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By T. E. Leonitis, F. N. Rhines

The oxide scale that forms upon magnesium at elevated temperatures is non-protective in the sense that the rate of oxidation is constant and thus does not decrease with the growth of the scale as it does with other common metals. This generality was first stated by Pilling and Bedworth' and has been verified by Suzuki2 and by ScheiL3 Pilling and Bcdworth argued that the nonprotective characteristic could be predicted from the fact that magnesium oxide occupies less space than does the metal from which it springs, wherefore the scale is not expected to cover the metal so completely as to exclude all direct access to the atmosphere. Linear oxidation is thought by Scheil to be common to all cases where the reaction occurs at the oxide-metal interface. According to Suzuki," he product of high-temperature oxidation in the air is MgO contaminated with no more than traces of a nitride. When the metal is allowed to burn freely a fume composed of cubic crystals of Mg04 is given off. Delavaults observed that excrescences form upon liquid magnesium and alloys in thc course of oxidation. Beyond this it is known that the use of atmospheres containing small quantities of sulphur dioxide6 or carbon dioxide serve to retard the oxidation of solid magnesium and that beryllium' and calciums minimize the oxidation of molten magnesium exposed to the air. Many studies have been devoted to the nature and rates of "protective" oxidation, as exemplified by the cases of copper and iron, wherein the rate is characteristically parabolic. The theory of parabolic oxidation is well developed.~ Linear oxidation, on the other hand, has received but little attention and the theories proposed by Pilling and Bedworth and by Schcil have yet to withstand careful examination. There exists no comprehensive survey of the high-temperature oxidation of magnesium (or of any other metal that exhibits linear oxidation) over a broad range of temperature, under a variety of atmospheric conditions and covering a large group of alloys. It has been the purpose of the present investigation to provide such a survey, with the object of gaining a fuller understanding of linear oxidation, especially as applied to magnesium. Experimental Procedure and Results The experimental studies undertaken were of two kinds: (I) measurement of the rate of oxidation as influenced by the 6c

Jan 1, 1946

By H. J. Wasson, E. B. Hopkins

Throughout 1928, production of oil from Venezuela steadily increased, and at the close of the year, the output was at the rate of nearly 400,000 bbl. a day. The total for the year was approximately 106,500,000 bbl., representing an increase of about 66 per cent. over the 63,000,000 bbl. produced in 1927. Venezuela now stands next to the United States as the second largest oil-producing country in the world; and there is abundant evidence to suggest that this relationship will endure for a number of years. Reserves were notably increased in the Lake shore fields, and the potential output of the Maracaibo Basin is much greater than the current production. In spite of this, the percentage of production increase was comparatively moderate, and the rate of this increase continued to fall off slightly, as has been the case for the last three years. This does not suggest that further annual increases in Venezuelan output will not materialize; only that the rate of these increases appears to be on the decline, and that with every succeeding year the future tendency will be in the direction of a stabilized level of output. The following table shows the production trend of the country since 1925: 1925 increase over 1924, 132 per cent. 1926 increase over 1925, 80 per cent. 1927 increase over 1926, 75 per cent. 1928 increase over 1927, 66 per cent. Many factors will work to prevent a reversal of this trend, but the principal ones are strong ownership in large-acreage units, and the probable indisposition of the world market to absorb a more rapidly increasing Venezuelan output at prices profitable to the producers. The distress oil element is not a factor in Venezuela; also, any unforeseen jump, such as results in the United States from the discovery of a Seminole or a deep sand at Long Beach, or Santa Fe Springs, is impossible in Venezuela, on account of lack of means for transporting a sudden surplus of oil, and the slowness with which additional transportation equipment in the form of shallow-draft tankers can be obtained.

Jan 1, 1929

By G. J. Saulnier, K. E. Goddard

The US Geological Survey has developed mathematical modeling techniques to assess potential impacts on the hydrologic system resulting from mining of coal and oil shale in northwestern Colorado. Potential impacts of oil shale mining on groundwater hydrology have been simulated using a quasi-three-dimensional, finite-difference model. The model has been used to simulate hypothetical mine dewatering operations at two proposed oil shale mines. Dissolved-solids distribution and solute transport were simulated with a three-dimensional, finite-difference model that was used to evaluate the effects of flooding in hypothetical abandoned mines. The potential impacts of coal and oil shale mining on water-sheds were investigated using a digital watershed model. This deterministic physical-process model predicts responses of the hydrologic system to modifications resulting from mining in basins having snow as the major source of runoff and recharge. Potential impacts of coal development on surface water quality were investigated using a river quality assessment model. The models developed by the US Geological Survey have been useful in defining the potential effects of mining in northwestern Colorado. They are an important first step in analyzing the existing data base and in predicting impacts and new data needs. The models may not be totally applicable on the local scale but are very meaningful on the regional level.

