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By David E. Hyatt

The chemical attributes of cyanides have long been exploited in ore pro- cessing schemes for the recovery of copper, molybdenum, gold, silver, and other metal values. Blast furnacing operations are significant unintentional producers of cyanides which find their way into process waters. Many of the more than 20,000 electroplating facilities in the United States utilize cyanide plating baths and generate cyanide containing wastes. As social, political, and economic pressures for water quality attainment, maintenance, and preservation grow, the requirements for the development of treatment technology to control cyanide levels in wastewater become increasingly apparent. Just as the chemistry of the cyanide ion 1s an integral part of its industrial applicability, so must this chemistry be a fundamental part of any decomposition or removal technology used to control its level in effluent or recycled waters. The complexity of this chemistry is substantial and it cannot be considered in a superficial or cursory manner if control system design is to be both efficient and reliable.

Jan 1, 1975

By Frank L. Nason

(New York meeting, February, 1912) IN the year 1904 an eminent Swedish geologist prepared a report on the iron-ore reserves of the world. His estimates follow: Countries. Tons. United States, 1,100,000,000 Great Britain, . 1,000,000,000 Germany, 2,200, 000, 000 Spain, 500,000,000 Russia and Finland, 1,500,000,000 France, 1.500, 000, 000 Sweden, . 1,000,000,000 Austria-Hungary, . 1,000,000,000 Other countries, 1,200,000,000 Total, . 10,000, 000, 000 The iron-ore allotted to the United States by the Swedish geologist is barely sufficient to last 20 years at the present rate of consumption. On the other hand (according to Edwin C. Eckel,1 from whom the above and following statistics are quoted), there is hardly need for worry on the part of our iron industries for the, next two centuries or more. Upon the basis of careful work by the U. S. Geological Survey, in which Mr. Eckel has taken an important part, the following estimates arc definitely, but by no means finally, given for the United States District. Tons. Lake Superior District, . . 1,500,000,000 to 2,000,000,000 Alabama, red hematite. . . 1,000,000,000 brown hematite, 725,000,000 Georgia, red hematite, 200,000,000 brown hematite, 125,000,000 Tennessee red hematite, . 6110,000,000 I brown hematite, 225,000,000 Virginia., red hematite, 50,000,000 brown hematite, 300,000,000 Total, . . 4,725,000,000 to :5,225,000,000

Jul 1, 1912

By Herbert Clark Hoover, Lou Henry Hoover

PREVIOUSLY I have dealt with the methods of separating silver from copper. There now remains the portion which treats of solidified juices ; and whereas they might be considered as alien to things metallic, nevertheless, the reasons why they should not be separated from it I have explained in the second book. Solidified juices are either prepared from waters in which nature or art has infused them, or they are produced from the liquid juices themselves, or from stony minerals. Sagacious people, at first observing the waters of some lakes to be naturally full of juices which thickened on being dried up by the heat of the sun and thus became solidified juices, drew such waters into other places, or diverted them into low-lying places adjoining hills, so that the heat of the sun should likewise cause them to condense. Subsequently, because they observed that in this wise the solidified juices could be made only in summer, and then not in all countries, but only in hot and temperate regions in which it seldom rains in summer, they boiled them in vessels over a fire until they began to thicken. In this manner, at all times of the year, in all regions, even the coldest, solidified juices could be obtained from solutions of such juices, whether made by nature or by art. Afterward, when they saw juices drip from some roasted stones, they cooked these in pots in order to obtain solidified juices in this wise also. It is worth the trouble to learn the pro- portions and the methods by which these are made. I will therefore began with salt, which is made from water either salty by nature, or by the labour of man, or else from a solution of salt, or from lye, likewise salty. Water which is salty by nature, is condensed and converted into salt in salt-pits by the heat of the sun, or else by the heat of a fire in pans or pts or trenches. That which is made salty by art, is also condensed by fire and changed into salt. There should be as many salt-pits dug as the circumstance of the place permits, but there should not be more made than can be used, although we ought to make as much salt as we can sell. The depth of salt-pits should be moderate, and the bottom should be level, so that all the water is evaporated from the salt by the heat of the sun. The salt-pits should first be encrusted with salt, so that they may not suck up the water. The method of pouring or leading sea-water into salt-pits is very old, and is still in use in many places. The method is not less old, but less common, to pour well-water into salt-pits, as was done in Babylon, for which Pliny is the authority, and in Cappadocia, where they used not only well-water, but also spring-water. In all hot countries salt-water and lake-water are conducted, poured or carried into salt-pits, and, being dried by the heat of the sun, are converted into

