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By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale forma¬tion) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. EXPERIMENTAL PROCEDURE Silver.-The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By C. F. Hardy, D. R. Mitchell

Bolts held up roofs as mining machines went on to set new records, but rising labor costs still plagued operators.

Jan 2, 1951

By Arthur R. MacPherson

The development of a simple method to predict the autogenous grinding possibilities of new ore deposits is attained. This method employs a 45-cm (18-in.) dry grinding Aerofall mill to grind small quantities of core or crushed samples in the top size range of 2 to 5 cm (1 to 2 in.). An extensive program has been carried out to correlate the data obtained in the 45-cm (18- in.) test mill with the actual results obtained in large commercial plants or autogenous test plants. Enough evidence now exists from these correlation programs that the 45-cm (18-in.) mill can be used to grind small samples from a new deposit and correctly predict the autogenous grinding mill requirements of a commercial plant to treat this ore.

Jan 1, 1978

By R. Priestner, R. F. Krause

Solid, cylindrical crystals of a iron have been fractured at 10°K by the simultaneous application of tension and torsion stresses. Thus, a complex distribution of normal (sN) and shear (ss) stresses existed in a cleavage plane at fracture. In every crystal the clearage-plane normal was inclined to the specimen axis, so that a unique point, M*, in the operative cleavage plane was defined where the quantities sn and s2 N + s2 S) were maximized. It is shown that the maxirrzum resolved normal stress on the cleavage plane at fracture decreased as the resolved shear stress in the cleavage plane at M* increased. Thus, a normal stress la?*! for fracture was not satisfied. A fracture law which takes shear stress into account. and which predicts that (s2 N +s2S) should be constant, is to be preferred. However, the data is best represented by a linear dependence of sN on sS, sS which 110 physical significance can be attached. It is suggested that the fracture-nucleating -mechanism is a short-range one. A critical stress law has not yet been unequivocally established for the propagation of cracks in metals. Measurements of the tensile fracture stresses of variously oriented zinc single crystals1 failed to establish the normal stress law expressed by In Eq. [1], sN is the fracture stress, P, resolved normal to the fracture plane, and 0 is the angle between the fracture -plane normal and the stress axis. Similarly, a comprehensive investigation failed to verify the normal stress law for the tensile fracture of a-iron single crystals.' However, a subsequent investigation,3 using iron from the same ingot, presented fracture data which obeyed the normal stress law. It has been shown previously4,5 that the Griffith criterion for fracture6 does not predict such a normal stress law. This result is of particular significance in considering the fracture of metals, such as zinc and iron, which may fail by cleavage. In these metals fracture propagates in a well-defined "cleavage" plane, whether or not an applied stress is normal to it. When the cleavage-plane normal deviates from the direction of application of a uniaxial stress, for example, the crack propagates under the combined action of normal (sN) and shear (ss) stresses. When the presence of a resolved shear stress in the crack plane is taken into account, the Griffith criterion is expressed by4

Jan 1, 1967

By H. A. Baumann, C. C. Wright, T. S. Spicer

A LTHOUGH the efficiency of coal utilization has A improved steadily since the turn of the century as a result of continued research and development, little of this increase in efficiency can be credited to improvements in the single retort stoker. There are still numerous problems connected with the burning of coal on this type of unit, the solution of which would be a stimulus to coal and stoker sales and a boon to the user. Among the more critical of these problems is that of burning slack bituminous coal of strong caking tendency and containing large percentages of fine material. With the increased trend toward mechanical mining, it may be expected that in the future an even larger percentage of the coal available for use on this class of stokers will contain higher percentages of the fine sizes, thus aggravating an already serious problem. During the war, the problem of efficient and economic burning of available coals on the single retort industrial stoker, particularly the class 4 stokers (301 to 1200 lb per hr), became quite critical in many localities. In addition to the inherent problems associated with the use of this class stoker, the coals available were frequently not those best suited for use on this equipment and the manpower shortage made it difficult as well as expensive for the consumer to provide the labor necessary to keep the iires in reasonably satisfactory condition. Although exact figures on the number of class 4 stokers are not available, the yearly tonnages of coal consumed are of considerable consequence and have been estimated* at between 15 and 20 million the stoker research staff of the Mineral Industries Experiment Station of The Pennsylvania State College was requested to study the performance of the single retort industrial stoker and to undertake a program of research on the more efficient burning of bituminous coal on this class of unit. Various aspects of overall problem have been investigated since the inception of this program in 1942, only one of which is here reported. General Considerations There are numerous factors which appear directly or indirectly to affect the overall performance of bituminous coal underfeed stokers, such as the caking or matting properties of the coal, the contact relationships between coal and air, the ash fusion characteristics, the burning rate, and the design of the stoker and furnace in which the coal is burned. An analysis of the influence of each of