Jan 1, 1983

By G. L. Oldright

NEARLY all of the present schemes for treating complex (i. e. lead¬silver-zinc-copper) ores are based on the idea that lead holds, and will hold for some time, the strongest economic place from the viewpoint of supply and demand of all the non-ferrous metals. Copper, it is thought, will come back to its own when European affairs are stabilized, although at that time competition from Chile, Peru, and Katanga, in particular, will be more severe than in pre-war days. The future for silver and for zinc is uncertain. New uses are developing for zinc, and the market has remained better than many expected, but the stabilization of world markets will bring in foreign competition instead of relief. The cost of producing zinc from simple zinc ores, by the retort process, will, from the nature of the labor required and the increasing cost of fuel, increase steadily. As a result, the small producers of purely zinc ores around Joplin are shutting down their mines, even with a good market price for zinc; on the other hand, the producer of lead from complex ores, in the Rocky Mountain states, is confident of a profit from the sale of his lead, and is seeking means to make the zinc in his ore pay some part of the cost of treatment. However, the tonnage costs for mining and ore dressing are much higher in the Rocky Mountain states, as may be seen by comparing tax-return statements from the various states. Even before the recent drop in the price of silver, many mines were operating on a very slender margin of profit; labor and supplies cost more. Mining at greater depth has shown most orebodies to grow increasingly more complex, so that improvements in mining and ore-dressing practice have not been sufficient too compensate for the additional expense involved in beneficiating these ores. The smelters have had to meet the same general economic situation, so they can only give

Jan 3, 1924

By C. G. Bieber, J. R. Mihalisin, R. T. Grant

A growing demand for longer service life of gas turbines has placed increasingly rigorous requiret~rents upon superalloys employed for that application. Long-titne testing at high temperature has revealed that phase transformations occur in all superalloys. A common one of particular interest is o formation. Presented here are studies made to identify a and to characterize its formation and effect on properties in three cast nickel-base superalloys—IN 100 alloy, alloy 713C, and alloy 713LC. Methods are discussed by which o can be eliminated or inhibited in IN 100 alloy and alloy 713C. Evidence was obtained to indicate that some types of o may be more detrimental than others. Limitations in the electron vacancy approach to o prevention are pointed out, and it is shown how alternative approaches, such as reducing a complex superalloy matrix to the form of a pseudo-ternary system permitting equilibrium diagram treatment, lead to additional insights into the formation of in these alloys. AROUND 1960. Beiber1 developed IN 100 alloy, which still remains one of the strongest commercially available nickel-base superalloys. The principle used in the design of this alloy was to produce large quantities of y' phase in a y matrix through the use of copious amounts of aluminum and titanium. In 1963, ROSS' showed that when certain heats of this alloy were held for a long time at 1650°F they formed an acicular phase, subsequently identified as a.3 a is a hard and brittle phase first discovered in the Fe-Cr system by Bain and Griffiths.4 They termed it the "B" constituent. Subsequently this same phase was found in other systems, primarily those of the transition elements, and acquired the name "a" by which it is now known. The crystal structure of the a phase was first determined in the Fe-Cr system in 1950.5 It was shown to be tetragonal with a c/a ratio of about 0.52. as is the case with a found in other systems. This characteristic crystal structure is now the means by which a is identified. In superalloys, such as IN 100 alloy. large amounts of o impair the high-temperature creep strength and drastically reduce room-temperature tensile ductility. Discovery of o phase in some heats of IN 100 alloy quickly led to investigations of other superalloys for similar transformations. It was found that many of the stronger, more highly alloyed. super-alloys were indeed susceptible to o formation. This investigation has been concentrated on three commercial alloys: IN 100 alloy, alloy 713C, and alloy 713LC. J.R.MIHALISIN,MemberAIME, and C.G.BIEBER are with The International Nickel Co., Inc., Paul D. Merica Research Laboratory, Sterling Forest, Suffern, N. Y. R. T. GRANT, Member AIME, is with The International Nickel Co., Inc., Pittsburgh, Pa. Manuscript submitted May 22. 1968. IMD A detailed study has been made of the phase transformations and their relation to a formation along with a consideration of electron vacancy approaches for predicting a-forming propensity in these alloys. EXPERIMENTAL PROCEDURE Phase transformations were studied by light and electron microscopy, electron diffraction, microprobe investigations, and X-ray diffraction. Specimens for light micrographic examination were prepared by conventional grinding and polishing followed by etching with glyceregia (2:l HC1/HNO3 + 3 glycerine by volume). Photomicrographs of stress-rupture specimens were taken adjacent to the fracture unless otherwise noted in the text. Negative replicas for electron microscopy were taken from surfaces electropolished with a solution of 15 pct H2SO4 in methanol. For carbon extraction replication, a solution of 10 pct HC1 in methanol was used. A Siemens Elmiskop I was used for all electron microscopy. Selected-area diffraction studies were made at 80 kv using evaporated aluminum for standardizing the patterns. A nondispersive electron microprobe attachment was used to analyze the extracted precipitates chemically. The fluorescent X-rays were recorded using a flow counter containing P10 gas (90 pct Ar-10 pct methane) with a beryllium window and a single-channel pulse-height analyzer. The pulses from the analyzer were passed to a scaler-ratemeter and differential curves of counting rate vs pulse amplitude were obtained. The base line of the analyzer was driven with a synchronous motor at 0.5 v per min and a channel width of 0.5 v. The time for 105 counts was printed out for each 0.5-v increment. The microscope was operated at 80 kv with beam currents of 1 to 20 pa. This equipment detects elements from atomic number 13 to 40. X-ray diffraction studies were usually made on residues electrolytically extracted in 10 pct HC1 in H2O, although in one case a pattern was obtained from an etched surface of a metallographic specimen. A Siemens Crystalloflex IV was used with iron-filtered CoKa radiation. X-ray patterns were recorded using a goniometer speed of : deg per min. The scintillation counter and pulse-height analyzer operated at a channel height of 10 v and a channel width of 12 v. The equipment was calibrated with a powdered gold standard. The residues usually contained a number of phases. several of which could not be found in the ASTM card file. In addition, as is shown for the case of a phase in IN 100 alloy, other phases had a somewhat different lattice parameter from that reported in the ASTM card file, making it difficult to separate and identify constituents by comparison with ASTM d spacings. For these reasons, phases were identified on the basis of the lattice parameter obtained by indexing the ob-