Jan 1, 1950

By Philip Bucky

THE term "longwall mining" is best known to coal men, although modifications of the method are continually being used in other fields. Longwall mining is of interest today because it makes for greater mecha-nization and better supervision at the working face, and therefore lower production costs and increased safety. It is an approach to the factory system of production, the high efficiency of which as compared to that in mines is well known. There is available an accumulation of experience regarding this work but coordination of experience is lacking and this series of experiments was undertaken to help serve this purpose. Model experiments were used for reasons of safety, cost and time, and because it has been previously shown1,2,3 that a scalar model built of the same material as the prototype will behave in a manner similar to that of the prototype, with time effects the same, if the effective weight of the model is increased in the same proportion as its linear dimensions are decreased. This is accomplished by substituting a centrifugal for the gravitational field; i.e., placing the model in a centrifuge and controlling the strength of the centrifugal field by varying the rate of rotation. Many factors affect the behavior of the geologic material overlying a bed, therefore results and conclusions contained in this paper apply only to the conditions presented herein.

Jan 1, 1938

By Joe B. Alford

Jan 1, 1971

By LEE H. CORNELL

Drilling activity in Kansas during 1945 continued at an accelerated pace to meet the demands of war; 1810 tests were drilled as compared with 1856 tests the previous year, 1771 tests in 1943, and 1516 tests in 1942. During the year 31 new oil pools and 10 new gas pools were discovered. Of a total of 364 wildcats drilled, 323 were dry; and of 1446 tests drilled in pools, 825 were oil wells, 197 gas wells, and 425 dry holes.

Jan 1, 1946

By F. W. Glaser

Iron-silicon alloys have had a great influence, in many ways, in modern industry. Silicon steels have been used almost exclusively for the construction of electrical machinery, but have also become an important material for structures which benefit by the high tensile and yield strengths of this material. In elaborating on the early history of work done on iron-silicon alloys, Greiner, Marsh and Stoughton1 went back as far as 1808, and pointed to Berzelius as the first producer of ferrosilicon. During the last twenty years some very important contributions in the form of studies of the iron-silicon system, as well as of the physical properties of these alloys, have been published. In consideration of the brit-tleness and poor machinability of alloys containing more than 5-6 pct Si, commercial interests have stimulated the research done on iron-silicon alloys, but mainly in the range of 0 to 6 pct Si. Yensen2 has shown the influence of im- purities, such as carbon, sulphur and phosphorus on the magnetic properties of 2, 4, and 6 pct Si alloys. Corson3 extended his investigation of physical properties to approximately 32 pct Si, and attributed the brittleness of the high-silicon material to the particular constitutional features of the alloys. Though mentioned earlier in the literature, the effect of nitrogen on crystal growth and magnetic permeability of iron-silicon alloys has been demonstrated recently by Morrill4 and Rostoker,5 respectively. In all the above quoted investigations, except that of Rostoker,5 sand or chill casting processes were employed for the preparation of samples. A major advantage of the powder metallurgy process is that it does away with time-consuming machining in many applications. The powder metal industry is always interested in pro- ducing a finished product employing a material which has presented considerably greater difficulties in manufacture by other methods. Steinit26 described preparation and testing of various Fe-Si alloys which were produced by the powder metallurgy process for the manufacture of armatures for small electric motors or generators. While Steinitz investigated alloys up to 6 pct Si, Rostoker5 went as high as 9 pct Si. The author7 previously discussed the diffusion of iron-silicon compacts containing 6 and 10 pct silicon. It is the object of this paper to study the progress of diffusion occurring in iron-silicon alloys by electrical resistivity measurements. All samples were prepared by pressing and sintering of compacts. Iron, silicon, and Fe-Si powders of various mesh size and compositions were employed to obtain test samples. It was assumed that complete diffusion had been obtained when the electrical resistivity reached a constant value characteristic for that particular alloy. To this end, electrical resistance measurements were used to follow the progress of alloying under various conditions.