Jan 1, 1951

By H. A. Baumann, T. S. Spicer, C. C. Wright

A LTHOUGH the efficiency of coal utilization has A improved steadily since the turn of the century as a result of continued research and development, little of this increase in efficiency can be credited to improvements in the single retort stoker. There are still numerous problems connected with the burning of coal on this type of unit, the solution of which would be a stimulus to coal and stoker sales and a boon to the user. Among the more critical of these problems is that of burning slack bituminous coal of strong caking tendency and containing large percentages of fine material. With the increased trend toward mechanical mining, it may be expected that in the future an even larger percentage of the coal available for use on this class of stokers will contain higher percentages of the fine sizes, thus aggravating an already serious problem. During the war, the problem of efficient and economic burning of available coals on the single retort industrial stoker, particularly the class 4 stokers (301 to 1200 lb per hr), became quite critical in many localities. In addition to the inherent problems associated with the use of this class stoker, the coals available were frequently not those best suited for use on this equipment and the manpower shortage made it difficult as well as expensive for the consumer to provide the labor necessary to keep the iires in reasonably satisfactory condition. Although exact figures on the number of class 4 stokers are not available, the yearly tonnages of coal consumed are of considerable consequence and have been estimated* at between 15 and 20 million the stoker research staff of the Mineral Industries Experiment Station of The Pennsylvania State College was requested to study the performance of the single retort industrial stoker and to undertake a program of research on the more efficient burning of bituminous coal on this class of unit. Various aspects of overall problem have been investigated since the inception of this program in 1942, only one of which is here reported. General Considerations There are numerous factors which appear directly or indirectly to affect the overall performance of bituminous coal underfeed stokers, such as the caking or matting properties of the coal, the contact relationships between coal and air, the ash fusion characteristics, the burning rate, and the design of the stoker and furnace in which the coal is burned. An analysis of the influence of each of

Jan 1, 1951

By Raymond M. Howe

Some time ago, a prominent engineer asked a representative of the firebrick industry to prepare a comprehensive paper on blast-furnace refractories. It was to have been the purpose of this paper to gather practical experiences from widely different sources, in the hope of determining what kind or kinds of firebrick were best adapted for certain uses. This engineer sent questionnaires to the large consumers of blast-furrace linings and stovebrick and received very detailed replies as to their experiences. These replies are conflicting, but, having been turned over to the writer, form the basis of this attempt to meet the request. Because of the impossibility of making final recommendations at this time, a few of the more interesting and commonly known methods of studying refractories are also discussed, as well as the more recent developments in this field. The first reply to the questionnaire stated that good service was being secured from the linings. This satisfactory condition was attributed to the use of a very good distributor. The writer believed that manufacturers try to and do produce a good product and that the proper handling of equipment is of the utmost importance, if good results are to be secured. The type of bricks used was not mentioned. The second reply stated that good life was secured from the furnace linings, but that the writer had had soft-fired stovebrick crumble and, for that reason, preferred a hard-fired product for use in this position. The type of bricks used was not mentioned. The third reply stated that firebrick had crumbled from the mantle up; the cause was not known. The fourth reply stated that the stove linings were satisfactory. Hand-made furnace linings failed after.4 years' service so a steam-pressed lining- was installed which was still good after 4 years of service. Consequently, a second steam-pressed lining was installed but this disintegrated at the top after the furnace had been in blast 7 months. The firebrick manufacturer attributed this failure to the expansion of iron blocks that had been installed at the stock line to prevent erosion. The fifth reply stated that the present "hard-burned" hand-made furnace lining had worn away very uniformly to the depth of only 5 in.