Jan 1, 1969

By W. P. Sykes

SINCE Honda and Murakami1 in 1918 proposed their constitutional diagram of the carbon-free iron-tungsten system, considerable effort has been expended by several investigators in attempts to define more positively the structural features of the alloys. The existence of an intermediate phase corresponding to the formula Fe3W2 (68.7 per cent W) was proposed from evidence of a purely metallographic nature by one of the present authors2 in 1926. Since that time the identity of this phase has been confirmed by Arnfelt3 and by Takeda,4 both of whom employed X-ray methods as well as the microscope and the chemical analysis of isolated microconstituents. According to Arnfelt, Fe3W2, as crystallized from the iron-rich melts at a temperature above 1450'C., contains by analysis 68.7 per cent W. The lattice of this phase is characterized by trigonal symmetry. Arnfelt, moreover, proposed a second intermediate phase formed at some temperature between 1450° and 1000° C. by a peritectoid reaction involving Fe3W2 and the iron-rich solid solution. A melt containing 25 per cent W was cooled to 1000° C. and heated for. 100 hr. The precipitated tungsten-rich constituent was separated and found by analysis to contain 62.6 per cent W. This composition agrees closely with that represented by the formula Fe2W (62.2 per cent W). Diffraction patterns from the concentrated precipitate showed a hexagonal unit cell. Takeda confirmed the data of Arnfelt regarding Fe3W2 but was unable to detect Arnfelt's second intermediate phase. While Takeda. failed to describe in detail the treatments employed, he stated that in alloys containing 40 per cent W which were quenched after heating at various temperatures between 1200° and 1450° C., no evidence of the second phase (Fe2W) was observed either in the microstructure or in the diffraction patterns of isolated residues. He therefore considered the existence of this low-temperature hexagonal compound as disproved.

Jan 1, 1932

By Karl S. Kurtenacker

In attempting to find a rapid and economical means for solving many of the subsurface problems that confront the highway engineer, the author for the past two years has utilized a Megger Ground Tester on resistivity surveys in conjunction with highway construction. Electrical surveys in connection with highway work are largely shallow depth surveys, thus differing from most other types of resistivity work. Consequently, the readings are affected by a great many qualifying factors such as the density and moisture content of the media under observation and the amount of weathering and leaching. In most cases the surface layer is decidedly heterogeneous in character, and, because of the great number of side hill cuts, the second layer, which in most cases is rock overlain by some sort of surface soil, silt, or debris, seldom lies in a horizontal position. Shallow strata, lacking homogeneity and not lying in a horizontal position, do not lend themselves readily to accurate theoretical interpretations, therefore the author has used empirical rules to a large extent in interpreting depth soundings. The following empirical rules of interpretation are surprisingly adequate for highway work, since much of the work is in the nature of reconnaissance surveying and the results are construed to be approximations. The writer is careful not to risk interpretation on some special feature of the curve, since such features are usually due to random errors or lack of homogeneity among the subsurface strata. Effect of Surface Medium A resistivity depth sounding taken to a depth of 200 or 300 ft. is not much affected by superficial conditions, but these conditions have a great effect in depth soundings to 25 or 30 ft. In shallow soundings the character of the surface medium has a very marked effect on the entire resistivity graph. Fig. 1 illustrates a very striking example. Graphs A and B are depth soundings taken in approximately the same place. The surface stratum is a clay loam but at the place where graph B was taken