Jan 1, 1950

By J. G. Giddings, R. Kobayashi

Residual viscosity, the ViSCOSitY at a given pressure and temperature minus the dilute gas viscosity at the same temperature, has been found to be independent of temperature for pure components and mixtures for simple molecules and light hydrocarbons. The residual viscosities for methane, ethane, propane and four mixtures were correlated as a function of reduced density and molecular weight. INTRODUCTION Earlier efforts in correlating the viscosity of light hydrocarbons and associated gases under pressure, primarily by some form of the corresponding states principle, have been reported elsewhere.7 The formal theory of corresponding states principle for viscosity from non-equilibrium statistical mechanical arguments for simple molecules has been developed by Helfand and Rice.13 The most serious obstacle to the development of a generalized corresponding states representation of viscosity data, even for simple molecules, has been the limited quantity of precise viscosity data of pure components and mixtures over a wide range of pressure and temperature conditions. Viscosity data on light hydrocarbons have recently been contributed by several laboratories.2,6,8,23,25,26 In the study of the viscosity of nitrogen, Michels and Gibson" observed that the viscosities of nitrogen as a function of density gave parallel isotherms. The same behavior has since been reported for other gases.".= The observed behavior indicates that the residual viscosity or the viscosity at a given pressure and temperature minus the dilute gas viscosity at the same temperature is a unique function of the density. Abas-Zade,1 Michels and Botzen,18 and Michels, Bot-Zen, Friedman and Sengers,19 observed similar behavior for thermal conductivity, the residual thermal conductivity being defined in a manner parallel to that of residual viscosity. Thodos and co-workers 4,15,24 applied the residual viscosity concept to the viscosity of pure monatomic and diatomic gases. Ellington and co-workers10,25 made the residual viscosity vs density plots for ethane and propane, but omitted the region below a residual viscosity of 15 micropoise and showed a systematic separation of the ethane isotherms in the low density region. Eakin correlated the residual viscosity of methane, ethane, propane and n-butane empirically as a function of density and molecular weight: Carmichael and Sage6 recently presented ethane residual viscosity vs density values in the gaseous liquid, and near critical regions as a single univariant function of density. Flynn, Hanks, Lemaire and ROSS" have contributed extremely accurate viscosity data to confirm that the residual viscosity concept is essentially correct, but may not be accurate within 0.1 per cent of the viscosity value for the gaseous state- The recent studies by Giddings12 indicate that the residual viscosity of methane, propane and each of four methane-propane mixtures are unique functions of density Over the temperature and the density ranges studied.

Jan 1, 1965

By J. V. Gluck

In the present paper," as in earlier publications, V1'2"1 the authors present experimentally obtained relations for the free energy of solution of oxygen in various metals as a function of temperature. The relations are linear and given in slope-intercept form. The authors give values for the "probable error" of the slope and intercept, citing Birge's method17 for obtaining these quantities. Birge discussed these methods as early as the period 1929-32.25726 In Ref. 25 the probable error is defined as "the numerical value which the true error is as likely to exceed as not", i.e., 50 pct probability. Ref. 26 is even more detailed and includes a lengthy discussion of the applicability of the Gaussian distribution to experimental data. However, the use of the "probable error" has come under some question. For example, Ezekiel'~ states that "the use of the probable error tends to make the results appear rather more accurate than the standard error". Moroney28 stated (in 1951) that "the term 'probable error' was used in former times to denote 0.67450 (50 pct confidence using the normal distribution)....the term, a poor one, is now very much obsolescent. It has been said that 'it is neither an error nor probable' ". Bennett and Franklin in 1954" in discussing statistical confidence levels mentioned that "the customary use of the 5 and 1 pct levels is not completely a matter of chance; these levels probably represent a balance between the desire to be correct and the desire to be specific. Also in most people's minds the borderline between something that could possibly happen and something that is not likely to happen is somewhere in this region. Certainly 5 or 1 pct confidence limits are to be preferred to limits such as the 'probable error' which has only a 50/50 chance of including the correct value." It may readily be seen that the 95 pct confidence level, which is given by 1.960 (assuming large sample size), thus corresponds to approximately three times the "probable error". Indeed, limits of one standard deviation correspond only to about 68 pct probability. Even if we triple the tolerances given by the authors in the equations of their Table 111, the deviations do not become excessive and would not detract from their excellent results. It could then be said with a high degree of confidence (95%) that the precision of the slope and intercept values is about *3-5 percent of their absolute levels rather than the 1-2 percent implied in Table 111. This is then compatible with an earlier suggestion of Gokcen~' of a probable accuracy of 5 pct in dissolved oxygen measurements by the technique employed. Alternatively, the authors could have

