding, or faulting. The results of a number of magnetic surveys are described and are correlated with results of drill-hole and mine exploration and developmerit. The magnetic anomalies obtained are discussed in relation to phases of formation of ore within the iron formation. General Information One hundred years ago a party of surveyors, applying the principles of geophysical prospecting, discovered iron ore in the state of Michigan in the Lake Superior district. This event was officially reported as follows:' On Sept. 19 (1844) while running the east line of Town 47 North, Range 27 West, they observed by means of the solar compass remarkable variations in the direction of the needle, amounting to 87" from the normal. Ascribing this phenomenon to iron ore, they sought and found it in ledges or outcrops at several points. The solar compass referred to was invented by William A. Burt, deputy surveyor in charge of this party.2 It is used for determining the true meridian by an observation on the sun. Eight years later, on July 7, 1852, the first iron 're, consisting of 6 bbl. of Ore, was shipped from Marquette, Michigan. It was another 40 years before the first or> shipment left the Mesabi Range in Minnesota, in October 1892. It totaled 4245 tons. Fifty years later, 90 years after the original shipment, during 1942 the Lake Superior district shipped 93,495,392 gross tons of iron ore. Production came from Minnesota, Michigan, Wisconsin, and Ontario, Canada. Throughout the 90-Year period it was known that magnetic properties of most of the ore bodies, and of the iron formations in which they occur, affected the compass. This phenomenon, later to be made use of to outline areas of ground favorable for exploration, was at first a

Jan 1, 1949

By J. Weertman

An explanation is advanced for the recent results of Barrett and Sherby on the high-temperature creep of fee metals. Their measurements indicate that metals with a low stacking fault energy creep at a much slower rate than metals with a high stacking fault energy. The explanation is based on the assumption that the rate of core diffusion is much smaller in partial dislocations than in perfect dislocations. An experiment is suggested to test this assumption. The explanation also requires that the jog density is small on widely split dislocations. SHERBY and Barrett1,2 recently established an important result in the field of high-temperature steady-state creep. They have shown that fee metals whose dislocations split into partial dislocations separated by a wide stacking-fault ribbon creep at a much slower rate than fee metals whose dislocations are not split appreciably. The creep rates in the two cases may differ by a factor as high as 6000. (For the purpose of comparison, the test temperature of each metal was chosen so that its rate of self-diffusion was equal to a standard value. Similarly the stress levels were such that the ratio of the stress to an appropriate elastic modulus was the same for each metal. In all cases the stresses were sufficiently low that the steady-state creep rate was proportional to the stress raised to a power.) It is the purpose of the present paper to attempt an explanation of this interesting and significant result of Sherby and Barrett. The activation energies of high-temperature creep of the metals tested by Sherby and Barrett (aluminum, nickel, copper, and silver) were equal to their self-diffusion activation energies. Hence it appears reasonable to assume that this type of creep is controlled by a dislocation-climb process, which in turn is controlled by the diffusion of vacancies to or from dislocation lines. (It will be assumed that the diffusion of interstitial atoms is unimportant in the climb process. The analysis could be repeated for the case in which interstitial atoms are important.) In prior papers374 I have treated dislocation climb by using the assumptions that core diffusion is extremely fast down a dislocation and that a dislocation always maintains an appropriate vacancy concentration in its immediate vicinity. In this

Jan 1, 1965

By E. A. Anderson, C. W. Siller, Gerald Edmunds

In the pressurc die-casting of zinc alloys it is customary to force the molten alloy under high pressure into a permanent steel die by means of a plunger moving in a bushing that has a clearance on the diameter of the order of 0.002 in. Successful operation of the plunger type of machine requires the presence in the zinc alloy of certain percentages of aluminum. Without these aluminum additions, the normal reaction of molten zinc on ferrous materials causes sticking of the plunger arid a complcte shutdown of the equipment. All of the zinc alloys used for pressure dir-rnsting today contain approximately 4 per cent of aLUminum, which is more than suffieient to make plunger opcration feasible. The clearancc bet,ween the plunger and its bushing is an important matter. As the space bccomes larger, there is a loss in effective metal pressure. Ordinary gray cast iron served fairly well and is still uscd in some machines. However, the rate at which the plunger c1earance. increases with this material is considered by many to be far too great. There is, therefore, a serious interest in finding new matcrinls more: capable of retaining the desired clearance during long periods of use. Today marly die casters are using special materials for plungers and bushings selected by the somewhat expensive and time-consuming test of actual experience. An analysis of the problem reveals two possible end points of plunger. operation: (1) the building up of zinc-alloy plunger-material reaction products in sufficient bulk to cause sticking and (2) rapid solution, wear or erosion, all of which will increase the clearance to an undesirable extent. If neither of these takes place, the pluriger will operatc for a long time, of course.. The authors have developed a laboratory apparat,us in which the action of a plunger moving in a bushing immersed in molten zinc alloy could be simulated closely. Such a machine made possible a more rapid and less expensive survey of the available construction materials and an analysis of the specific alloying reactions taking place in the clearance area.

Jan 1, 1940