Jan 1, 1934

By M. Shelef, A. W. Fletcher

The effect of alkali sulfates in promoting the sul-fation of nickel and copper in a bulk sulfide flota -tion concentrate by fluidized bed roasting has been studied in the laboratory, and it was shown that the various alkali sulfates promote sulfation to approximately the same extent. The sulfation of a mixture of synthetically prepared iron and nickel oxide and of nickel ferrite has also been studied. Nickel sulfation was promoted by high ratios of Fe:Ni and by the presence of sodium sulfate. THE work described in this paper was a continuation of earlier studies into the role of alkali sulfates in promoting the sulfation roasting of nickel sulfides1,2 in an endeavor to determine how the system was affected by the presence of compounds of iron and copper. The earlier work1 showed that, in the sulfation of NiO at 680°C, the reaction was limited by the formation of an impermeable film of nickel sulfate on the oxide surface. The relative effect of the various alkali sulfates in promoting nickel sulfation varied in the order: Li > Na >Cs > Rb > K A study of alkali sulfate/ nickel sulfate interactions at high temperatures showed that the promoting action was due to the fact that the nickel sulfate product layer sintered and agglomerated only when the more active additives were present. This resulted in the formation of discontinuities in the nickel sulfate layer so that diffusion of the sulfating gases to the NiO surface was no longer impeded and the reaction could proceed to completion. A similar explanation was used for the observation that sodium and lithium sulfates promote the oxidation of NiS to NiO at temperatures below 750°C since small amounts of nickel sulfate were formed during oxidation.2 It was of interest to study the effect of alkali sulfates on the sulfate roasting of a sulfide flotation concentrate which is typical of material treated commercially. In order to control temperature it is essential to roast sulfides in a fluidized bed and this technique was therefore used, although the batchwise operation of a small-scale laboratory reactor does not reproduce all conditions which prevail in full-scale continuous plant. The results obtained are therefore only comparative, and cannot be used for predicting the optimum conditions for metal extraction. The sulfation of synthetically prepared mixed oxides of nickel + copper and nickel + iron and of nickel ferrite was also studied to evaluate the relative effects of alkali sulfates with more complex systems. SULFATION ROASTING OF A SULFIDE FLOTATION CONCENTRATE The bulk sulfide flotation concentrate used in this work contained 7.92 pct Ni, 1.74 pct Cu, 35.66 pct Fe, and 31.28 pct S. The sulfide minerals present in order of abundance were pyrrhotite FeS, pyrite FeS2, pentlandite (FeNi)S, and chalcopyrite CuFeS2. Two samples described as coarse and fine were used. The coarse sample, which was a flotation concentrate (58 pct plus 300 mesh), was ground to 100 pct minus 350 mesh to produce the fine sample. Before roasting, the sample of sulfide concentrate was agglomerated by wetting witli a solution of the alkali sulfate (or water), thoroughly mixing, and drying at 110°C. This gave a cake which was gently crushed and screened, the -18 +100 mesh fraction being used for fluidized bed roasting. A similar-size fraction had been used by the authors in pilot plant work with a 4-in.-diam fluidized bed reactor.' In this work it was found that the molar ratio of additive to the total iron + nickel + copper content of the sulfide sample should be adjusted to a value of approximately 0.06, as this was the optimum amount necessary for nickel sulfation. Experimental. The fluidized bed reactor consisted of a quartz tube approximately 60 cm long and 30 mm in diameter resting in a vertical tube furnace. The sulfide bed (30 g) was supported on a bed of -4 +12 mesh quartz particles 3 cm high, which rested on a sintered quartz disc welded to the tube. The temperature of the furnace was controlled with a variable transformer to give a final bed temperature of 680°C. The bed was fluidized with air or mixtures of air + 10 pct v/v SO2, at a total apparent gas velocity of 60 to 65 cm per sec at 680°C. The SO2 was introduced into the fluidizing air stream only when the oxidation of the sulfides was completed. At the end of the roasting period the calcine was leached with boiling water and the

Jan 1, 1964

By C. S. Finney, John Mitchell

The introduction of ovens for the production of metallurgical coke is believed to be due to L. L. Norton who operated an iron foundry in the vicinity of Connellsville, Pa. Persuaded by his foreman, an English immigrant named Nickols from Durham, L. L. Norton put up a 12-ft square oven which produced coke in 1833. The coal used was taken from a local mine at Mounts Creek. The oven seems to have been used in conjunction with the customary method of coking in mounds. It was in the Connellsville district also, in 1841, that two carpenters, Provence McCormick and James Campbell, formed a partnership with John Taylor, a stone mason, for the manufacture and sale of oven coke. The task of the mason was to construct the ovens, while the carpenters were to build the arks by which the coke could be taken by water to the market at Cincinnati. The following account of the enterprise was given by McCormick: "James Campbell and myself heard in some way that I do not now recollect that the manufacturing of coke might be made a good business. Mr. John Taylor, a stone mason, who owned the farm on which the Fayette coke works now stand, and who was mining coal in a small way, was spoken to regarding our enterprise, and proposed a partnership-he to build the ovens and make the coke and Mr. Campbell and myself to build a boat and take the coke to Cincinnati, where we heard there was a good demand. This was in 1841. Mr. Taylor built two ovens. I think they were about 10 feet in diameter. My recollection is that the charge was 80 bushels. The ovens were built in the same style as those now used, but had no iron ring at the top to prevent the brick from falling in when filling the oven with coal, nor had we any iron frames at the mouth where the coke was drawn. The top and mouth had to be repaired when they fell in. In the spring of 1842 enough coke had been made to fill two boats 90 feet long-about 800 bushels each-and we took them to Cincinnati down the Youghiogheny, Monongahela, and Ohio, but when we got there we could not sell. Mr. Campbell, who went with the boats, lay at the landing some two or three weeks, retailing out one boatload and part of the other in small lots at about 8 cents a bushel. Miles Greenwood, a foundryman of that city, offered to take the balance if he would take a small patent flour mill at $125.00 hi pay, which Mr. Campbell did. He had it shipped here. We tried it, but it was no good, and we sold it to a man in the mountains for $30.00, and thus ended our coke business." So successful did the coke subsequently prove to be in use that the three partners were asked to deliver more. Evidently they had had enough of the coke business, however, for they refused to have anything more to do with it. Few ovens were built between 1841 and 1855, and it is reported that in the latter year, "there were only 26 coke ovens along the river above Pittsburgh". Successful coke makers of these years included Mordecai Cochran, Richard Brookius, and Colonel A. M. Hill. It was the use of coke in 1859 in the Clinton furnace erected by Graff, Bennett and Co. in a plant on West Carson Street, Pittsburgh, that brought the real beginning of the coke-iron era in America. Here the successful use of Connellsville coke as a blast-furnace fuel was demonstrated beyond all possible doubt, and from the year 1859 the coking industry expanded tremendously. The era of beehive coke ovens During the latter half of the nineteenth century and the early years of the twentieth, the major percentage of metallurgical coke produced in the United States came from beehive ovens. It was not until 1893 that the first battery of by-product ovens came