Jan 1, 1967

By J. F Haseman, J. E. Davenport

In the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1,2 results in inadequate beneficiation. Investigation of Flotation Methods Flotation has been used in 'Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate. 3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P2O5 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P2O5, 20; SiO2, 40; CaO, 29; Fe2O3, 2; Al2O3, 3; F, 2.3. The particle-

Jan 1, 1948

By J. F. Haseman, J. E. Davenport

In the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1,2 results in inadequate beneficiation. Investigation of Flotation Methods Flotation has been used in 'Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate. 3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P2O5 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P2O5, 20; SiO2, 40; CaO, 29; Fe2O3, 2; Al2O3, 3; F, 2.3. The particle-

Jan 1, 1948

By A. P. Cohen, D. W. Fuerstenau

Methods of accounting for the feed size in analyzing the size distribution shift during comminution have been discussed in a number of papers.1,2,3 Based on experiments which charles2 performed with single Pyrex specimens, Schuhmann4 pointed out that the size modulus of an assembly of particles should be determined by the energy expended per unit volume (or mass), independent of the size of particle being comminuted. In this same paper, Schuhmann derived the Charles energy-size reduction relationship by considering that complex comminution operations can be considered to be the summation of many individual comminution events, each of which must be governed by Were 6wi is the mass of a particle receiving the impact, 6Ei is the energy delivered to the particle, ki is the size modulus of the product resulting from the impact, a is the distribution modulus of the assembly of particles, and A is a constant. Recent experiments on the compression loading of Pyrex spheres ranging in size from 1/8 to l-in. diam have shown that the size modulus of the fragments is determined by the strain energy at fracture per unit mass, independent of sphere diameter.' The objective of the present investigation has been to determine experimentally whether the size distribution of the product from such a complex comminution process as rod milling is determined only by the energy expended per unit mass independent of feed size. Samples of each Tyler sieve fraction ranging from 4x6 to 48x65 mesh were prepared from crushed Brazilian quartz crystals. One kilogram of each fraction was ground at 60 pct solids in an 8x9 1/4-in. mill containing 17.5 kg of rods (26 rods, 5/8-in.; 10 rods, 3/4-in.; and 5 rods, 7/8-in. diam). In each test, the mill was run at 77 rpm for 15 min. Size distributions were determined by a wet-dry sieving technique. Table I presents the size distribution of the products obtained by grinding each of the size fractions. Because the size distributions are so nearly alike, they are plotted in Fig. 1 by shifting each size distribution for the different feed sizes one screen fraction to the right. Thus, the lowest point in each size distribution represents 400 mesh and each of the other sieve sizes must be shifted accordingly. A single regression line was calculated by combining the data for the six tests, excluding the coarsest feed and the two finest feed fractions. 6 This regression line, which is given by (Y \0.88 where y is the cumulative percentage of material