Jan 1, 1920

By Robert B. Paul

This paper describes the new lead smelter and refinery recently completed by the American Smelting and Refining company in Southeast Missouri.

Jan 1, 1970

By John R. Gould

A mathematical treatment of multiple-pass floating-zone refining of semiconductors, including the evaporation of solutes from the melt at reduced pressure, is presented. Vapor pressures and evaporation rate constants for phosphorus, arsenic, and antimony in germanium have been determined from floating-zone experiments conducted at 10 mm Hg. Rate sensi-tivity of arsenic in germanium has been examined over the range of 1 to 10 in. per hr growth rate. The equilibrium value of the segregation coefficient of arsenic in germanium, as determined by an extrapolation of these data, was found to be 0.09. PFANN has treated the segregation of nonvolatile solutes in the zone-melting process, Bradshaw and Mlavsky2 considered the evaporation of solutes in a vacuum during the growth of crystals by pulling from the melt, and van den Boomgaard3 has shown that it is possible to bring a volatile impurity element homogeneously into an ingot by means of zone-melting under a constant pressure of that element. This paper is concerned with the volatilization of solutes during zone - melting in a vacuum. The mathematical analysis by Lord4 of multiple-pass zone melting is extended to include evaporation of solutes. A method is presented in which evaluations of vapor pressures, evaporation rate constants, and distribution coefficients may be derived from the variation of solute concentration in the floating-zone refining of germanium at 105 mm Hg. EXPERIMENTAL Ingots of zone refined germanium, approximately 1/4 in. in diam and 10 to 12 in. in length, were subjected to several floating-zone passes at 105 mm Hg in order to provide intrinsic material for these studies. These ingots were then seeded in a [Ill] direction and solid-doped to a constant impurity concentration of approximately 1015 atoms per cmS in a forming gas ambient (10 pct H - 90 pct A) at 1/2 atm gage. The resulting crystals were subjected to repeated floating-zone passes at 105 mm Hg and a concentration profile along the length made after termination of each pass. Concentrations were determined from four-point probe resistivity measurements, and proper precautions were taken to prevent contamination during handling. A constant zone length, crystal cross section, and growth rate were maintained during zoning. A stationary coil and moving crystal system were employed for floating-zone growth with neither the section of crystal above nor below the melt rotated.

Jan 1, 1962

By R. W. Bartlett

Hydrometallurgical processes for copper flotation concentrates avoid the SO2 emission problems associated with smelting, but they require oxidation of copper to obtain solubilization during leaching. The resulting copper ions must be reduced to metal, which normally requires large amounts of energy or energy equivalent reagents such as hydrogen or iron. The conventional reduction method is electrowinning which is labor intensive and involves 35 to 40% of both the entire operating and capital cost of the better hydrometallurgical processes. There is considerable incentive to reduce the cost and energy required for producing copper ions from solution. Furthermore, it is thermodynamically possible to do this using sulfur contained in the concentrate itself. In fact, the thermodynamic potential of oxidizing sulfur from S+4 to the S+6 state is greater than required to reduce cupric ion to metallic copper.1 Realization of this potential in a practical process would significantly reduce the cost of hydrometallurgical processing of sulfide concentrates because sulfur would become a cost-free reducing agent. An apparently practical method is to use SO: and HSO3 ions, obtained by ammonia scrubbing of SO2 from a concentrate roaster gas, to reduce leached copper to metal in an autoclave. This reduction step is the Jumau 1907 A series of steps, including sulfite reduction, constituting a crude flowsheet was suggested by Parker in 1976.3 The present paper describes a detailed complete. sulfite process flowsheet based on materials and energy balances, discusses the chemistry, and discusses further work that is required to develop this process. Process materials, utilities costs, and energy requirements are projected to be unusually low because of the utilization of sulfur from the concentrate. Process Description The sulfite reduction process requires a copper concentrate containing approximately as much sulfur on a weight basis as copper. For those few concentrates that are deficient in sulfur, additional sulfur can generally be obtained by allowing more pyrite to float in the concentration process. The process steps, shown in [Fig. 1], are (1) a fluid bed roast of the concentrate, (2) a leach of the roaster calcine using recycled barren liquor from the reduction autoclave, (3) scrubbing of the SO2 gas with ammonium sulfite liquor to produce ammonium bisulfite, (4) reduction and precipitation of copper in an autoclave by combining part of the SO2 scrubber effluent (SO5