Jan 1, 1961

Shoemaker: We've all heard a lot about epoxy liner backings. This brings up the question-do zinc furnaces still have a place in a new plant? Meaders: I would, you must understand, be prejudiced in this question because we introduced epoxy backing into the industry. Naturally, we wouldn't have done so if we didn't think it should be done. With that background maybe I could give a little more information on this particular subject than some of the others, because we now have been in this business for some three or four years.

Jan 11, 1967

By Chester O. Ensign

Results of the application of geologic knowledge to grade control have been remarkable. Grade reduction from dilution has been diminished from greater than 9% at the time of the program's beginning to about 2% at present. This has resulted in an increase of about 1.8 lb of copper per ton of ore mined and has made a substantial contribution to earnings at White Pine during the past two years. Even more improvement is expected in the future. The White Pine orebody, situated in the southwestern portion of the Keweenaw peninsula of upper Michigan, is a gently dipping stratiform or bedded deposit. Copper distribution is stratigraphically controlled with higher values being confined to specific beds in the ore column. Room-and-pillar mining is practiced. Mining technique and geologic characteristics present a special array of problems in controlling the grade of ore.

Jan 4, 1964

By Avnulf Muan, Egil Aukrust

The activity-composition curve for cobalt oxide in (Co,Fe)304 solid solutions with spinel-type stmcture has been determined experimentally by studying the equilibrium between the spinel phase and a coexisting cobaltowüstite phase, "(Co,Fe)O", at 1200°C. A large negative deviation from ideal behavior prevails in the spinel at low cobalt oxide concentrations and a positive deviation at high cobalt oxide concentrations. The activity-composition curve for iron oxide in the solid solution is determined from the above curve by integvation of the Gibbs-Duhem equation along the join Co3O4,-Fe3O4. The standard free energy of formation of cobalt ferrite, CoFe2O4, from the oxide components CoO and Fe2O3 is calculated to be -8.2 kcal. ThERMODYNAMIC properties of (CO,Mn)3O4 solid solutions with spinel-type structure have been presented recently.' The present paper deals with similar relations in another spinel solid-solution phase, that represented by the system Co3O4-Fe3O4. The principles involved in measurements and calculations of thermodynamic properties for the system Co3O4-Fe3O4 are analogous to those used and discussed in detail in the work on (CO,Mn)3O4. A (CO,Fe)3O4 solid solution coexists in equilibrium with a (Co.Fe)Ot solid solution over a considerable Here acOo1.33 and aao are the activities of cobalt oxide in the spinel and the oxide solid solutions, respectively, pO2, is the oxygen pressure of equilibration, and pb, is the oxygen pressure at which CoO and CosO4 coexist in equilibrium in the binary system Co-O at the same temperature. The activity-com position curve for cobalt oxide in the (Co,Fe)O solid solution in contact with metal has been determined in a previous investigation by the present authors.' The system shows a small positive deviation from linear behavior. Because of the large defect concentration in wiistite and in (Co,Fe)O solid solutions, one cannot assume that the activity-composition relations in the oxide phase coexisting with a spinel phase at relatively high oxygen pressures are the same as those prevailing in the oxide solid solution coexisting with metal. However, a Gibbs-Duhem integration over the ternary Co-Fe-0 solution can be used to determine activities of cobalt and iron, and hence of CoO and FeO, from a knowledge of the oxygen potentials. Several papers have dealt with the subject of application of the Gibbs-Duhem equation to multi-component systems. 3-6 In the present case, it was

Jan 1, 1964

By Albert Ledoux

SEVERAL years ago my firm was representing the Mt. Lyell Co. of Australia, which was shipping its blister copper to a refining works in the United States. After the contract had been running for many months, the superintendent of these works discovered that if water was poured upon the surface of the bars much of it would disappear into the interior through blow holes. -Some experiments made by him showed that this could be a considerable amount, so that copper which had been rained on before it was weighed, although the surface appeared dry, nevertheless would contain water. It had frequently occurred in our experience-as samp-lers that the drillings from a lot taken by boring would come out quite wet, and in some cases, indeed, water would drip into the sample pan placed below the bars, due to the fact that the drill had penetrated a cavity or cavities containing water, which presumably got into the cavities at the time the copper was water-cooled after casting, there being, perhaps, no outlet to the surface. So far as I know, until this discovery at the refining works, no. one had thought that rain could penetrate into the interior of blister copper; at least in any quantity sufficient to be considered.