Jan 1, 1962

Prospectors were digging silver in the Ray mine area in 1873, and by 1880 high-grade copper ore was feeding a 30-ton copper furnace. In 1910, D. C. Jackling and his associates organized the Ray Consolidated Copper Company, known in mining circles as Ray Con, to exploit the Ray orebody. For 50 years, all mining was underground and the Ray mine was known the world over for innovations in mining methods. It was the first to mine important tonnage (8,000 tpd) by block caving methods. The mill at Hayden, 26 miles (41.6 km) from the mine, kept pace with the new mining methods developed at Ray and in the early 1920's flotation replaced gravity concentration by the vanner machines. First mining by open pit methods began in 1950 and in January 1955 all underground mining was discontinued. The new primary crushing plant, installed in early 1967, featured design simplicity with a low capital cost. The 54 in. gyratory crusher was installed within a total height of 6 1 ft (18.65 m) from the truck dump road bed to the floor beneath the feeder-conveyor under the surge pocket. The crusher is fed by 120-ton trucks dumping from one side only into a 200-ton hopper equipped with a horizontal splitter bar to protect the crusher spider. The crushed ore pocket, of 120 -ton live capacity underneath the crusher, discharges to a 0 to 200 fpm (61.2 mpm), variable-speed, 72 in. by 80 ft long (1.83 m by 24.4 m) sloped belt feeder, probably a first in the industry. Wood-picking stations are provided on either side of the belt so that old mine timbers and tramp iron can be removed from the crushed ore and the wood can be dropped into Dempster containers located below the belt. Counter-weighted finger gates control the bed depth on the belt at 14 in. (356 mm) and a low- level radiation unit automatically maintains a minimum of a 3 ft bed (900 mm) of material on the belt directly under the surge pocket. The conveyor is skirted for its full length and is approximately 60 in. (1.52 m) wide inside its metal skirt liners. Ten impact idlers at 12 in. (305 mm) spacing are provided under the loading pocket and remaining idlers are spaced at 18 in. (457 mm). The belt is 1 ¼ in. (31. 8 mm) thick; and, while it has occasionally been damaged by tramp material, belt life averages 11 million tons. When the belt is changed, the coiled new belt is lowered into position onto one of two belt stands mounted over the feeder, the old belt is cut, and one end is attached temporarily to the new belt. The other end of

Jan 1, 1978

By G. R. Speich, L. Zwell, H. A. Wriedt

HORNBOGEN1 has recently shown that it is possible to measure the degree of segregation accompanying cellular precipitation in ferritic Fe-Zn alloys by measuring the lattice parameter of the ferrite phase within the cell. In extending this work to study a wider range of composition and to evaluate the free-energy change accompanying the growth of the cells, the lattice parameter and the boundary of the a! phase in Fe-Zn alloys were redetermined to check the earlier work of Schramm.2 This appeared to be necessary since the Fe-Zn diagram has been drastically revised since the work of Schramm. Stadelmaier and Bridgers3 have recently shown that, contrary to prior belief: the y iron field is closed and the a phase boundary extends to an a + T + L peritectic at 782°C where peritectic a contains 42 at, pet Zn. The phase T in equilibrium with the a solid solution has a composition near Fe3Zn10 and a cubic 081 type structure.' The alloys were prepared by two different methods. In the first method carbonyl iron powder (400 mesh, 99.8 pet pure) and high-purity zinc powder (200 mesh, 99.99 pet pure) were mixed in a ball mill and then pressed in a die at 40,000 psi pressure to make compacts with a diameter of 5/8 in. and a thickness of l/4 in. These were sealed in evacuated quartz capsules, gradually heated to 1100°C over a period of 1 week (3 days at 600°C) 3 days at 800°C, 1 day at (1100°C), and then quenched in iced brine. For the alloys containing 23.4 and 30.1 at. pet Zn, the final homogenization anneals were performed at 1000" and 850°C) respectively, to prevent melting. In the second method, alloys were prepared by saturating high-purity iron millings (0.001 in. thick, 99.9 pet pure) in zinc vapor. For each alloy the impregnation was conducted at a fixed vapor pressure of zinc and a fixed temperature between 750' and 800°C. When saturated, the millings were quenched in water. The compositions of the alloys prepared by both methods are shown in Table I. The lattice parameters of the ferritic solid solutions were determined by comparing the 26 values of their 310, peaks (using Co Ka) or of their 211 , peaks (using Cr Ka) with those of corresponding peaks for high-purity a iron. The 20 values were measured at room temperature with an X-ray dif-fractometer (G.E.-XRD5). By using a fiducial value of 2.8664Å for the lattice parameter of pure a iron at 25oC,5 the lattice parameters of the zinc-bearing