Jan 1, 1980

By Lester Guttman

THE connection between short-range order and thermodynamic activities in binary solid solutions has been pointed out by Birchenall1 who calculated approximate values of the energy of interaction of Zn and Cu and of the degree of short-range order in alpha-brass at one composition and two temperatures. The purpose of this note is to call attention to a somewhat more accurate theory than that used by Birchenall and to extend the calculations to a wider range of temperatures and compositions as a means of testing its applicability. This is an example of the well-known general method of comparing measured thermo-dynamic functions of a system with those calculated from a microscopic model by means of statistical mechanics. In this case, mathematical approximations must be used which make difficult any decision about the validity of the model. Birchenall's statistical method resembles closely that called by Fowler and Guggenheim2 the "quasi-chemical" method which has been shown to lead in certain cases to results identical with those obtained by the method of Bethe.3 The quasi-chemical method has been extended by Takagi4 to give general formulae for the free energy of binary solid solutions based on several lattices at all compositions and temperatures. Specifically, he treats the four systems typified by: I. ß-brass; 2. a- brass; 3. AuCu3; 4. AuCu. When the temperature is so high that no long-range order exists, these formulae reduce to the same form for all lattice types, namely: [ ] Here the symbols have the following meanings: [F-Helmholtz free energy E-energy S-entropy k-the gas constant per molecule z-coordination number, (e.g. 12 in. a-brass). N-total number of atoms c-atomic fraction of A] VAA, VBB, VAB-energy per bond of the corresponding bonds log means log, throughout The superscript 0 denotes the thermo- dynamic function in the standard state, which has been chosen to be pure A or B with the same crystal structure as the solid solution. The quantity x is the ratio of the number of A-A bonds to the total number and for minimum F satisfies the equilibrium condition [ ] The free energy may also be written in terms of µA and µB, the chemical potentials or partial free energies per atom:

Jan 1, 1948

By G. B. Walker

THE sink-float methods designated by heavy-media separation processes were pioneered by C. Erb Weunsch for the treatment of base metal ores as an improvement over jigs. The work of Weunsch was further developed by Victor Rakowsky and The American Zinc, Lead and Smelting Co. Early in the development of the processes, the inherent unsuitability of galena as the solid constituent of the medium was recognized and ferrous media amenable to magnetic recovery and control were developed. The high efficiency and low cost of magnetic recovery and cleaning of ferrous media regardless of particle size, slime contamination, or surfacial oxidation had led to the adoption of ferrous media by all of the sink-float plants operating under the heavy-media separation processes patents controlled by American Zinc, Lead and Smelting Co. Approximately 2,000,000 tons of base metal and nonmetallic minerals are treated each month by these methods.