Jan 10, 1922

By E. W. Filer, R. P. Smith, L. S. Darken

The solubility of nitrogen gas in purified iron and low alloy steels is determined for the y region (930° to 1350°C). The diffusivtiy of nitrogen is estimated from the rate of approach to equilibrium. The investigation of aluminum-killed steels, held in nitrogen, discloses precipitation of aluminum nitride, the solubility of which is determined. ALTHOUGH several investigations of the solu-bility of nitrogen gas in y iron have been reported, all have made use of the method adopted by Sieverts in his classic work, whereby the solubility is determined by the pressure or volume change of the gas. The agreement between different investigators* is rather poor, particularly as compared to the self-consistency of results of several individual investigators. The present report represents a portion of our investigation of the equilibrium of nitrogen and nitrogenous atmospheres with iron and steels. The method adopted in this temperature region (910" to 1400°C) consists of holding the specimen in gaseous nitrogen, quenching (or cooling), and determining the nitrogen content by direct analysis (solution in acid followed by distillation and titra-tion of the ammonia).** Up to 1050°C a 20 in. vertical wire-wound (Kan-thal) furnace was used; this was wound in three sections so that by proper adjustment of relative currents, and use of a modulator1 and a commercial controller (using a chromel-alumel control couple), a zone almost 6 in. long could be maintained uniform within a few tenths of a degree. Since the temperature coefficient of the nitrogen solubility is low, the full precision was not utilized and a variation of l° to 2" was tolerated; a variation of a similar amount also occurred occasionally between the beginning and end of the experiment. At higher temperature a vertically mounted, tubular Globar furnace and control unit was used; the zone of uniformity (l° to 2"C) was here limited to about 2 in.; fluctuations with time were comparable to those in the wire-wound furnace. Reported temperatures were measured by use of a platinum-platinum-rhodium thermocouple, which was frequently com- pared with a similar standard couple which was calibrated at the gold and palladium points and also compared with one certified by the Bureau of Standards; error from this source is believed to be less than 1 "C. Nitrogen gas from a commercial cylinder was mixed with slightly over 1 pct H by use of a gas mixer described previously.' This mixture was passed over hot copper and through ascarite and phosphorus pentoxide to remove oxygen and water vapor. The purified gas contained 1.05 pct H. This procedure was adopted to prevent the formation on the specimens of oxide film, which is well known to be nearly impervious to nitrogen; its success was attested by

Jan 1, 1952

By Leland H. Johnson

THE Tennessee Coal, Iron & Railroad Co.'s ore mines began experimental tests with trackless mining units early in 1947. The units had many weaknesses to overcome, but are now well beyond the experimental stage and are becoming a necessity to ore seams that are amenable to this type of equipment. The development of this type of mining with the problems of increased underground supervision, maintenance, and training personnel, along with the benefits derived, are discussed.