Jan 1, 1964

By J. E. Breen, J. Weertman

The creep rate of polycrystalline tin was studied as a function of temperature and stress in constant stress experiments. The temperature was varied from room temperature to almost the melting point of tin. Activation energies were calculated from tests run at the same stress. It was found that on a log creep rate vs inverse temperature plot the experimental points did not fall on one straight line but on a line which changed its slope in the 90° to 160°C region. Two activation energies for the creep of tin can be calculated from the data: a value around 26,000 cal per mol at high temperatures and a value around 11,000 cal per mot at low temperatures. It is suggested that the discrepancies between the creep activation energies and those of self-diffusion can be accounted for if self-diffusion takes place predominately by Zener's ring mechanism rather than through vacancy or interstitial movement. SHERBY, Orr, and Dorn' and Dorn' have recently reviewed some of the data on high temperature creep of metals. -The data show that the activation energy of high temperature creep is approximately equal to the activation energy of self-diffusion. This same correlation has also been successfully made between the activation energy of grain boundary relaxation and that of self-diffusion.3,4 The metal tin does not fit into this simple picture. Its activation energies of self-diffusion differ appreciably from that of grain boundary relaxation and of creep. Fensham,5 from a precisely performed experiment, has determined that the activation energies of self-diffusion of tin are 10,500 and 5,900 cal per mol along the C and A axes, respectively. There are two energies because of the anisotropic nature of tin. Rotherham, Smith, and Greenough6 have shown that the grain boundary relaxation activation energy is 19,000 cal per mol (measurements made from room temperature to 100°C). Puttick and King7 found the same activation energy for grain boundary slip in bicrystals of tin (180° to 225°C region). Until recently, there was no high temperature large strain creep data on tin suitable for activation energy calculations. At rather small strains (up to 0.01), Tyte8 had made a series of measurements on tin from which activation energies can be calculated. In Fig. 1 are plotted some of his data on a log creep rate vs inverse temperature graph. It can be seen that Tyte's work indicates that at a relatively low temperature the activation energy is around 7,400 cal per mol but at higher temperatures the activation energy increases. Since Tyte measured the creep only for small strains, it is doubtful if a

Jan 1, 1956

By J. A. Fellows, Earnshaw Cook, Howard S. Avery

HEAT-RESISTANT alloys of the higher nickel and chromium ranges have been empirically developed through the practical experience of the past two decades to a position of significant industrial importance. Few quantitative metallurgical data have been published, however, that could be related directly to engineering specifications and design. Inadequate information led to the inauguration, in 1934, of a research directed toward a better understanding of the properties and performance of these steels at temperatures between 1400° and 2000°F. Investigation was concentrated upon the 26 per cent Cr:12 per cent Ni type, which owes its extensive application to an excellent combination of economy, strength and surface stability at elevated temperatures. The requirements of the oil-refining industry have been prominent in influencing the scope and evolution of the program. Creep strength at the maximum allowable deformation ranges has been employed to evaluate the merits of these alloys. Permissible elongation rates vary from 1.0 per cent in one million hours for turbine blades to 1.o per cent in ten thousand hours for tube supports and heating-furnace equipment. Throughout this paper, the limiting creep stress (L.C.S.) for a given temperature has been defined as the stress that will produce a uniform elongation rate (stage II) of one per cent in ten thousand hours as extrapolated from rates per hour or tests of less than two thousand hours duration. Certain current specifications require a minimum L.C.S. of 1600 lb. per sq. in. at 1800°F., of 3600 lb. per sq. in. at 1400°F., and include a tensile acceptance test at room temperature, after aging for 24 hr. at 1400°F., as a measure of embrittlement in service. An elongation of 4 per cent is considered satisfactory for general use, while a minimum of 9 per cent is prescribed on occasion. Many differences of opinion concerning the properties and performance of these alloys appear to result from their sensitivity to unappreciated variations of chemical analyses which, for example, may change their L.C.S. from 3500 to 350 lb. per sq. in. at 1800°F. Within broad chemical limits, it is possible to balance the six or more important elements present to attain desirable properties with a number of different combinations. One method for adjusting the composition has been described under the sponsorship of the Alloy Casting Institute,1 in which, by maintaining a substantially austenitic* alloy, optimum creep strength and minimum tendency to embrittle after aging are expected. Unless, however, the limits are undesirably dose, it has not been possible to ensure a moderate range of strength and of ductility by any chemical specification alone. There is a definite need