Jan 1, 1949

By P. D. Hunt, B. Tani, M. G. Chasanov, R. Schablaske

The Zn-Vphase diagram was studied by thermal. metallographic, X-ray, and sampling techniques. Three ternary phase equilibria were observed: Mutual solid solubilities in vanadium and zinc appear to be negligible. The liquidus line is retrograde from 670° to 756°C. 1 HE only information in the literature relating to the Zn-V system was a study of corrosion of vanadium by liquid zinc' and an examination of the effectiveness of zinc coatings in protecting vanadium-base alloys from oxidation at high temperatures.2 Establishment of the Zn-V phase diagram was undertaken as part of a study of transition metal solubilities in liquid metal solvents. Chemical, metallographic, thermal, and X-ray diffraction analyses were used to determine the diagram. MATERIALS AND EXPERIMENTAL PROCEDURES Vanadium (99.86 pct) in the form of powder and small chips was employed. Stick zinc (99.99 pct; major impurities: 10 to 15 ppm Pb and 20 ppm Cu) was used in the liquidus determinations and thermal analyses; zinc powder (98.80 pct) was used to prepare intermediate compositions. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The apparatus and sampling techniques were similar to those described by Martin, et al.3 The entire metal sample was dissolved to preclude analytical errors due to segregation on cooling. Vanadium was determined amperometrically, using iron (11) as the titrant,4 to an estimated accuracy of 1 pct. Standard techniques of thermal analysis were employed to examine alloy specimens contained in alumina crucibles under helium. Heating and cooling rates were about 1°C per min. At least five heating and cooling cycles over the range 420° to 700°C were performed for each of two Zn-15 pct V alloys. A Zn-0.2 pct V alloy was used in the determination of the eutectic temperature. The separation of intermediate phases from zinc-rich alloys was carried out by selective leaching with ammonium nitrate solutions. For further investigation of intermediate phases 1/4 in. diam powder compacts were prepared by pressing at 80,000 psi and were annealed in argon at 415" to 450°C for 10 days. Larger quantities of intermediate phases were prepared in sealed tantalum capsules heated in a rocking furnace. Temperatures were determined to an estimated accuracy of 0.5°C with a Pt/Pt-10 pct Rh thermo-

Jan 1, 1963

By J. Rogers, H. F. A. Hergt, K. L. Sutherland

IN 1938 Ralston4 reviewed the many attempts to find a satisfactory collector for the separation of cassiterite from its ores and in 1944 Dean and Ambrose2 summarized some further attempts. Generally, soaps and amines are effective but nonselective collectors. We have discovered that reagents containing either the polar group -SO4- or _S03- are excellent collectors for cassiterite and promise to be selective.1 The response to these reagents of cassiterite and of minerals commonly associated with it was studied, using the captive-bubble technique. Using these fundamental data, the practicability of separation and concentration of tin was investigated by flotation tests in a 2000gram Denver cell. EXPERIMENTAL METHODS Reagents All inorganic reagents were of Analar grade. The preparation and purification of sodium cetyl sulphate, cetyl trimethyl-ammonium bromide, laurylamine and cetylamine have been previously described.5 The other collectors were commercial surface-active agents, which were used without purification. Tests Captive-bubble Tests and Cylinder Flotation Tests have been previously described.5-10 The full lines shown in the figures relating solution composition to contact (flotation) distinguish solutions in which contact (flotation) is possible from those in which it is not. The curve is derived by successive approximation and the accuracy is ±0.2 pH units and ± 5 mg. per liter of collector or depressant. Solution compositions for which it was shown experimentally that contact or flotation is possible are marked by a circle, those for which it is not possible, by a cross, and those for which it is doubtful by a cross within a circle. It is assumed that at all other solution compositions within (without) the curve, contact or flotation is possible (not possible). After testing in the collector solution, the mineral was removed, washed, and tested by the captive-bubble method in water, or floated in a cylinder with frother only. In this way the composition of solutions in which a mineral was conditioned but in which properties of the collector solution prevented contact or flotation can be defined. The composition of solutions in which conditioning was possible lie between the full and broken curve, and the experimental results are indicated by a square. The curves show the limits of composition of solutions in which flotation in a cell would be possible but many factors other than those considered in these tests determine recovery and grade of a given mineral in practice. Flotation Tests in 500 and 2000-gram Denver Submachines.--Melbourne tap water, containing 12 parts calcium, 6 parts