Jan 12, 1950

By W. Philippoff

ALTHOUGH Gaudin1 and more recently Sutherland2 have calculated the probability of collision of a falling mineral particle with a rising bubble, there is no published information concerning the details of the mechanism of attachment of a collector-coated particle to a bubble. During the past year the writer has developed a theory for the mechanism of attachment, which has been substantiated experimentally. Funds for the investigation and for some of the equipment used have been supplied by the Mines Experiment Station of the University of Minnesota. Motion picture studies of the phenomena involved in the collision between mineral particles and bubbles, such as those of Spedden and Hannan," show that the contact can be completed within 0.3 millisec. Formulas developed for rigid bodies have hitherto been used' for the calculation of the motion of bubble and particle, but it is obvious that a bubble cannot be regarded as a rigid body. On the contrary, Spedden and Hannan's pictures show a great degree of deformation during the collision. The time of attachment was calculated as the time the particle drifted past the bubble. Time of Collision The theory presented in this paper enables calculation of the time of collision, using the concept that the bubble, or more generally, a liquid-air interface, acts as an elastic body. The elasticity, defined as the restoring force on a mechanical deformation, is caused by the surface tension and is the result of the principle of the minimum of free surface energy. It is well known that an elasticity together with a mass determines a frequency of vibration. The vibrations of jets and drops caused by the elasticity of the interface are known to comply exactly with the classical theory of capillarity.' However, the vibrations of isolated bubbles, as distinct from foams, have not been investigated previously. The following equation, presented elsewhere,' has been deduced for these frequencies: 3_____________________ fB = 9.20.vV.vn. (n-1).(n+2)/8 [I] in which fB is the frequency of a harmonic of the bubble in cycles per second, V the volume of the bubble in cc, n a number determining the order of the harmonic, and n = 2 the basic vibration. The first (basic) harmonic describes a change of the spherical bubble to an ellipsoidal bubble. The higher harmonics are more complicated, for the circumference of the bubble is divided approximately into as many parts as the order of the harmonic. As an example, Spedden and Hannan's published motion picture of a vibrating bubble corresponds to the sixth harmonic. Eq 1 shows that only the first and third harmonics are simple multiples (1 and 3), all the others being irrational fractions of the basic frequency. This means that the shape of the vibration can change with time and is in general unsym-metric in respect to the time axis. Such conditions prevail when there is a distributed elasticity or mass, as in the case of vibrating membranes or rods. The constant 9.20 is valid for water at room temperature, but a general solution involving the physical constants of the liquid has not been found. The case of the floating particle is much easier to treat than that of the bubble. It can be assumed that the elasticity is caused exclusively by the interface and that the mass is concentrated in the particle together with some adhering water. The following expression for the frequency of a system of one degree of freedom can be applied: fP = -1/2-vE/m [2] Here fp is the frequency of the particle vibration in cycles per second, E the elasticity in dynes per cm, and m the mass in grams. The classical theory of impact phenomena gives the time of collision during the striking of a spring (in this case the surface of the bubble) by a mass, as: t, = 2/f = nvm/E [3] It is now possible to develop an expression for the elasticity of a floating cylindrical particle. The force equilibrium of a cylinder floating end on at the air-liquid interface is given by the well-known equation (Poisson7 1831) P = /4 D2-pL-g-h + D.y sin a [4] which accounts for the buoyancy and the action of the surface tension where P is the force acting on the particle in dynes (weight-buoyancy), D the diameter of the cylinder in cm, PL the density of the liquid in grams per cc, g the acceleration of gravity = 981 cm per sec2, h the depression of the cylinder below the surface of the liquid in cm, y the surface tension in dynes per cm and a the supporting angles or the one required to insure equilibrium, a being smaller than the contact angle 0. Although demonstrated by Poisson, it has not

Jan 1, 1953

By W. Philippoff

ALTHOUGH Gaudin1 and more recently Sutherland2 have calculated the probability of collision of a falling mineral particle with a rising bubble, there is no published information concerning the details of the mechanism of attachment of a collector-coated particle to a bubble. During the past year the writer has developed a theory for the mechanism of attachment, which has been substantiated experimentally. Funds for the investigation and for some of the equipment used have been supplied by the Mines Experiment Station of the University of Minnesota. Motion picture studies of the phenomena involved in the collision between mineral particles and bubbles, such as those of Spedden and Hannan," show that the contact can be completed within 0.3 millisec. Formulas developed for rigid bodies have hitherto been used' for the calculation of the motion of bubble and particle, but it is obvious that a bubble cannot be regarded as a rigid body. On the contrary, Spedden and Hannan's pictures show a great degree of deformation during the collision. The time of attachment was calculated as the time the particle drifted past the bubble. Time of Collision The theory presented in this paper enables calculation of the time of collision, using the concept that the bubble, or more generally, a liquid-air interface, acts as an elastic body. The elasticity, defined as the restoring force on a mechanical deformation, is caused by the surface tension and is the result of the principle of the minimum of free surface energy. It is well known that an elasticity together with a mass determines a frequency of vibration. The vibrations of jets and drops caused by the elasticity of the interface are known to comply exactly with the classical theory of capillarity.' However, the vibrations of isolated bubbles, as distinct from foams, have not been investigated previously. The following equation, presented elsewhere,' has been deduced for these frequencies: 3_____________________ fB = 9.20.vV.vn. (n-1).(n+2)/8 [I] in which fB is the frequency of a harmonic of the bubble in cycles per second, V the volume of the bubble in cc, n a number determining the order of the harmonic, and n = 2 the basic vibration. The first (basic) harmonic describes a change of the spherical bubble to an ellipsoidal bubble. The higher harmonics are more complicated, for the circumference of the bubble is divided approximately into as many parts as the order of the harmonic. As an example, Spedden and Hannan's published motion picture of a vibrating bubble corresponds to the sixth harmonic. Eq 1 shows that only the first and third harmonics are simple multiples (1 and 3), all the others being irrational fractions of the basic frequency. This means that the shape of the vibration can change with time and is in general unsym-metric in respect to the time axis. Such conditions prevail when there is a distributed elasticity or mass, as in the case of vibrating membranes or rods. The constant 9.20 is valid for water at room temperature, but a general solution involving the physical constants of the liquid has not been found. The case of the floating particle is much easier to treat than that of the bubble. It can be assumed that the elasticity is caused exclusively by the interface and that the mass is concentrated in the particle together with some adhering water. The following expression for the frequency of a system of one degree of freedom can be applied: fP = -1/2-vE/m [2] Here fp is the frequency of the particle vibration in cycles per second, E the elasticity in dynes per cm, and m the mass in grams. The classical theory of impact phenomena gives the time of collision during the striking of a spring (in this case the surface of the bubble) by a mass, as: t, = 2/f = nvm/E [3] It is now possible to develop an expression for the elasticity of a floating cylindrical particle. The force equilibrium of a cylinder floating end on at the air-liquid interface is given by the well-known equation (Poisson7 1831) P = /4 D2-pL-g-h + D.y sin a [4] which accounts for the buoyancy and the action of the surface tension where P is the force acting on the particle in dynes (weight-buoyancy), D the diameter of the cylinder in cm, PL the density of the liquid in grams per cc, g the acceleration of gravity = 981 cm per sec2, h the depression of the cylinder below the surface of the liquid in cm, y the surface tension in dynes per cm and a the supporting angles or the one required to insure equilibrium, a being smaller than the contact angle 0. Although demonstrated by Poisson, it has not