Jan 1, 1942

By J. A. Fellows, Earnshaw Cook, H. S. Avery

THE increased use of heat-resistant alloys (26 per cent Cr, 12 per cent Ni, 16 per cent Cr, 35 per cent Ni, 12 per cent Cr, 60 per cent Ni, etc ) in recent years has been accompanied by continued demands by the consumer for improvement in properties The manufacturers of these materials, of necessity, have resorted to more critical studies of the basic causes of variations in fundamental properties To keep pace with the need for augmented information, previous techniques of investigation have been refined and new test methods and instruments created It is the purpose of this paper to describe the apparatus, experimental technique and precision of measurement that were employed in the exploration of properties of heat-resistant alloy presented in a companion paper† The detailed precautions in experimental procedure essential for attainment of accurate and comparable data at elevated temperatures cannot be too highly emphasized THE CREEP TEST Since the fundamental concepts of creep testing have been recognized for the past 20 years, present interest is restricted to refinements in equipment and experimental procedure The creep-test laboratory constructed for the American Brake Shoe and Foundry Co is designed to permit 1000-hr tests in the temperature range of 1200° to 2200°F with a choice of applied stress extending from 50 to 50,000 lb per sq in in increments of 50 lb per sq in To simplify the calculation of weight combinations, the loading beams (Fig I) are provided with counterweights to eliminate the tare The precision of the knife-edges (10 1 ratio) is such that a 10-gram weight placed on the upper specimen grip will be exactly balanced by a 1-gram weight attached to the loading shackle Check of the loading weights proved the maximum error to be 0 06 per cent Axial alignment is provided by crossed knife-edges in the grip seats The furnaces are similar in design to those of Crane and Company, Battelle Memorial Institute, and the U S Steel Corporation An 80 per cent Pt, 20 per cent Rh No 19 B and S gauge wire is used as the heating element The details of construction are shown in the radiograph reproduced in Fig 2 The windings are held in place on an alundum tube with alundum cement, the distribution of turns is adjusted to give a maximum temperature gradient of ± 1°F over a 4-in gauge length (Fig 3) To avoid sharp temperature differentials at the ends of the test section, the length of the furnace is four times the gauge length Sixteen-inch coupons are used to reduce the temperature of the threaded

Jan 1, 1942

By Earnshaw Cook, J. A. Fellows, Howard S. Avery

Heat-resistant alloys of the higher nickel and chromium ranges have been empirically developed through the practical experience of the past two decades to a position of significant industrial importance. Few quantitative metallurgical data have been published, however, that could be related directly to engineering specifications and design. Inadequate information led to the inauguration, in 1934, of a research directed toward a better understanding of the properties and performance of these steels at temperatures between 1400° and 2000°F. Investigation was concentrated upon the 26 per cent Cr:I2 per cent Ni type, which owes its extensive application to an excellent combination of economy, strength and surface stability at elevated temperatures. The requirements of the oil-refining industry have been prominent in influencing the scope and evolution of the program. Creep strength at the maximum allowable deformation ranges has been employed to evaluate the merits of these alloys. Permissible elongation rates vary from 1.0 per cent in one million hours for turbine blades to I .o per cent in ten thousand hours for tube supports and heating-furnace equipment. Throughout this paper, the limiting creep stress (L.C.S.) for a given temperature has been defined as the stress that will produce a uniform elongation rate (stage 11) of one per cent in ten thousand hours as extrapolated from rates per hour for tests of less than two thousand hours duration. Certain current specifications require a minimum L.C.S. of 1600 lb. per sq. in. at I800°F., of 3600 lb. per sq. in. at 1400°F., and include a tensile acceptance test at room temperature, after aging for 24 hr. at 1400°F., as a measure of embrittlement in service. An elongation of 4 per cent is considered satisfactory for general use, while a minimum of 9 per cent is prescribed on occasion. Many differences of opinion concerning the properties and performance of these alloys appear to result from their sensitivity to unappreciated variations of chemical analyses which, for example, may change their L.C.S. from 3500 to 350 lb. per sq. in. at 1800°F. Within broad chemical limits, it is possible to balance the six or more important elements present to attain desirable properties with a number of different combinations. One method for adjusting the composition has been described under the sponsorship of the Alloy Casting Institute,' in which, by maintaining a substantially austenitic* alloy, optimum creep strength and minimum tendency to embrittle after aging are expected. Unless, however, the limits are undesirably close, it has not been possible to ensure a moderate range of strength and of ductility by any chemical specification alone. There is a definite need