Jan 1, 1947

By George B. Langford

The McIntyre mine is in the Pearl Lake section of the Porcupine gold area. The rocks are Keewatin lavas intruded by quartz porphyries and albitite dies of Algoman age. Gold-bearing quartz veins are found in the Keewatin rocks near the porphyry stocks. The whole area has been highly compressed by forces acting along a N. 20°W. line. These forces folded the Keewatin rocks before the intrusion of the Algoman rocks, and later schisted both the Keewatin and Algoman rocks. Vein fractures were developed after the folding but before the development of the schist by the compres-sive forces being locally broken up into couples. These couples were set up by the differential resistance to deformation of porphyries and basalts, and also by the competency of the dacites and incompetency of the tuffs and fragmental rocks. During the important period of vein formation, two zones were developed—an inner productive zone in which the quartz veins are ankerite-bearing and an outer barren zone in which the quartz veins are calcite-bearing. The vein solutions originated in the same magrna that supplied the albitite dikes. Introduction The McIntyre mine, in the Porcupine gold area of northern Ontario, has passed its twenty-sixth birthday and has been producing gold since early in 1912. During this time approximately ten million tons of ore has been mined and over three and a half million ounces of gold recovered. This amount of ore would be sufficient to fill 2300 standard railway freight trains, each of 100 cars, and the gold produced, although only equivalent to a cube 51/2 ft. to the side, would weigh approximately 100 tons, a load for three freight cars. Silver has been produced in the ratio of 1 oz. of silver to every 4.4 oz. of gold, so that the total silver recovery is in the neighborhood of 700,000 ounces. The early history of the mine, like that of many others, shows that for several years it fought an uphill struggle for existence. One of the important features in winning this fight was the early recognition of some of the geological conditions responsible for the ore deposits, and the application of this knowledge in the search for ore and in the acquiring of adjoining properties. As early as 1913—only two years after the mine was opened—a geological department was organiaed. It has functioned almost continuously since that date and has demonstrated the importance

Jan 1, 1941

By George B. Langford

The McIntyre mine is in the Pearl Lake section of the Porcupine gold area. The rocks are Keewatin lavas intruded by quartz porphyries and albitite dies of Algoman age. Gold-bearing quartz veins are found in the Keewatin rocks near the porphyry stocks. The whole area has been highly compressed by forces acting along a N. 20°W. line. These forces folded the Keewatin rocks before the intrusion of the Algoman rocks, and later schisted both the Keewatin and Algoman rocks. Vein fractures were developed after the folding but before the development of the schist by the compres-sive forces being locally broken up into couples. These couples were set up by the differential resistance to deformation of porphyries and basalts, and also by the competency of the dacites and incompetency of the tuffs and fragmental rocks. During the important period of vein formation, two zones were developed—an inner productive zone in which the quartz veins are ankerite-bearing and an outer barren zone in which the quartz veins are calcite-bearing. The vein solutions originated in the same magrna that supplied the albitite dikes. Introduction The McIntyre mine, in the Porcupine gold area of northern Ontario, has passed its twenty-sixth birthday and has been producing gold since early in 1912. During this time approximately ten million tons of ore has been mined and over three and a half million ounces of gold recovered. This amount of ore would be sufficient to fill 2300 standard railway freight trains, each of 100 cars, and the gold produced, although only equivalent to a cube 51/2 ft. to the side, would weigh approximately 100 tons, a load for three freight cars. Silver has been produced in the ratio of 1 oz. of silver to every 4.4 oz. of gold, so that the total silver recovery is in the neighborhood of 700,000 ounces. The early history of the mine, like that of many others, shows that for several years it fought an uphill struggle for existence. One of the important features in winning this fight was the early recognition of some of the geological conditions responsible for the ore deposits, and the application of this knowledge in the search for ore and in the acquiring of adjoining properties. As early as 1913—only two years after the mine was opened—a geological department was organiaed. It has functioned almost continuously since that date and has demonstrated the importance