Jan 1, 1953

By Halbert Powers Gillette

FROM the known laws of physical chemistry I believe it can be shown that progressive mass movement of water solutions in channels has seldom been the means of ore-concentration in veins. It is my purpose in this paper to show that the force known as “osmosis” has been the principal factor in ore-formation. Convection-currents have doubtless supplemented osmosis, and the two working together have been the agencies that have gathered the scattered particles of rare minerals into the larger masses which are called ore. Osmosis is commonly thought of as a vague, feeble force that causes slow diffusion of dissolving matter through the solvent. That it is a measurable force, often of great intensity, few know, except those who are familiar with the laws of modern physical chemistry. Therefore, I may be pardoned for going briefly into the elementary mathematics of osmotic pressure and of convection-currents. The velocity of water moving through any channel is given by the Chézy formula: (1) v = c [/rs], in which r is the hydraulic mean radius; s, the slope of the channel in which gravity is the sole propulsive force; and c, the coefficient of roughness of the sides of the channel. From this formula it is evident that the smaller the channel, the smaller the velocity of water under a constant head. In rock-crevices, therefore, where the head is constant, water moves much more slowly than in large fissures, and in moving through sand or porous rock it is to an even greater degree retarded. Hence, if a mass of water-saturated sand be heated, the finer the sand-grains, the more slowly will the temperature rise at parts remote from the source of heat. Conversely, cooling is retarded the smaller the interstices or channels through which the convection-currents move. The importance of this

Jan 1, 1913

By A. B. Hersberger, R. S. Dean

Although it is obvious that in any flotation process we must have a froth, in recent years the development of collecting reagents has caused the possibilities of better frothing agents to be overlooked. Some investigators have even gone so far as to say that the number of satisfactory frothing agents was sufficient. A little consideration will show, however, that the reagents available in the past were far from ideal frothers. The properties of an ideal frother for flotation work may be set down as follows: 1. It must form in low concentrations a copious but not too persistent froth. 2. It must be insensitive to hydrogen-ion concentration of the pulp; that is, it must froth equally well in an acid or alkaline medium. 3. It must be insensitive to salts, even in high concentration. 4. It must be absolutely noncollecting to both sulfides and nonsulfides. 5. Its frothing properties must not be affected by collecting reagents, including soap, the most generally used nonsulfide collector. 6. It must readily emulsify and disperse any insoluble collecting agent that is likely to be used. Clearly the existing frothers do not qualify. Pine oil, for example, is an acceptable frother for many purposes but if used in soap flotation a delicate balance between pine oil and soap must be struck because, as pointed out by Coghill1, these two reagents are incompatible in certain concentrations. The objections to soap itself as a frother are obvious, and the cresols and their substitution products all have some collecting power and very little emulsifying power. The mechanism of frothing in flotation was early explained on the basis of the Harkins-Langmuir theory of oriented molecules.2 These investigators showed that if an organic compound having an unsym-metrical molecule (in which one end of the molecule contained water-

Jan 1, 1939

By R. S. Dean, A. B. Hersberger

Although it is obvious that in any flotation process we must have a froth, in recent years the development of collecting reagents has caused the possibilities of better frothing agents to be overlooked. Some investigators have even gone so far as to say that the number of satisfactory frothing agents was sufficient. A little consideration will show, however, that the reagents available in the past were far from ideal frothers. The properties of an ideal frother for flotation work may be set down as follows: 1. It must form in low concentrations a copious but not too persistent froth. 2. It must be insensitive to hydrogen-ion concentration of the pulp; that is, it must froth equally well in an acid or alkaline medium. 3. It must be insensitive to salts, even in high concentration. 4. It must be absolutely noncollecting to both sulfides and nonsulfides. 5. Its frothing properties must not be affected by collecting reagents, including soap, the most generally used nonsulfide collector. 6. It must readily emulsify and disperse any insoluble collecting agent that is likely to be used. Clearly the existing frothers do not qualify. Pine oil, for example, is an acceptable frother for many purposes but if used in soap flotation a delicate balance between pine oil and soap must be struck because, as pointed out by Coghill1, these two reagents are incompatible in certain concentrations. The objections to soap itself as a frother are obvious, and the cresols and their substitution products all have some collecting power and very little emulsifying power. The mechanism of frothing in flotation was early explained on the basis of the Harkins-Langmuir theory of oriented molecules.2 These investigators showed that if an organic compound having an unsym-metrical molecule (in which one end of the molecule contained water-

Jan 1, 1939