Jan 1, 1942

By J. A. Fellows, Earnshaw Cook, Howard S. Avery

Heat-resistant alloys of the higher nickel and chromium ranges have been empirically developed through the practical experience of the past two decades to a position of significant industrial importance. Few quantitative metallurgical data have been published, however, that could be related directly to engineering specifications and design. Inadequate information led to the inauguration, in 1934, of a research directed toward a better understanding of the properties and performance of these steels at temperatures between 1400° and 2000°F. Investigation was concentrated upon the 26 per cent Cr:I2 per cent Ni type, which owes its extensive application to an excellent combination of economy, strength and surface stability at elevated temperatures. The requirements of the oil-refining industry have been prominent in influencing the scope and evolution of the program. Creep strength at the maximum allowable deformation ranges has been employed to evaluate the merits of these alloys. Permissible elongation rates vary from 1.0 per cent in one million hours for turbine blades to I .o per cent in ten thousand hours for tube supports and heating-furnace equipment. Throughout this paper, the limiting creep stress (L.C.S.) for a given temperature has been defined as the stress that will produce a uniform elongation rate (stage 11) of one per cent in ten thousand hours as extrapolated from rates per hour for tests of less than two thousand hours duration. Certain current specifications require a minimum L.C.S. of 1600 lb. per sq. in. at I800°F., of 3600 lb. per sq. in. at 1400°F., and include a tensile acceptance test at room temperature, after aging for 24 hr. at 1400°F., as a measure of embrittlement in service. An elongation of 4 per cent is considered satisfactory for general use, while a minimum of 9 per cent is prescribed on occasion. Many differences of opinion concerning the properties and performance of these alloys appear to result from their sensitivity to unappreciated variations of chemical analyses which, for example, may change their L.C.S. from 3500 to 350 lb. per sq. in. at 1800°F. Within broad chemical limits, it is possible to balance the six or more important elements present to attain desirable properties with a number of different combinations. One method for adjusting the composition has been described under the sponsorship of the Alloy Casting Institute,' in which, by maintaining a substantially austenitic* alloy, optimum creep strength and minimum tendency to embrittle after aging are expected. Unless, however, the limits are undesirably close, it has not been possible to ensure a moderate range of strength and of ductility by any chemical specification alone. There is a definite need

Jan 1, 1942

By D. W. McGlashan, K. N. Mcleod

IN the use of free bubbles with precise temperature control and continuous pH measurement, the contact angle apparatus differs from all previous equipment. Experimental procedures differ sharply from the captive bubble method1,2 of introducing the gaseous phase in the three-phase system. When freed from the tube and captured by a solid surface, a bubble more closely conforms to the spherical ideal set up by the usual mathematical analysis of surface free energy or surface tensional relationships of the forces involved. The assembled equipment, Fig. 1, departs from the usual contact angle apparatus in providing: 1) water circulation for fixing temperature, 2) instruments to measure and record pH during testing, and 3) a system for producing and using free bubbles. The apparatus allows testing over a broad range of closely controlled conditions, and the use of free bubbles gives contact angles independent of operator manipulation, which was unavoidable in the older captive bubble method. A bubble released below the specimen rises through the liquid and contacts the mineral. If the mineral is gas-avid the bubble adheres, developing a finite contact angle. Reaction cells (1), 2x33/8x5 3/16 in. ID, are of pyrex glass 5 mm thick. To prevent optical distortion, the sides are optical flats and are planed parallel to within five wave lengths of light over the entire surface. Special cement is required to withstand chemical attack and thermal shock. The cell is placed in a thermal jacket (2) made of welded aluminum. A water seal for the optical ports is made by using O-rings tightened against the flats of the cell by fine-threaded and adjustable ports, Fig. 2. In-flow water is discharged downward from a manifold located near the bottom of the cell jacket. Water overflows the weirs at each end of the cell jacket, discharging from both sides to a collecting manifold (24). A hose (26) leads the overflow water to the thermal-conditioner well (4), which is recessed to accommodate a reaction cell and two beakers (150 ml). Both the thermal jacket and the thermal-conditioner well are insulated to minimize the effects of temperature differentials. Water, discharging from the thermal-conditioner well, returns to a thermostat bath and pump (3), from which it is pumped to the thermal jacket. The thermostat bath permits temperatures to be adjusted from 1" or 2°C to 80°C and will maintain the selected temperature within 0.2ºC. An electrode support (22) groups the four electrodes (8) so that they fit conveniently into the reaction cell, Fig. 2. This assembly holds the glass electrode, the calomel electrode, the temperature-

Jan 1, 1957