Jan 1, 1941

By E. T. Turkdogan, J. H. Swisher

The solubility of oxygen in zone-refined iron was determined in the temperature range.from 881" to 1350°C. The solubility in a iron at 881°C ms found to be about 2 to 3 ppm; in y iron, the solubility was found to increase from about 2 to 3 ppm at 950°C to about 25 ppm at 1350°C. The permeability of oxygen in an iron -0.1 pct Al alloy was determined in the y iron range, using an internal oxidation technique. By combining the permeability and solubility data, the diffzisivity of oxygen in y and a iron was calculated. The oxygen diffusivity in solid iron may be s~immarized as follows: 8820 For 6 iron and IN a recent paper, Hepworth, Smith, and Turkdogan1 reported on the solubility, permeability, and diffusivity of oxygen in 6 iron, together with permeability data for oxygen in a iron. In the present investigation, similar measurements were made in the ? phase region. In addition, a solubility measurement was performed in the a phase region to permit calculation of the diffusivity of oxygen in a, iron. References to early work on this subject are given in the previous publication.' EXPERIMENTAL Solubility Measurements. The oxygen solubility was determined by equilibrating cylindrical samples 0.3 in. diam by 14 in. long of zone-refined iron in water vapor-hydrogen gas mixtures. The zone-refined iron was prepared by B. F. Oliver of this laboratory, using an apparatus and technique described elsewhere.2'3 Six zone-melting passes were used to achieve a total impurity level of about 30 ppm. Of this 30 ppm, the combined nickel and cobalt content was about 20 ppm, oxygen was 4 ppm, and all oxidizable impurities less than 1 pprn each. A vertical resistance furnace wound with molybdenum wire was used for the experiments. The temperature was measured before and after each experiment with a Pt/Pt-10 pct Rh thermocouple. In the gas train, flow rates of hydrogen and argon were measured with capillary flow meters, and the resulting mixtures were passed through a column containing 90 pct oxalic acid dihydrate and 10 pct anhydrous oxalic acid to obtain predetermined ratios of H2O to H2. The vapor pressure of H2O above this mixture as a function of temperature is well-known.4 The exit gas was ana- lyzed periodically for H2O, and good agreement (+3 pct) with the calculated composition was obtained. The zone-refined iron specimens were held in the furnace for a sufficient length of time for equilibration, e.g., 18 hr at 1350°C and 1 week at 881°C, then quenched in a brine solution. After removing the surface oxide from the samples by machining, duplicate analyses were obtained by a combined vacuum fusion-infrared method; oxygen analysis was reproducible within 2 ppm. Permeability Measurements. The permeability of oxygen in alloys containing about 0.1 pct A1 was determined by internal oxidation and measurement of the subscale thickness as a function of time. The experimental alloys were prepared by adding aluminum to electrolytic iron (grade 104A plastiron) that had previously been vacuum-carbon deoxidized. The resulting ingots contained about 20 ppm O, 100 pprn C, 40 pprn Si, 50 ppm Mo, 20 ppm P, 20 ppm S, and 20 pprn Zr as the principal impurities. After hot rolling the ingots to 1-in.-thick slabs, specimens were machined from the stock in the form of rectangular plates, 4 by 5 by 2 in. The general procedure for the permeability experiments was the same as those for the solubility measurements. The specimens were cooled in a reducing atmosphere rather than quenched, however, in order to maintain a clean surface for measurement of the sub-scale thickness. This measurement was made on a polished cross section of each specimen, using a microscope with a micrometer stage. The inclusions formed at the lowest temperature 1033°C were too small to be seen with an optical microscope. An electron micrograph showing the size and shape of individual particles is shown in Fig. 1. The dark band in the picture is a boundary between two subgrains. The subscale thickness in these samples was measured with an optical microscope after heavily etching in 2 pct nital, which gave contrast between the subscale and the unoxidized zone.

Jan 1, 1968

By Ralph Hultgren, David W. Mitchell

Magnesium alloys usually are superheated before casting in order to ensure fineness of grain. Superheat temperatures in common use range from 1600" to r 7o0°F.; the casting temperature, which depends upon the mold shape, is usually 200° to 300°F. lower. The process of superhcating requires considerable time and seriously shortens the life of the iron pots used. Recently it has been reported1 that if acetylene, carbon dioxide or natural gas is bubbled through molten electrolytic A.S.T.M. No. 4 alloy at 1400°F. for 5 min., grain refinement equivalent to that of superheating will take place. Addition of certain solids such as graphite or aluminum carbide accomplishes the same results? As will be shown in this paper, it is possible to achieve grain refinement in magnesium casting alloys at low temperatures by mechanical stirring of the molten metal for a short time. This process was developed in the course of research work, supervised by the War Metallurgy Committee under the "Restricted' project NRC-550, for the Office of Production Research and Development of the War Production Board. This paper, based on that work, has been released for publication by the O.P.R.D. Materials and Methods The alloys studied were the most common American sand-casting alloys designated as No. 4 and No. 17 by the American Society for Testing Materials. The magnesiun used in these alloys was of both carbothermic3 and electrolytic' origin. Chemical analyses supplied by the producers are shown in Table I. Each heat consisted of approximately 5 lb. of alloy melted in a Tercod crucible. It was refined by fluxing with Permanente No. 7* refining flux at 1300° to 1350°F. After cooling to 1200° to 1250°F., portions of approximately one pound each, were ladled into iron crucibles contained in an electric furnace at about 1250°F. The molten metal was covered with Permanente No. 21 † covering flux and then heated to the temperature to be investigated. Normally each of the four portions was given a different treatment. In a typical case one portion was stirred vigorously for 5 min., acetylene gas was passed through a second portion for 5 min., a third portion was superheated to 1600°F. for 15 min., then . cooled to casting temperature, and the fourth was held for 5 min. at the temperature of stirring or gassing without other treatment. Each portion was then cast into one-inch diameter cylinders in three "nonturbulent" molds of identical shape. One mold was made of cast iron and the other two of baked sand. The cast-iron mold and one of the baked sand molds were heated to 360°F., the other baked sand mold was at room temperature. The freezing times in these molds were

Jan 1, 1945

By Elwood Haynes

As in organic nature certain animal and vegetable forms have undergone modifications, and thus, as it were, fitted themselves to live in a new environment, so it has been found possible in certain instances to form new metallic combinations which are practically immune to the natural conditions that exist on the earth at the present time. A few of the metals, such as gold, silver, and the metals of the platinum group, are found native, but the commoner heavy metals are nearly always found in the form of oxides or sulphides. For a number of years I have made experiments with a view to finding certain metallic combinations or alloys which would not only resist oxidation and other harmful influences, but would also possess valuable physical properties, which would render them fit for special service. The first decisive step made in this direction was the discovery of an alloy of nickel and chromium in 1898. The properties of this alloy have already been described in a previous paper.' Immediately following the discovery of the nickel-chromium alloy, I produced an alloy of cobalt and chromium, which has likewise been described in the reference given, but the range of proportion between the cobalt and chromium is so great, and the combination is modified to such a marked degree by the introduction of other substances, that I have felt justified in reading another paper on this subject, describing more fully my researches in this particular direction. As early as 1907 and 1908,I made alloys or combinations of cobalt, chromium, and tungsten; cobalt, chromium, and molyb-

Jan 1, 1913

By Charles E. Locke

IN gathering material for this review the aid of the individual members of the Milling Committee was invoked and the assistance received is hereby most grate- fully acknowledged. The replies were much alike; almost everyone stated that in 1932 his operations had been cur- tailed or stopped entirely, that the only activity and progress were in milling gold ores, and that the Hadsel mill' looked like a coming machine in the crushing and grinding field. However, further inquiry and search have shown that the year was not quite so barren of developments as the foregoing statement would indicate.

Jan 1, 1933